MXPA98008814A - Process to produce 1,6-hexanodium - Google Patents

Abstract

This invention relates to processes for producing one or more substituted or unsubstituted 1,6-hexane diols, e.g. 1,6-hexanediol, which comprises subjecting one or more substituted or unsubstituted alkadienes to hydrocarbonylation, in the presence of a hydrocarbonylation catalyst, e.g. a metal complex catalyst and organophosphorus coordinating group, and a promoter and optionally a free coordinating group to produce one or more of the substituted or unsubstituted 1,6-hexanediols. The substituted and unsubstituted 1,6-hexanediols produced by the process of this invention may undergo additional reaction (s) to provide the desired derivatives thereof, e.g., epsilon caprolactone. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted 1,6-hexanediols as a main reaction product (s).

Description

'PROCESSES FOR. PRODUCE 1, 6-HEXANODIOLS " SHORT DIGEST OF THE INVENTION TECHNICAL FIELD This invention relates in part to processes for selectively producing one or more substituted or unsubstituted 1, 6-hexanediols. This invention is also related in part to reaction mixtures containing one or more substituted or unsubstituted 1, 6-hexanediols, such as the desired reaction product (s).

BACKGROUND OF THE INVENTION The 1,6-hexanedione is a valuable intermediate that is useful, for example, in the production of polyesters. The processes currently used to produce 1,6-hexanediols have several disadvantages. For example, the starting materials used to produce 1,6-hexanodols are relatively expensive. In addition, the selectivity with respect to the 1,6-hexanediols in the processes of the prior art has been low. Accordingly, it would be desirable to selectively produce 1,6-hexanediols from a relatively inexpensive starting material, and by a process that can be used commercially.

EXHIBITION OF THE INVENTION It has been found that alkadienes can be converted into linear diols in a one-step process. It has also been discovered that alcohols possessing internal olefinic unsaturation can be converted into linear diols. In particular, it has surprisingly been discovered that penten-1-ols, e.g. 3-penten-1-oles, can be converted to 1,6-hexanediols, e.g. 1,6-hexanediol, using catalysts having hydrocarbonation / isomerization capabilities. It has further been discovered that large selectivities and high ratios of the normal isomer: branched may result from carrying out the hydrocarbonylation in the presence of a complex metal catalyst and coordinating group and optionally a free coordinating group, wherein the coordinating group is preferably a organophosphine coordinating group of high basicity and low steric bulk, and in the presence of a promoter, i.e., an organic or inorganic compound with a pKa ionizable hydrogen of about 1 to about 35. This invention relates to processes for producing one or plus 1, 6-substituted or unsubstituted hexanodiols, eg, 1,6-hexanediol, comprising subjecting one or more substituted or unsubstituted alkadienes to hydrocarbonylation in the presence of a hydrocarbonylation catalyst, e.g. a complex catalyst of the metal and an organophosphorus coordinating group, and a promoter and optionally a free coordinating group to produce one or more of the substituted or unsubstituted 1, 6-hexanediols. This invention also relates to processes for producing one or more substituted or unsubstituted 1, 6-hexanediols, eg 1,6-hexanediol, which comprises subjecting one or more of the substituted or unsubstituted pentenales to hydrocarbylation, in the presence of a hydrocarbonylation catalyst, eg, a metal complex catalyst and an organophosphorus coordinating group, and a promoter and optionally a free coordinating group, in order to produce one or more of the substituted or unsubstituted 1, 6-hexanediols. This invention also relates to processes for producing one or more substituted or unsubstituted 1,6-hexanediols, eg, 1,6-hexanediol, which comprises subjecting one or more substituted or unsubstituted penten-1-yl to hydrocarbonylation, presence of a hydrocarbonylation catalyst, eg a metal complex catalyst and an organophosphorus coordinating group, and a promoter and optionally a free coordinating group, to produce one or more substituted or unsubstituted 1, 6-hexanediols. This invention is still further related to processes for producing one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexanedione, which comprises: (a) subjecting one or more substituted or non-substituted alkadienes. substituted, eg, butadiene to hydrocarbonylation in the presence of a hydrocarbonylation catalyst, eg, a metal complex catalyst and an organophosphorus coordinating group, and a promoter and optionally a free coordinating group to produce one or more substituted penten-1-oles or not replaced; and (b) subjecting one or more of the substituted or unsubstituted penten-1-ols to hydrocarbonization in the presence of a hydrocarbonation catalyst, eg, a metal complex catalyst and an organophosphorus coordinating group, and a promoter and optionally a group free coordinator to produce one or more substituted or unsubstituted 1, 6-hexanediols. The hydrocarbonation reaction conditions in steps (a) and (b) may be the same or different, and the hydrocarbonation catalysts in steps (a) and (b) may be the same or different. This invention also relates to processes for producing one or more substituted 1,6-hexanodols or not substituted, eg, 1,6-hexanedione, which comprises reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a group free coordinator in order to produce one or more substituted or unsubstituted 1,6-hexanediols. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organophosphorus coordinating group and the promoter is one or more of the starting materials, intermediates or process products. This invention is further related to processes for producing one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexanedione, which comprises reacting one or more of the substituted or unsubstituted pentenales with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group, and a promoter and optionally a free coordinating group in order to produce one or more of the substituted or unsubstituted 1, 6-hexanediols. In a preferred embodiment, the metal complex catalyst and the coordinator group is a metal complex catalyst and an organophosphorus coordinating group and the promoter is one or more than the starting materials, intermediates or products of the process. This invention, furthermore, is still related to processes for producing one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexanediol, which comprises reacting one or more substituted or unsubstituted penten-1-ols with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a free coordinating group, to produce one or more of the substituted or unsubstituted 1, 6-hexanediols. In a preferred embodiment, the metal complex catalyst and coordinator group is a metal complex catalyst and a phosphorus body coordinator group and the promoter is one or more of the starting materials, intermediates or products of the process. with processes for producing one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexanediol, comprising: (a) reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group, and a promoter and optionally a J ibre coordinating group, in order to produce one or more of the substituted or unsubstituted penten-1-ols, and (b) reacting one or more of the substituted or unsubstituted penten-1-ols with carbon monoxide and hydrogen in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, to produce one or more of the substituted or unsubstituted 1,6-hexanediols. The hydrocarbonylation reaction conditions in steps (a) and (b) may be the same or different and the hydrocarbonylation catalysts in steps (a) and (b) may be the same or different. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organophosphorus coordinating group and the promoter is one or more of the starting materials, intermediates or process products. This invention also relates in part to processes for producing an intermittently or continuously generated reaction mixture, comprising: (1) one or more substituted or unsubstituted 1,6-hexanediols, e.g., 1,6-hexanediol; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 6-hydroxyhexanals, e.g. 6-hydroxyl hexanal; (4) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or the cyclic lactol derivatives thereof, e.g., 2-methyl-5-h? Droxipentanal; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or the cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; (8) optionally one or more substituted or unsubstituted pentenales, e.g., c? S-2-pentenal, trans-2-pentenal, c? S-3-pentenal, trans-3-pentenal and / or 4-pentenal; (9) optionally one or more 1,6-hexanedioles, substituted or unsubstituted, e.g., adipaldehyde; (10) optionally one or more substituted 1, 5-pentanediols, e.g., 2-methylglutaraldehyde; (11) optionally one or more substituted 1,4-butanedials, e.g., 2, 3-dimethylsuccinaldehyde and 2-ethylsuccmaldehyde; and (12) one or more substituted or unsubstituted butadienes, e.g., butadiene; where the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9), ( 10) and (11) is greater than about 0.1, preferably greater than about 0.25, and especially especially greater than about 1.0; and the weight ratio of component (1) to the sum of components (1), (2), (3), (4), (5), (6), (7), (8), (9) ), (10) and (11) is from about 0 to about 100, preferably from about 0.001 to about 50; whose process comprises reacting one or more of the butadienes substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and Optionally a free coordinating group, to produce the reaction mixture generated intermittently or continuously. In a preferred embodiment, the metal complex catalyst and coordinator group is a metal complex catalyst and an organophosphine coordinating group and the 0 promoter is one or more of the starting materials, intermediates or process products. This invention also relates in part to a process for producing an intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 1, 6-hexanediols, e.g., 1,6-hexanedione; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more 6-hydroxyl substituted or unsubstituted hexanals, e.g. 6-hydroxyhexanal; (4) optionally one or more substituted or unsubstituted 5-h? Droxipentanales and / or the cyclic lactol derivatives thereof, e.g., 2-met? L-5-hydrox? Pentanal; (5) optionally one or more of the substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof, e.g., 2-et? 1-4-hydroxybutanal; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; and (8) one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; wherein the weight ratio of component (1) to the sum of components (2), (3), (4), (5), (6) and (7) is greater than about 0.1, preferably greater than from about 0.25, more preferably more than about 1.0; and the weight ratio of the component (8) to the sum of the components (1), (2), (3), (4), (5), (6) and (7), is from about 0 to about 100, preferably from about 0.001 to about 50; which process comprises reacting one or more of the pentenales substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinator and promoter group and optionally a free coordinating group, to produce the reaction mixture generated intermittently or continuously. In a preferred embodiment, the metal complex catalyst and a coordinating group is a metal complex catalyst and an organophosphine coordinating group and the promoter is one or more of the starting materials, intermediates or process products. This invention also relates in part to a process for producing an intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 1,6-hexanediols, e.g., 1,6-hexanediol; (2) one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more 6-hydroxyl substituted or unsubstituted hexanals, e.g. 6-h? drox? hexanal; (4) optionally one or more substituted or unsubstituted 5-hydroxyspinals and / or the cyclic lactol derivatives thereof, e.g., 2-met? L-5-hydrox? Pentanal; (5) optionally one or more substituted or unsubstituted 4-hydroxysubstituted butanales and / or the cyclic lactol derivatives thereof, e.g., 2-et? L-4-hydrox? Butanal; Y (6) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4), (5) and (6) is greater than about 0.1, preferably greater than about 0.25, especially preferred greater than about 1.0; and the weight ratio of component (2) to the sum of components (1), (3), (4), (5) and (6) is from about 0 to about 100, preferably from about 0.001 to about fifty; which process comprises reacting one or more substituted or unsubstituted penten-1-ols with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a free coordinating group, to produce the mixture of reaction generated intermittently or continuously. In a preferred embodiment, the metal complex catalyst and the The coordinating group is a complex metal catalyst and an organophosphine coordinating group and the promoter is one or more of the starting materials, intermediates or process products. This invention is also related in part to a process for producing an intermittently or continuously generated reaction mixture comprising: (1) one or more 1,6-hexanediols, substituted or unsubstituted, eg, 1,6-hexane ? ol; (2) optionally one or more penten-1-oles, substituted or unsubstituted, eg, c-s-2-penten-1-ol, trans-2-penten-1-ol, 3-penten- l-ol, trans-3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 6-hydrox? hexanals, eg the 6-hydrox? ? hexanal; (4) optionally one or more substituted or unsubstituted 5-hydroxyspinals, and / or the cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof, e.g., 2-et? L-4-hydroxybutanal; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; (8) optionally one or more substituted or unsubstituted pentenales, e.g., c? S-2-pentenal, trans-2-pentenal, c? S-3-pentenal, trans-3-pentenal and / or 4-pentenal; (9) optionally one or more substituted or unsubstituted 1, 6-hexanediols, e.g., adipaldehyde; (10) optionally one or more substituted 1, 5-pentanediols, e.g., 2-met? Lglutaraldehyde; (11) optionally one or more substituted 1,4-butanediols, e.g., 2, 3-d? Met? Lsucc? Naldehyde and 2-ethylsuccmaldehyde; and (121) one or more substituted or unsubstituted butadienes, eg, butadiene, wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) is greater than about 0.1, preferably greater than about 0.25, especially preferably greater than about 1.0, and the weight ratio of component (12) to the sum of components (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11), is from about 0 to about 100, preferably from about 0.001 to about 50; which process comprises: (a) reacting one or more of the substituted or unsubstituted butadienes with carbon monoxide or hydrogen in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, for produce substituted or unsubstituted 1-penten-l-oles, and (b) reacting one or more penten-1-ols substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group to produce the reaction mixture generated intermittently or continuously. The hydrocarbonylation reaction conditions in steps (a) and (b) may be the same or different, and the hydrocarbonation catalysts in steps (a) and (b) may be the same or different. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organophosphine coordinating group, and the promoter is one or more of the starting materials, intermediates or process products. This invention is still further related to a process for producing a reaction mixture comprising one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexanedione, which process comprises reacting one or more alkadienes substituted or not substituted, with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a free coordinating group, to produce the reaction mixture comprising one or more substituted 1,6-hexanediols or unsubstituted, eg, 1, 6-hexanod? ol. In a preferred embodiment, the metal complex catalyst and a coordinating group is a metal complex catalyst and an organophosphine coordinating group and the promoter is one or more of the substituted or unsubstituted starting materials, intermediates or process products. This invention also relates to a process for producing a reaction mixture comprising one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexanedione, which process comprises reacting one or more pentenales substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally the free coordinating group to produce the reaction mixture comprising one or more 1,6-hexanod? oles substituted or unsubstituted, eg 1, 6-hexanod? ol. In a preferred embodiment, the metal complex catalyst and coordinator group is a complex metal catalyst and an organophosphine coordinating group and the promoter is one or more of the substituted or unsubstituted starting materials, intermediates or process products. This invention is further related to a process for producing a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols, eg, 1,6-hexanediol, which process comprises reacting one or more Penten-1. -substituted or unsubstituted, with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a free coordinating group to produce the reaction mixture comprising one or more 1, 6- substituted or unsubstituted hexanediols, eg 1, 6-hexanediol. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organosphosphine coordinating group and the promoter is one or more of the substituted or unsubstituted starting materials, intermediates or process products. This invention still further relates to a process for producing a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols, eg, 1,6-hexanediol, which process comprises: (a) reacting one or more alkadienes substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, to produce a reaction mixture comprising one or more substituted or unsubstituted penten-1-ols, and (b) reacting one or more of the penten-1 -ols substituted or unsubstituted with carbon monoxide and hydrogen in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, to produce the reaction mixture comprising one or more 1, 6- substituted or unsubstituted hexanodols. The hydrocarbonation reaction conditions in steps (a) and (b) may be the same or different, and the hydrocarbonylation catalysts in steps (a) and (b) may be the same or different. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organosphosphine coordinating group and the promoter is one or more of the substituted or unsubstituted starting materials, intermediates or process products. The processes of this invention can achieve large -addivities of alkadienes, in 1, 6-hexanediols, e.g. butadiene selectivities in 1,6-hexanodols up to 10 weight percent or more that can be achieved by the processes of this invention. Likewise, the problems of this invention can achieve relationships High levels of normal isomer: branched, e.g., hydrocarbonyl butadiene in 1,6-hexanediols, at high ratios of the normal isomer: branched. This invention also relates in part to the intermittently or continuously generated reaction mixture, comprising: (1) one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1,6-hexansd? Ol, ( 2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, c-3-penten-1 ol, trans-3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more 6-hydroxyl substituted or unsubstituted hexanals, e.g. 6-hydroxy? Hexanal, (4) optionally one or more substituted or unsubstituted 5-hydroxetaphenals, and / or the cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales and / or the cyclic lactol derivatives thereof, e.g., 2-et? 1-4-idroxybutanal; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; (8) optionally one or more substituted or unsubstituted pentenales, e.g. c? s-2-pentenal, trans-2-pentenal, c? s-3-pentenal, trans-3-pentenal and / or 4-pentenal; (9) optionally one or more substituted or unsubstituted 1, 6-hexanediols, e.g., adipaldehyde; (10) optionally one or more substituted 1, 5-pentenodols, e.g. 2-methyglutaraldehyde, (11) optionally one or more substituted 1,4-butanediols, e.g. 2, 3-d? Met? Lccmaldehyde and 2-ethylsuccmaldehyde; and (1) one or more substituted or unsubstituted butadienes, e.g. butadiene; where the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9), (10) ) and (11) is greater than about 0.1, preferably greater than about 0.25, particularly preferably greater than about 1.0, and the weight ratio of the component (12) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11), is from about 0 to about 100, preferably from about 0.001 to about 50; This invention furthermore relates in part to the intermittent-or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 1,6-hexanediols, e.g., 1,6-hexanediol; (2) optionally one or more substituted or unsubstituted penten-1-ols, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, trans -3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more substituted or unsubstituted 6-hydroxyhexanals, e.g. the 6-hydroxyhexanal; (4) optionally one or more substituted or unsubstituted 5-hydroxypentanalnes, and / or the cyclic lactol derivatives thereof, e.g., 2-methyl-5-hydroxypentanal; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives of the same, e.g., 2-ethyl-4-hydroxybutanal; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; and (8) one or more substituted or unsubstituted pentenales, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and / or 4-pentenal; wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6) and (7), is greater than about 0.1, preferably greater than about 0.25, and especially preferably greater than about 1.0; and the weight ratio of component (8) to the sum of components (1), (2), (3), (4), (5), (6) and (7), is from about 0 to 100. , preferably from 0.001 to about 50. This invention is still further related in part to an intermittently or continuously generated reaction mixture comprising: (1) one or more substituted or unsubstituted 1, 6-hexanediols, eg, 1, 6-hexanodol; (2) one or more substituted or unsubstituted penten-1-oles, eg, cis-2-penten-1-ol, trans-2-penten-1-ol, c -s-3-penten-1 ol, trans-3-penten-l-ol and / or 4-penten-l-ol; (3) optionally one or more 6-hydroxyl substituted or unsubstituted hexanals, e.g. 6-h? drox? hexanal; (4) optionally one or more substituted or unsubstituted 5-hydroxyspinals and / or the cyclic lactol derivatives thereof, e.g., 2-met? L-5-hydrox? Pentanal; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof, e.g., 2-et? 1-4-hydroxybutanal; Y (6) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4), (5) and (6) is greater than about 0.1, preferably greater than about 0.25, especially prefereride greater than about 1.0, and the weight ratio of the component (2) to the sum of the components (1), (3), (4), (5) and (6) is from about 0 to about 100, preferably from 0.001 to about 50. This invention also relates in part to a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols, wherein the reaction mixture is prepared by a process comprising, making reacting one or more alkadienes substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, to produce the reaction mixture comprising one or more 1, 6-hexanodols, substitute gone or not replaced. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organophosphine coordinating group and the promoter is one or more of the materials of substituted or not replaced, intermediate or process products. This invention is further related in part to a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols, wherein the reaction mixture is prepared by a process comprising reacting one or more substituted or unsubstituted pentenales. with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, in order to produce the reaction mixture, comprising one or more substituted 1,6-hexanediols or not replaced. In a preferred embodiment, the metal complex catalyst and coordinator group is a metal complex catalyst and organophosphine coordinating group, and the promoter is one or more of the substituted or unsubstituted starting materials, intermediates or process products. This invention still further relates in part to a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols, wherein the reaction mixture is prepared by a process comprising reacting one or more penten-1. oles substituted or unsubstituted with carbon monoxide and hydrogen in the presence of a complex metal catalyst and a coordinating group and a promoter, and optionally a free coordinating group for producing the reaction mixture comprising one or more substituted or unsubstituted 1, 6-hexanediols. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organophosphine coordinating group and the promoter is one or more of the substituted or unsubstituted starting materials, intermediates or process products. This invention also relates in part to a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols, wherein the reaction mixture is prepared by a process comprising: (a) reacting one or more alkadienes substituted or unsubstituted, with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter, and optionally a free coordinating group, to produce one or more substituted or unsubstituted penten-1-ols, and (b) reacting one or more penten-1-oles substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinator group and a promoter, and optionally a free coordinating group to produce the reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols. The hydrocarbonylation reaction conditions in steps (a) and (b) may be the same or different, and the hydrocarbonylation catalysts in steps (a) and may be the same or different. In a preferred embodiment, the metal complex catalyst and the coordinating group is a metal complex catalyst and an organosphosphine coordinating group, and the promoter is one or more substituted or unsubstituted starting materials, intermediates or process products. The reaction mixtures of this invention are different, since the processes for their preparation achieve the generation of large selectivities of the 1,6-hexanediols, in a way that can be appropriately employed in a commercial process for the manufacture of 1,6-hexanediols. -hexanod? oles. In particular, the reaction mixtures of this invention are different since the processes for their preparation allow the production of 1,6-hexanediols in relatively high yields, without generating large amounts of byproducts, eg, pentanols and 2-met? Ll, 5-pentanediols.

DETAILED DESCRIPTION The hydrocarbonylation process of this invention involves converting one or more alkadienes substituted or unsubstituted in one or more substituted or unsubstituted 1,6-hexanediols, convert one or more substituted or unsubstituted alkadienes into one or more substituted or unsubstituted penten-1-ols, and / or convert one or more penten- 1-Oles substituted or unsubstituted in one or more substituted or unsubstituted 1, 6-hexanediols. The hydrocarbonylation processes of this invention can be carried out in one or more steps or steps preferably in a one-step process. As used herein, the term "hydrocarbination" is proposed as including all permissible hydrocarbon processes that involve converting one or more of the substituted or unsubstituted alkadienes to one or more of the substituted 1, 6-hexanediols or unsubstituted, converting one or more of the substituted or unsubstituted alkadienes into one or more substituted or unsubstituted penten-1-ols, and / or converting one or more of the substituted or unsubstituted penten-1-ols into one or more of the 1, 6-hexanediols substituted or unsubstituted. A preferred hydrocarbonylation process useful in this invention is disclosed in U.S. Patent Application Serial Number (D-17761) filed on the same date as this one, the disclosure of which is incorporated herein by reference.

The hydrocarbonylation process involves the production of 1,6-hexanediols and / or unsaturated alcohols by reacting an alkadiene and / or unsaturated alcohol with carbon monoxide and hydrogen, in the presence of a complex metal catalyst and a coordinating group and optionally a free coordinating group, in a liquid medium that also contains a promoter. The reaction can be carried out in a continuous one-pass continuous mode of continuous gas recycling or more preferably in a manner of recycling the continuous liquid catalyst as will be described below. The hydrocarbonation processing techniques employable herein may correspond to any of the known processing techniques. Mixtures of the hydrocarbonylation process employable herein include any solution derived from any corresponding hydrocarbonylation process which may contain at least a certain amount of four different ingredients or major components, i.e., the diol product, a complex or metal catalyst and a coordinating group, a promoter and optionally a free coordinating group, these ingredients correspond to those employed and / or produced by the hydrocarbonalation process from where the starting material of the mixture of the hydrocarbonylation process can be derived. By the term "free coordinating group" is meant a coordinating group that is not complexed with (joins or remains linked to) metal, e.g., a rhodium atom, of the complex catalyst. It should be understood that the hydrocarbonylation process mixture compositions employable herein may contain and will usually contain small amounts of additional ingredients such as those that have been deliberately employed in the hydrocarbonylation process or formed in situ during that process. Examples of these ingredients that may also be present include unreacted alkanediene or unsaturated alcohol starting materials, carbon monoxide and hydrogen gases, and products of type formed in situ, such as saturated alcohols and / or iso-olefins isolated without reacting that correspond to the starting materials of alkadiene or unsaturated alcohol, and liquid byproducts of high boiling temperature as well as other inert co-solvent type materials or hydrocarbon additives, if they are used.

Catalysts useful in the hydrocarbonylation process include metal complex catalysts and a coordinating g. The permissible metals that make up the metal complexes and the coordinating g include G 8, 9 and 10 of metals that are selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, the preferred metals being rhodium, cobalt, iridium and ruthenium, more preferably rhodium, cobalt and ruthenium, especially rhodium. The permissible coordinating gs include, for example, coordinating gs of organophosphorus, organo-arsenic and organo-antimony or mixtures thereof, preferably organophosphorus coordinating gs. The permissible organophosphorus coordinating gs which constitute the metal complexes and the organophosphorus coordinating g and the free organophosphorus coordinating g include the higher mono-, di-, tri- and poly-organophosphorus compounds of preference those of great basicity and low spherical volume. The permissible organophosphorus coordinating gs include, for example, organophosphines, organophosphites, organophosphites, organophosphinites, coordinating gs containing organophosphorus nitrogen, coordinating gs containing organophosphorus sulfur, coordinating gs containing organophosphorus silicon and the like. Other permissible coordinating gs include, for example, coordinating gs that contain a heteroatom as described in the Request for US Patent Serial Number (D-17646-1), filed March 10, 1997, the disclosure of which is incorporated herein by reference. The mixtures of these coordinating gs can be used if desired in the metal complex catalyst and the coordinating g and / or the free coordinating g and these mixtures can be the same or different. It should be noted that the satisfactory practice of this invention does not depend and is not predicted on the exact structure of the metal complex species and a coordinating g that may be present in their mononuclear, dinuclear and / or higher nuclearity forms. Of course, the exact structure is not known. Although it is not intended herein to be bound by any theory or mechanistic dissertation, it appears that the catalytic species may in their simplest form consist essentially of the metal in complex combination with the coordinating g and the carbon monoxide when used. The term "complex" as used herein and in the claims means a coordination compound formed by the joining of one or more electronically rich molecules or atoms, capable of independently existing with one or more electronically deficient molecules or atoms, each of which is also capable of existing independently. By example, the coordinating gs employable in the present, that is, the organophosphorus coordinating gs, may possess one or more phosphorus donor atoms, each having an electron pair available or not shared that each is capable of forming a covalent bond co-ordinated independently or possibly in agreement (eg, thh chelation) with the metal. Carbon monoxide (which is also appropriately classified as a coordinating g) can also be present and complexed with the metal. The final composition of the complex catalyst may also contain an additional coordinating g, e.g., hydrogen or an anion that satisfies the coordination sites or the nuclear charge of the metal. Additional illustrative coordinating gs include, e.g. halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF3, C2F5, CN, (R) 2P0 and RP (O) (0H) 0 (wherein each R is the same or different and is a radical of substituted or unsubstituted hydrocarbon, eg alkyl or aryl), acetate, acetylacetonate, SO4, BF4, PF6, N02, NO3, CH3O, CH2 = CHCH2, CH3CH = CHCH2, C6H5CN, CH3CN, NO, NH3, pyridine, (C2H5 ) 3N, mono-olefins, diolefins and triolefins, tetrahydrofuran, and the like. Of course, it should be understood that complex species of preference are exempt from any additional organic coordinating g or anion that it could contaminate the catalyst and have an undue detrimental effect on the operation of the catalyst. It is preferred in the hydrocarbonylation processes catalyzed by the metal complex and a coordinating group that the active catalysts are free of halogen and sulfur directly bound to the metal, even when this is not absolutely necessary. Preferred metal complex catalysts and coordinating group include complex rhodium catalysts and the organophosphine coordinating group. The number of coordination sites available in these metals is well known in the art. Therefore, the catalytic species may comprise a mixture of the complex catalyst, in its monomeric, dimeric or higher-nucleotide forms, which are preferably characterized by at least one phosphorus-containing molecule formed in complex by metal, e.g., rhodium. As mentioned above, it is considered that the catalytic species of the preferred catalyst used in the hydrocarbonylation process can be complexed with carbon monoxide and hydrogen, in addition to the organophosphorus coordinating groups, in view of carbon monoxide and the hydrogen gas they use through the hydrocarbonylation process.

Among the organophosphines which can serve as the coordinating group of the metal-organophosphine complex catalyst and / or the free organophosphine coordinating group of the hydrocarbonylation process mixture, the starting materials are mono-, di-, tri- and poly- (organophosphines) such as triorganophosphines, trialkylphosphines, alkyldiarylphosphines, dialkylarylphosphines, dicycloalkylarylphosphines, cycloalkyldiarylphosphines, triaralkylphosphines, tricycloalkylphosphines, and triarylphosphines, and mono- or diphosphines and diphosphines and alkyl and / or aryl bisphosphines, as well as ionic triorganophosphines containing at least one ionic residue which is selected from salts of sulfonic acid, carboxylic acid, phosphonic acid and quaternary ammonium compounds, and the like. Of course, any of the hydrocarbon radicals of these non-ionic and ionic tertiary organophosphines can be substituted, if desired, with any appropriate substituent that does not unduly detrimentally affect the desired result of the hydrocarbonylation process. The organophosphine coordinating groups employable in the hydrocarbonylation process and / or the methods for their preparation are known in the art. The illustrative triorganophosphine coordinating groups can be represented by the formula: R1 / P R1 R1 (I) wherein each R1 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical, e.g., an alkyl, cycloalkyl or aplo radical. In a preferred embodiment, each R1 is the same or different and is selected from primary alkyl, secondary alkyl, tertiary alkyl and aryl. Suitable hydrocarbon radicals may contain from 1 to 24 carbon atoms or more. Illustrative substituent groups that may be present on the hydrocarbon radicals include, v.gr, substituted or unsubstituted alkyl radicals, substituted or unsubstituted alkoxy radicals, substituted or unsubstituted silyl radicals such as -S? (R2) 3, - radicals of such as -N (R2> 2, acyl radicals such as -C (0) R2, carboxy radicals such as -C (0) 0R2, acyloxy radicals such as -0C (0) R2, amide radicals such as -C (0) N (R2> 2 and -N (R2) C (O) R2; ionic radicals such as -SO3M, wherein M represents inorganic or organic cationic atoms or radicals; sulfonyl radicals such as -S02R2; ether radicals such as -OR2; sulfinyl radicals such as -SOR2; selenyl radicals such as -SeR2; sulfenyl radicals such as -SR2 as well as halogen, nitro, cyano, trifluoromethyl and hydroxy radicals, and the like, wherein each R2 individually represents the substituted or unsubstituted monovalent hydrocarbon radical the same or different, with the proviso that in the substituents of such as -N (R2) 2, each R2 that is taken together can also represent a divalent linking group that forms a heterocyclic radical with the nitrogen atom and in the substituents of to such as C (0) N (R2) 2 and -N (R2) C (0) R2 each R2 linked to N can also be hydrogen. Illustrative alkyl radicals include, e.g., methyl, ethyl, propyl, butyl, octyl, cyclohexyl, isopropyl and the like. Exemplary aryl radicals include, e.g., phenyl, naphthyl, fluorophenyl, difluorofemlo, benzoyloxypheme, carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl; carboxyl ilo, trifluoromethylphemyl, methoxyethylphenyl, acetamidophenyl, dimethylcarbaphenylphenol, tolyl, xylyl, 4-d-methylamphoxyphenyl, 2,4,6-trimethoxy phenyl and the like. Exemplary specific organophospheres include e.g., methylphenylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, diethylbutylphosphine, diethyl-n-propylphosphine, diethyl isopropylphosphine, dietilbencelfosfma, dietilciclopentilfosfina, dietilciclohexilfosfina, tpfenilfosfina, tris-p-tolylphosphine, tris-p-methoxyphenylphosphine, tps-dimetilaminofenilfosfina, propyldiphenylphosphine, t-butildifenilfosfma, n-butyldiphenylphosphine, n-hexyldiphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tribencilfosfma, DIOP, ie , (4R, 5R) - (-) -0-? - sopropylidene-2,3-dihydrox? -l, 4-bis (diphenylphosphino) butane, and / or (4S, 5S) - (+) - 0-isoprop? l-den-2, 3-d? h? drox? -l, 4-bis (diphenylphosphino) butane and / or (4S, 5R) - (-) -O-isopropylidene-2,3-d? h? drox ? -l, 4-bis (diphenylphosphinobutane, substituted or unsubstituted bicyclic bisphosphines such as 1,2-bis (1,4-cyclooctylenphosphino) ethane, 1,3-bis (1,4-cyclooctylenphosphino) propane, 1, 3-bis (1,5-cyclooctylphosphino) propane and 1,2-b? S (2,6-d? Meth? Ll, 4-cyclooctylenphosphino) ethane, bis (2,2'-diphenylphosphinoethyl) biphenyl substituted or not substituted such as bis (2,2'-diphenylphosphinomethyl) biphenyl and bis. {2, 2 '- di (4-fluorophenyl) phosphinomethyl} biphenyl, MeC (CH2PPh2) 3 (tpfos), Na03S (CgH4) CH2C (CH2PPh2) 3 (sulfos), bis (diphenylphosphino) ferrocene, bis (diisopropylphosphino) ferrocene, bis (diphenylphosphino) ruthenocene, as well as the alkali metal salts and alkaline earth metal of triphenylphosphines sulphonated, e.g., of (tp-m-sulfophenyl) phosphine and of (m-sulfophenyl) diphenylphosphine and the like. The preferred organophosphorus coordinating groups that constitute the metal complex catalysts and the organophosphorus coordinating group and the free organophosphorus coordinating groups are highly basic coordinating groups. In general, the basicity of the organophosphorus coordinating groups must be greater than or equal to the basicity of tp-phenylphosphine (pKb of 2.74), eg, from about 2.74 to about 15. The appropriate organophosphorous coordinating groups have a pKb of about 3. or greater, preferably a pKb of from about 3 to about 12, and especially preferably a pKb of from about 5 to about 12. The pKb values for the illustrative organophosphorous coordinating groups useful in this invention are given in Table I below. is presented below. In addition, the organophosphorus coordinating groups useful in this invention have sufficient estepic volume to promote the hydrocarbonylation reaction. The spherical volume of monodentate organophosphor coordinating groups should be less than or equal to a Tolman cone angle of 210 °, preferably less than or equal to the estepic volume of tpccyclohexylphosphine (Tolman cone angle = 170 °). The Organophosphorus coordinating groups having the desired basicity and volume desired include, for example, substituted or unsubstituted tri-primary-alkylphosphine (e.g., trioctylphosphine, diethylbutylphosphine, diethyl isobutylphosphine), di-primary alkylarylphosphines (eg, diethylphenylphosphine, diethyl-pN, N-dimethylphenylphosphma), di-primary-alkyl-mono-secondary-alkyl phosphines (e.g., diethyl isopropylphosphine, diethylcyclohexylphosphine), di-ppmaria-alkyl-ter-alkylphosphines (eg, diethyl-tert-butylphosphine), ono-primary-alkyl-diarylphosphines (eg, diflemylmethylphosphine), mono-primary-alkyl-di-secondary-alkylphosphines) (eg, dicyclohexylethylphosphine), tpaplfosphines (eg, tp-for-N, Nd? methylaminophen? lfos? ina) , tri-secundapa-alkyl phosphines (eg, tricyclohexylphosphine), mono-primary-alkyl-mono-secondary, alkyl-mono-tertiary-alkyl phosphines (eg, ethyl isopropyl-butyl-phosphine) and the like. The permissible organophosphorus coordinating groups can be substituted with any of the appropriate functionalities and can include the promoter as will be described below.

Table I Organophosphorus Coordinating Group ^. pKb Tp ethylphosphine 8.7 Triethylphosphine 8.7 Tri-n-propilfosfma 8.7 Tri-n-butylphosphine 8.4 Tri-n-octyl phosphma 8.4 Tp-tert-butylphosphine 11.4 Diethyl-tert-butylphosphine 10.1 Triciclohex lfosfma 10 Diphenylmethylphosphine 4.5 Diethylphenylphosphine 6.4 Diphenylcyclohexylphosphine 5 Diphenylethylphosphine 4.9 Tri (p-methoxyphenyl) phosphma 4.6 Triphenylphosphine 2.74 Tri (p-N, N-dimethylaminophen? L) phosphine 8.65 Tri (p-methylphenyl) phosphine 3.84 More specifically, the illustrative metal and organophosphine complex catalysts and exemplary free organophosphine coordinating groups include, for example, those disclosed in U.S. Patent Nos. 3,239,566, 3,527,809, 4,148,830, 4,247,486, 4,283,562, 4,400, or "48, 4,482,749 and 4,861,918, the disclosures of which are incorporated herein by reference Other illustrative permissible organophosphorus coordinating groups that constitute the complexes of the metal-coordinating group and the coordinating group organophosphorus and free organophosphorus coordinating groups include, for example, those disclosed in U.S. Patent Nos. 4,567,306, 4,599,206, 4,668,651, 4,717,775, 3,415,906, 4,567,306, 4,599,206, 4,748,261, 4,769,498, 4,717,775, 4,885,401, 5,202,297, 5,235,113 , 5,254,741, 5,264,616, 5,312,996, 5,364,950 and 5,391,801, the North American Patent Application Serial Number (D-17646), filed on November 26, 1996 and the US Patent Application Serial Number (D-17459-1), filed on the same date as the present one, the exposures of which are incorporated herein by reference. The coordinating group employable in this invention can be formed by methods known in the art. The metal complex catalysts and the coordinating group can be in homogeneous or heterogeneous form. For example, preformed metal hydrido-carbonyl-organosphosphorus coordinating group catalysts can be prepared introduce into the reaction mixture a hydrocarbonylation process. More preferably, the metal complex catalysts and the coordinating group can be derived from a metal catalyst precursor that can be introduced into the reaction medium for in situ formation of the active catalyst. For example, rhodium catalyst precursors such as rhodium dicarbonyl acetylacetonate, Rh203, Rh4 (CO) 2, Rhg (CO) γ, Rh (N03) 3 and the like can be introduced into the reaction mixture together with the organophosphorus coordinating group for the in situ formation of the active catalyst. In a preferred embodiment of this invention, rhodium dicarbonyl acetylacetonate is used as a rhodium precursor and is reacted in the presence of a promoter with the organophosphine coordinating group to form a rhodium catalytic complex precursor and the organophosphine coordinating group which it is introduced into the reactor together with the excess of the free organophosphine coordinating group for the in situ formation of the active catalyst. In any case, it will be sufficient for the purposes of this invention that the carbon monoxide, hydrogen and organophosphorus compounds are all coordinating groups that are capable of forming a complex with the metal and that an active metal catalyst and coordinating group is present. of organophosphorus in the reaction mixture, under the conditions used in the hydrocarbonation process. More specifically, a catalyst precursor composition consisting essentially of a metal complex precursor catalyst and a solubilized coordinator group, a promoter and a free coordinating group can be formed. These precursor compositions can be prepared by forming a solution of a metal starting material, such as metal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or may not be in complex combination with an organophosphorus coordinating group as defined herein. Any suitable metal starting material can be used, e.g. rhodium dicarbonyl acetylacetonate, Rh2? 3, R4 (CO)? 2 'Rhg (CO)? g, Rh (N03) 3, rhodium carbonyl hydrides of the organophosphorus coordinating group. The carbonyl and organophosphor coordinating groups, if not already complexed with the initial metal, can be complexed with the metal either before or during the in situ hydrocarbonation process. By way of illustration, the precursor composition of the preferred catalyst of this invention consists essentially of a complex precursor catalyst of the solubilized rhodium carbonyl and the coordinating organophosphine group, a promoter and the coordinating group of free organophosphine prepared by forming a solution of rhodium dicarbonyl acetylacetonate, a promoter and a coordinating group as defined herein. The organophosphine coordinating group readily replaces one of the carbonyl coordinating groups of the rhodium acetylacetonate complex precursor at room temperature as evidenced by the evolution of carbon monoxide gas. This substitution reaction can be facilitated by heating the solution if it is desired. Any suitable solvent in which both the rhodium dicarbonyl acetylacetonate complex precursor and the rhodium organophosphine coordinating group are soluble may of course be used. The amounts of the rhodium complex catalyst precursor, the organic solvent and the organophosphine coordinating group as well as their preferred embodiments present in these catalyst precursor compositions may obviously correspond to those amounts employable in the hydrocarbonylation process of this invention. Experience has shown that the acetylacetonate coordinating group of the precursor catalyst is replaced after the hydrocarbonation process has been started with a different coordinating group, e.g. hydrogen, carbon monoxide or an organophosphine coordinating group to form the active complex catalyst as explained above. In a continuous process, the acetylacetone that is released from the precursor catalyst under hydrocarbonylation conditions is removed from the reaction medium with the alcohol produced and therefore, is not in any way detrimental to the hydrocarbonylation process. The use of these preferred rhodium complex catalytic precursor compositions provides a simple, economical and efficient method for handling the rhodium precursor metal and melamine hydrocarbon. Correspondingly, the complex metal catalysts and coordinating group used in the process of this invention consist essentially of the metal formed in complex with carbon monoxide and a coordinating group, the coordinating group being bound (formed in complex) with the metal in a chelated manner and / or not chelated. In addition, the terminology "consists essentially of" as used herein, does not exclude but rather includes the hydrogen formed in complex with the metal, in addition to the carbon monoxide and the coordinating group. Also, this terminology does not exclude the possibility of other organic coordinating groups and / or anions that could also form in a complex with the metal. Materials in quantities that detrimentally pollute improperly inactivate the catalyst are undesirable and therefore thus, the most desirable catalyst is free of contaminants such as halogen bound to the metal (e.g., chlorine and the like), although this may not be absolutely necessary. Hydrogen and / or carbonyl coordinating groups of an active metal complex catalyst and an organophosphine coordinating group may be present as a result of the coordinating groups linked to a precursor catalyst and / or as a result of the in situ formation e.g. due to the hydrogen and carbon monoxide gases used in the hydrocarbonylation process of this invention. As will be seen, the hydrocarbonylation process involves the use of a complex metal catalyst and a coordinating group as described herein. Of course, mixtures of these catalysts can be used if desired. The amount of the metal complex catalyst and coordinating group present in the medium of reaction of a particular hydrocarbonylation process need only be that minimum amount necessary to provide the determined concentration of the metal that is desired to be employed and which will provide the basis for minus the catalytic amount of metal necessary to catalyze the specific hydrocarbonylation process involved as disclosed, for example, in the aforementioned patents. Usually, the Catalyst concentration can vary from several parts per million up to a certain percentage by weight. Organophosphorus coordinating groups may be employed in the aforementioned catalysts in a molar ratio generally of about 0.5: 1 or less to about 1000: 1 or more. The concentration of the catalyst will depend on the conditions of the hydrocarbonylation process and the solvent used. In general, the concentration of the organophosphorus coordinating group in the hydrocarbonylation process mixtures can vary from about 0.005 percent to 25 percent by weight based on the total weight of the reaction mixture. Preferably, the concentration of the coordinating group is between 0.01 percent and 15 percent by weight and especially preferably between about 0.05 percent and 10 percent by weight on that basis. In general, the concentration of the metal in the hydrocarbonylation process mixtures can be as high as about 2000 parts per million by weight or more based on the weight of the reaction mixture. Preferably, the metal concentration is between about 50 and 1500 parts per million by weight based on the weight of the reaction mixture and most preferably is between about 70 and 1200 parts by weight. million by weight based on the weight of the reaction mixture. In addition, the metal complex catalyst and the coordinating group, the free coordinating group (i.e., the coordinating group which has not been complexed with the rhodium metal) may also be present in the middle of the hydrocarbonylation process. The free-coordinating group may correspond to any of the coordinating groups defined above that have been discussed above as capable of being employed herein. It is preferred that the free coordinating group be. same as the coordinating group of the complex metal catalyst and coordinating group used. However, these coordinating groups do not need to be equal in any given process. The hydrocarbonylation process can involve up to 100 moles or more of the free coordinating group per mole of metal, in the middle of the hydrocarbonylation process. Preferably, the hydrocarbonylation process is carried out in the presence of about 1 to about 50 moles of coordinating phosphorus, more preferably about 1 to about 20 moles of the coordinating phosphorus, and especially preferably about 1 to about 8 moles. of coordinating phosphorus, by mole of the metal present in the reaction medium; these amounts of Coordinable phosphorus being the sum of both the quantity of the coordinative phosphorus that is bound (complex form) with the rhodium metal present as the amount of the free coordinate phosphorus (not formed in complex) present. Of course, if desired, the coordinating replenishing phosphor may be supplied to the reaction medium of the hydrocarbonation process at any time and in any appropriate manner, e.g., to maintain a predetermined level of the free coordinating group in the medium of reaction. As indicated above, the hydrocarbonation catalyst may be in heterogeneous form during the reaction and / or during the separation of the product. These catalysts are particularly advantageous in the hydrocarbonylation of alkadienes to produce high temperature and boiling or thermally sensitive alcohols so that the catalyst can be separated from the products by filtration or decantation at low temperatures. For example, the rhodium catalyst can be fixed to a support such that the catalyst retains its solid form during both the hydrocarbonation and separation steps, or is soluble in a liquid reaction medium at high temperatures and then precipitates upon cooling. As an illustration, the rhodium catalyst can be impregnated in any solid support, such as inorganic oxides (e.g. alumina, silica, titania or zirconia) carbon, or ion exchange resins. The catalyst can be supported in or intercalated within the pores of zeolite or glass; the catalyst can also dissolve in a liquid, coating the film to the pores of the zeolite or glass. These zeolite-supported catalysts are particularly advantageous for producing one or more regioisomeric alcohols in high selectivity as determined by the pore size of the zeolite. The techniques for supporting the catalysts in solids, such as incipient humidity, will be those known to those skilled in the art. The solid catalyst formed in this way can still be complexed with one or more coordinating groups defined above. Descriptions of these solid catalysts can be found, for example, in: J. Mol. Cat. 1931, 70, 363-368; Catal. Lett. 1991, 8, 209-214; J. Organomet. Chem. 1991, 403, 221-227; Nature, 1989, 339, 454-455-; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259. The rhodium catalyst can be attached to a thin film or membrane support such as cellulose acetate or polyphenylene sulfone, as described for example in J. Mol. Cat. 1990, 63, 213-221, The rhodium catalyst can be attached to an insoluble polymer support via a coordinating organophosphorus containing group such as phosphine or phosphite, incorporated in the polymer. These polymer-based coordinating groups are well known and include commercially obtainable species such as triphenylphosphine supported by divinylbenzene / polystyrene. The coordinating group supported is not limited by selecting the polymer or the species that contains the phosphor incorporated in it. The descriptions of the catalysts supported by polymers can be found, for example, in: J. Mol. Cat. 1993, 83, 17-35; Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127. In the heterogeneous catalysts described above, the catalyst can remain in its heterogeneous form throughout the hydrocarbonylation process and catalyst separation. In another embodiment of the invention, the catalyst can be supported on a polymer which, by the nature of its molecular weight, is soluble in the reaction medium at elevated temperatures, but precipitates on cooling, thereby facilitating the separation of the catalyst from the catalyst. the reaction mixture. These "soluble" polymer-supported catalysts are described, for example, in: Polymer, 1992, 33, 161; J. Org. Chem. 1989, 54, 2726-2730.

When the rhodium catalyst is in sustained or heterogeneous form, the reaction can be carried out in the gas phase. More preferably, the reaction is carried out in the slurry phase due to the high boiling temperatures of the products and to avoid the decomposition of the alcohols produced. The catalyst can then be separated from the product mixture by filtration or decantation. The processes of this invention can be operated through a wide range of reaction regimes (m / L / h = product moles / liter of the reaction solution / hour) Typically, the reaction regimes are at least 0.01 m / L / H or greater preferably at least 0.1 m / L / H or higher, and especially preferably at least 0.5 m / L / H or higher. Higher reaction rates are usually preferred from an economic point of view, e.g. a smaller reaction size, etc. Substituted and unsubstituted alkadiene starting materials useful in hydrocarbonation processes include, but are not limited to, conjugated aliphatic diolems represented by the formula: Rl R2 I I CH2 = C - C = CH2 (II) wherein R x and R 2 are the same or different and are hydrogen, halogen or a "substituted or unsubstituted hydrocarbon radical" The alkadienes may be linear or branched and may contain substituents (e.g., alkyl groups), halogen atoms, amino groups or silyl groups). Suitable illustrative alkadiene starting materials are butadiene, isoprene, dimethylbutadiene, cyclopentadiene and chloroprene. Particularly preferably, the alkadiene starting material is butadiene itself (CH2 = CH-CH = CH2) • For the purposes of this invention, the term "alkadiene" is intended to include all permissible substituted and unsubstituted conjugated diolefins including all permissible mixtures comprising one or more of the substituted and unsubstituted conjugated diolefins. Illustrative of the appropriate substituted and unsubstituted alkadienes (including the alkadiene derivatives) include those permissible substituted and unsubstituted alkadienes described in Kirk-Othmer Chemical Technology Encyclopedia, Fourth Edition, 1996, the relevant portions of which, incorporated herein by reference.

The specific hydrocarbonation reaction conditions are not narrowly critical and can be any of the effective hydrocarbon processes sufficient to produce one or more 1,6-exanodiols and / or the unsaturated alcohols. The exact reaction conditions will be regulated by the best compromise between achieving high catalyst selectivity, activity, duration and ease of operation as well as intrinsic reactivity of the starting materials in question and the stability of the starting materials and the reaction product. desired with respect to the reaction conditions. The hydrocarbonation process conditions may include any of the appropriate hydrocarbon-type conditions employed hitherto to produce alcohols. The total pressure employed in the hydrocarbonation process can generally vary from about .0703 to kilogram per absolute square centimeter to about 703 kilograms per absolute square centimeter preferably from about 1.41 to 210.90 kilograms per absolute square centimeter and more preferably about 3.52. to approximately 140.60 kilograms per absolute square centimeter. The total pressure of the hydrocarbonation process will depend on the specific catalyst system used.

More specifically, the partial pressure of the carbon monoxide from the hydrocarbonation process can generally range from about .0703 to about 210.90 kilograms per absolute square centimeter, and preferably from about .211 to about 105.48 kilograms per absolute square centimeter, while the partial pressure of hydrogen can generally vary from about .0703 to about 210.90 kilograms per absolute square centimeter, and preferably from about .211 to about 105.48 kilograms per absolute square centimeter. Generally, the molar ratio of carbon monoxide to gaseous hydrogen can vary from about 100: 1 or more to about 1100 or less, and the preferred molar ratio of carbon monoxide to hydrogen gas is from about 1-10 to about 10. :1. The partial pressures of carbon monoxide and hydrogen will depend in part on the specific catalyst system used. It will be understood that the carbon monoxide and the hydrogen can be used separately, either alone or mixed with one another, ie synthesis gas, or they can be produced in situ under reaction conditions and / or derived from the promoter or solvent (not necessarily involving free hydrogen or carbon monoxide). In one embodiment, the partial pressure of hydrogen and the partial pressure of carbon monoxide are sufficient to prevent or minimize the derivatization, e.g., the hydrogenation of penten-1-ols or the hydrogenation of alkadienes. In addition, the hydrocarbonylation process can be carried out at a reaction pressure of from about 20 ° C to about 200 ° C, preferably from about 50 ° C to about 150 ° C, and especially preferably from about 65 ° C to approximately 115 ° C. The temperature must be sufficient for the reaction to occur (which may vary with the catalyst system used), but not so high that decomposition of the coordinating group or the catalyst occurs. It can also be understood that the conditions of the hydrocarbonylation process used will be regulated by the type of alcohol product desired.

To allow maximum levels of 3-penten-l-oles and / or 4-penten-l-oles and to minimize 2-penten-l-oles, it is desirable to maintain some partial pressure of alkadiene or when the conversion of the alkadiene is complete, the partial pressures of carbon monoxide and hydrogen they must be sufficient to prevent or minimize the derivation, e.g. the hydrogenation of penten-1-oles or the hydrogenation of alkadienes. In a preferred embodiment, the hydrocarbylation of the alkadiene is carried out at a partial pressure of alkadiene and / or partial pressures of carbon monoxide and hydrogen sufficient to prevent s minimizing the derivatization, eg, the hydrogenation of penten-1-ols or hydrogenation of alkadienes. In an especially preferred embodiment, the alkadiene, e.g. butadiene, the hydrocarbonylation is carried out at a partial pressure of alkadiene of more than 0 kilogram per square centimeter, preferably greater than 352 kilogram per square centimeter, and especially preferably greater than 633 kilogram per square centimeter; at a carbon monoxide partial pressure greater than 0 kilogram per square centimeter, preferably greater than 1.76 kilograms per square centimeter, and especially preferably greater than 2.31 kilograms per square centimeter; and at hydrogen partial pressure of more than 0 kilogram per square centimeter, preferably greater than 1.76 kilograms per square centimeter and more preferably greater than 5.62 kilograms per square centimeter. The hydrocarbonylation process is also carried out in the presence of a promoter. As used in the present, the term "promoter" means an organic and inorganic compound with a soluable hydrogen of a pKa of from about 1 to about 35. Illustrative promoters include, for example, protic solvents, organic and inorganic acids, alcohols, water, phenols, thiols , thiophenols, nitroalkanes, ketones, nitplos, amines (eg, pyrroles and diphenylamine), amides (eg acetamide), salts of mono-, di- and tp-alkylammonium, and the like. The approximate pKa values for the illustrative promoters useful in this invention are given in Table II below. The promoter may be present in the hydrocarbonation reaction mixture either alone or incorporated in the structure of the coordinating group, either as the metal complex catalyst and the coordinating group or as a free coordinating group, or in the alkadiene structure. The desired promoter will depend on the nature of the coordinating groups and the metal of the metal complex catalysts and coordinating group. In general, a catalyst with a more basic acyl linked to the metal or other intermediate, will require a lower concentration and / or less amount of the acidic promoter. Although it is not intended in the present to be linked to any theory or mechanistic dissertation, it seems that the promoter can function to transfer an ion of hydrogen arises or otherwise activates an acyl linked to the catalyst or other intermediate. Mixtures of the promoters in any permissible combination may be useful in this invention. A preferred class of promoters includes those which undergo hydrogen bonding, eg, the groups containing NH, OH and SH and the Lewis acids, since this is believed to facilitate the transfer of the hydrogen ion or activation of the acyl linked to the metal or other intermediate. Generally, the amount of promoter can vary from about 10 parts per million plus or minus to about 99 weight percent or more, based on the total weight of the starting materials of the hydrocarbonylation process mixture.

Table II Promoter pKa ROH (R = alkyl) 15-19 ROH (R = aryl) 8-11 RCONHR (R = hydrogen or alkyl, (eg acetamide) 15-19 R3NH +, R2NH2 + (R = alkyl) 10-11 RCH2N02 8-11 RCOCH2R (R-alkyl) 19-20 RSH (R = alkyl) 10-11 RSH (R = aryl) 8-11 CNCH2CN 11 Diarylamine 21-24 Pirrol-20 Pyrrolidine 34 The concentration of the promoter used will depend on the details of the catalyst system used. Without wishing to be bound by any theory, the promoter component must be sufficiently acidic and in sufficient concentration to transfer a hydrogen ion to or otherwise activate the acyl linked to the catalyst or other intermediate. It is believed that the acidity or concentration of the promoter component is insufficient to transfer a hydrogen ion or to otherwise activate the acyl linked to the catalyst or other intermediate, will result in the formation of aldehyde products instead of the preferred alcohol products. The ability of a promoter component to transfer a hydrogen ion to or otherwise activate the acyl linked to the catalyst or other intermediate can be regulated by several factors, for example the concentration of the promoter component, the intrinsic acidity of the promoter component (the pKa), the composition of the reaction medium (e.g., the reaction solvent) and temperature. The promoters are selected on the basis of their ability to transfer a hydrogen id to or otherwise activate this acyl linked to the catalyst or other intermediate, under sufficient reaction conditions to result in the formation of alcohol products, but not so elevated as to result in damaging side reactions of the catalyst reactants or products. In cases where the acidity or concentration of the promoter component is insufficient to do this, the aldehyde products (e.g., pentenales) are formed initially which may or may not subsequently be converted to alcohols e.g. penten-1-ols. In general, the acyl bound to the less basic metal will require a higher concentration of the promoter component or a more acidic promoter component to protonate or otherwise activate it completely, so that the products are alcohols, more desirable instead of aldehydes. This can be achieved by appropriate selection of the promoter component. For example, a concentration of acyl protonated or bound to the catalyst activated in another way or another intermediate, can be achieved through the use of a large concentration of the slightly acidic promoter component, or through the use of lower concentration of a more acidic component The promoter component is selected based on its ability to produce the desired concentration of the acyl bound to the protonated or otherwise activated catalyst, or other intermediate in the reaction medium under reaction conditions. In general, the intrinsic resistance of the acidic material is generally defined in an aqueous solution such as pKa, and not in a reaction medium commonly employed in hydrocarbon illation. The selection of the promoter and its concentration is carried out based in part on the theoretical pH or equivalent in which the promoter alone at this concentration provides in aqueous solution at 22 ° C. The theoretical desired pH or equivalent of the solutions of the promoter component should be greater than 0, preferably from about 1 to 12, more preferably from about 2 to 10 and especially preferably from 4 to 8. The theoretical or The equivalent can be easily calculated from the pKa values at the appropriate concentration of the promoter component by reference to the normal tables such as those found in "Organic Acid Ionization Constant in Aqueous Solution" (IUPAC Chemical Data Series - Number 23) by EP Serjeant and Boyd Dempsey, Pergamon Press (1979) and "Dissociation Constants of Inorganic Acids and Bases in an Aqueous Solution" (IUPAC Chemical Data Series Number 19, by D.D. Aqueous Solution "(IUPAC Chemical Data Serles - Number 19, by DD Perpn, Pergmamon Press.) Depending on the specific catalyst and reagents employed, suitable promoters preferably include solvents, for example, alcohols (eg, alcohol products such as penten-1-oles or hexanediols), thiols, thiophenols, selenoles, tellurols, alkenes, alkanes, aldehydes, byproducts of higher boiling temperature, ketones, esters, amides, primary and secondary amines, alkylaromatic compounds and the like. that does not unduly detrimentally interfere with the proposed hydrocarbylation process, can of course be employed The permissible protic solvents having a pKa of about 1 to 35, preferably a pKa of about 3 to 30, and more preferably pKa of about 5 to 25. Mixtures of one or more of the different solvents may be employed, if desired. regarding the production of 1,6-hexanodols, it is preferred to employ alcohol promoters corresponding to the desired alcohol products to be produced and / or the higher boiling temperature byproducts, such as the major protic solvents. These byproducts can also be preformed, if desired, and used accordingly. Illustrative preferred protic solvents usable in the production of alcohols, eg, hexanediols, include alcohols (eg, pentenoles, octanols, hexanediols), amines, thiols, thiophenols, ketones (eg, acetone and methylethyl ketone), hydroxyaldehydes (eg, 6-hydroxy aldehyde), lactoles (eg, 2-methanediol), esters (eg, ethyl acetate), hydrocarbons (eg, diphenylmethane, triphenylmethane), nitrohydrocarbons (eg, nitromethane), 1,4-butane? oles and sulfolane. Suitable protic solvents are disclosed in US Patent Number 5, 312, 996. As indicated above, the promoter that can be incorporated into the structure of the coordinating group either as the metal complex catalyst and coordinator group or as the free coordinating group. Promoters of the appropriate organophosphorus coordinating group that may be useful in this invention include, for example, tris (2-hydroxyl et? L) phosphine, tris (3-hydroxypropyl) phosphine, tris (2-hydroxyl)? fen? lfosfma), tris (4-hydroxifemlfosfma), tris (3-carbox? prop? l) phosphma, tris (3-carboxamidopropyl) phosphma, diphenyl (2-hydrox? phen?) phosphme, diethyl (2- anllmofen? l) phosphma, and tris (3-p? rro? l) phosphma. The use of coordinator group promoters can be particularly beneficial in those cases when the Alcohol product is not effective as a promoter. As with the organophosphorus coordinating groups which constitute the metal complex catalysts and the organophosphorus coordinating group and the free organophosphorus coordinating groups, the promoters of the organophosphorus coordinating group are preferably highly basic coordinating groups having a more spherical volume under or equal to a Tolman cone angle of 210 ° C, preferably less than or equal to the spherical volume of tricyclohexylphosphine (Tolman cone angle = 170 °). Of course, the promoters of the organophosphorus coordinating group can be used as organophosphorus coordinating groups which constitute the metal complex catalysts and the organophosphorus coordinating group and the free organophosphorus coordinating groups. Mixtures of promoters comprising one or more coordinating group promoters and mixtures comprising one or more coordinating group promoters and one or other promoters, e.g., protic solvents, may be useful in this invention. In one embodiment of the invention, the mixture of the hydrocarbonation process can consist of one or more liquid phases, v., A polar phase and a non-polar phase. These processes are often advantageous, for example, for separating catalyst products and / or reagents dividing in any phase. In addition, the selectivities of the product that depend on the properties of the solvent can be increased by carrying out the reaction in that solvent. One application of this technology is the aqueous phase hydrocarbination of alkadienes employing sulfonating phosphine coordinating groups, hydroxylated phosphine coordinating groups and phosphine coordinating groups as are for the rhodium catalyst. A process carried out in an aqueous solvent is particularly advantageous for the preparation of alcohols because the products can be separated from the catalyst by extraction in a solvent. As described herein, the phosphorus-containing coordinating group for the rodis hydrocarbonation catalyst may contain any of a number of substituents, such as cationic or ammonic substituents, which will make the catalyst soluble in a polar phase, eg, water. . Optionally, a phase transfer catalyst can be added to the reaction mixture to facilitate transport of the catalyst, reagents or products to the desired solvent phase. The structure of the coordinating group or the phase transfer catalyst is not critical and will depend on the choice of conditions, the reaction solvent, and the desired products.

When the catalyst is present in a multiphase system, the catalyst can be separated from the reactants and / or the products by conventional means such as extraction or decantation. The reaction mixture itself can consist of one or more phases, alternatively, the multiphase system can be created at the end of the reaction by, for example, adding a second solvent to separate the products from the catalyst. See, for example, U.S. Patent Number 5,180,854, the disclosure of which is incorporated herein by reference. In one embodiment of the process of this invention, an olefin may be hydrocarbylated together with an alkadiene using the above-described metal complex complexes and coordinating group. In these cases, an alcohol derivative of olefin is also produced, together with alcohols e.g., hexanediols. The mixtures of different olefinic starting materials can be used, if desired, in the hydrocarbonylation processes. More preferably, the hydrocarbonylation process is especially useful for the production of 1,6-hexanediols, hydroformylating the alkadienes in the presence of alpha-olefins containing from 2 to 30, preferably from 4 to 20 carbon atoms, including isobutylene, and the internal olefins that contain 4 to carbon atoms as well as the mixtures of the starting material of these alpha-olefins and internal olefins. The alpha-olefins which contain 4 or more carbon atoms may contain small amounts of corresponding internal olefins, and / or their corresponding saturated hydrocarbon and these commercial olefins do not necessarily have to be purified thereof before being hydroformylated. Illustrative of other olefinic starting materials include alpha-olefins, internal olefins, 1,3-dienes, 1,2-dienes, alkylalkenoates, alkenylalkenoates, alkenylalkyl ethers, alkenols, alkenes and the like, e.g. ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1- hexadecene, 1-heptadecene, 1-nonadecene, 1-ecosose, 2-butene, 2-methylpropene (isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexane, 2-heptene, cyclohexene, propylene dimers , propylene trimers, propylene tetramers, piperylene, isoprene, 2-ethyl-1-hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cycle -l-butene, aulic alcohol, auric butyrate, hex-1-en-4-ol, oct-l-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, propionate Aulic, methyl methacrylate, ether vinylethyl, vinylmethyl ether, vinyl cyclohexene, alylleyl ether, methyl pentenoate, n-propyl-7-octenoate, pentenales, e.g. 2-pentenal, 3-pentenal and 4-pentenal; penten-1-oles, e.g. 2-penten-1-ol, 3-penten-1-ol and 4-penten-1-ol; 3-butenonitrile, 3-pentenonitrile, 5-hexenamide, 4-methyl styrene, 4-isopropyl styrene, 4-tertiary butyl styrene, alpha-methyl styrene, 3-tert-butyl-alpha-methyl styrene, 1,3-diisopropenylbenzene, eugenol, iso-eugenol, safrole, isosafrole, anethole, 4-allyl alisol, indene, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camphene, linalool and the like. Other exemplary olefinic compounds may include, for example, p-isobutyl-styrene, 2-vinyl-6-methoxynaphthylene, 3-ethylphenylphenyl ketone, 4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl, 4- (1, 3-dihydro-l-oxo-2H-isoindol-2-yl) styrene, 2-ethenyl-5-benzoylthiophene, 3-ethylphenylphenyl ether, propenylbenzene, isobutyl-4-propenylbenzene, phenylvinyl ether and the like. Other olefinic compounds induce substituted aryl ethylenes as described in U.S. Patent Number 4,329,507, the disclosure of which is incorporated herein by reference. In those cases where the promoter is not the solvent, the hydrocarbonation processes covered by this invention they are carried out in the presence of an organic solvent for the metal complex catalyst and coordinating group and the free coordinating group. The solvent may also contain dissolved water up to the saturation limit. Depending on the catalyst and specific reagents employed, suitable organic solvents include, for example, alcohols, alkanes, alkenes, alkanes, ethers, aldehydes, hydrocarbonation byproducts of higher boiling temperature, ketones, esters, amides, tertiary amines, aromatics and similar. Any suitable solvent that does not unduly detrimentally interfere with the proposed hydrocarbonation reaction can, of course, be employed. Mixtures of one or more of the different solvents can be used if desired. Illustrative preferred solvents employable in the production of alcohols include ketones (eg, acetone and methylethyl ketone), esters (eg, ethyl acetate, hydrocarbons (eg, toluene), nitrohydrocarbons (eg, nitrobenzene), ethers (eg, tetrahydrofuran ( THF) and sulfolane The appropriate solvents are disclosed in US Pat. No. 5,312,996; "The amount of the solvent employed is not critical to the present invention and only needs to be that amount sufficient to solubilize the catalyst and the free coordinating group. the hydrocarbonylation reaction mixture to be treated. Generally, the amount of the solvent may vary from about 5 weight percent to about 99 weight percent or more, based on the total weight of the starting material of the hydrocarbonylation reaction mixture. Illustrative substituted unsubstituted and unsaturated alcohol intermediates and starting materials useful in the processes of this invention include one or more of the following: alkenoles such as ds-3-penten-1-ol, trans-3-penten-1 -ol, 4-penten-1-ol, cis-2-penten-1-ol and / or trans-2-penten-1-ol, including mixtures comprising one or more of the above-mentioned unsaturated alcohols. unsubstituted substituted and unsubstituted unsaturated alcohols (including derivatives of unsaturated alcohols) include those permissible substituted and unsubstituted unsaturated alcohols described in Kirk-Othmer Chemical Technology Encyclopedia, Fourth Edition, 1996, the relevant portions of which are incorporated herein by reference Illustrative substituted and unsubstituted 1, 6-hexanediols that can be prepared by the processes of this invention include alkane diols such as 1,6-hexanediol and 1,6-hexanediol. -hexanediols substituted (e.g., 2-methyl-l, 6-hexanediol and 3,4-dimethyl-l, 6-hexanediol) and the like. Suitable illustrative substituted and unsubstituted 1, 6-hexanediols (including 1, 6-hexanediols derivatives) include those permissible substituted and unsubstituted 1,6-hexanediols described in the Kirk-Othmer Chemical Technology Encyclopedia , Fourth Edition, of 1996, the pertinent portions of which are incorporated herein by reference. As indicated above, it is generally preferred to carry out the hydrocarbonylation process of this invention in a continuous manner. In general, continuous hydrocarbonation processes may involve: (a) hydrocarbonating the alkadiene starting material (s) with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture comprising a solvent, the metal complex catalyst and the coordinating group, and the free coordinating group; (b) maintaining the reaction temperature and pressure conditions favorable to the hydrocarbonylation of the alkadiene starting material (s); (c) supplying replacement amounts of the alkadiene starting material (s), carbon monoxide and hydrogen to the reaction medium as these reagents are used; and (d) recover the desired diol hydrocarbon product (s), in any desired manner. The continuous reaction can be carried out in a single-pass mode, ie, wherein a vaporous mixture comprising the unreacted alkadiene starting material (s) and the vaporized diol product is removed from the liquid reaction mixture. from where the diol product and the replacement alkadiene starting material (s) are recovered, and carbon monoxide and hydrogen are supplied to the liquid reaction medium for the next individual step without recycling the starting material (s) of unreacted alkadiene. However, it is generally desirable to employ a continuous reaction involving either a liquid and / or gas recycling process. These types of recycling process are known in the art and can involve the liquid recycling of the metal complex catalyst solution and coordinating group, separated from the desired diol reaction product (s). As indicated above, the hydrocarbonylation process may involve a liquid catalyst recycling process. These liquid catalyst recycling processes are known in the art. For example, in these liquid catalyst recycling processes it is common to continuously or intermittently remove a portion of the product medium from liquid reaction containing, e.g. the alcohol product, the metal complex catalyst and solubilised coordinating group, the free coordinating group and the organic solvent, as well as the byproducts produced in situ, by the unreacted alkadiene starting material and the hydrocarbonylation, the carbon monoxide and the hydrogen (synthesis gas) dissolved in that medium, from the hydrocarbonation reactor, to a distillation zone, eg, a vaporizer / separator in which the desired diol product is distilled in one or more stages under reduced or elevated normal pressure , as appropriate, and it is separated from the liquid medium. The desired, vaporized or distilled diol product thus separated may be condensed and recovered in any conventional manner as discussed above. The remaining non-volatilized liquid waste containing the metal complex catalyst and coordinating group, the solvent, the free coordinating group and usually a certain amount of the undistilled diol product is then recycled again with or without additional treatment as desired, together with any by-products and non-volatilized gaseous reactants still to be dissolved in the recycled liquid residue, in any desired conventional manner, to the hydrocarbonation reactor, as disclosed, eg in the aforementioned patents.

In addition, the reactive gases thus removed by distillation from the vaporizer can also be recycled back to the reactor, if desired. The recovery and purification of the diol products can be carried out by any appropriate means and can include distillation, phase separation, extraction, precipitation, absorption, crystallization, membrane separation, derivatization and other appropriate means. For example, a crude reaction product may be subjected to a distillation-separation at atmospheric or reduced pressure, through a packed distillation column. Reactive distillation can be useful to carry out the hydrocarbonylation reaction.

As indicated above, the conclusion of (or during) the hydrocarbylation process, the desired diols e.g. the 1,6-hexanediols can be recovered from the reaction mixtures used in the process of this invention. For example, in a recycling reaction of the continuous liquid catalyst, the portion of the liquid reaction mixture (containing the product of 1,6-hexanediol, the catalyst, etc.), removed from the reactor, can be passed to a vaporizer / separator wherein the desired alcohol product can be separated by distillation, in one or more steps, under normal, reduced or elevated pressure, from the reaction solution Liquid, condensed and collected in a container of the product and purified further if desired. The liquid reaction mixture containing the remaining non-volatilized catalyst can be recycled back to the reactants, as well as if desired, any other volatile materials, e.g. unreacted alkadienes, together with any hydrogen and carbon monoxide dissolved in the liquid reaction after separation thereof from the condensed 1,6-hexanediol product, e.g. by distillation in any conventional manner. In general, it is desirable to employ an organophosphorus coordinating group whose molecular weight exceeds that of the higher boiling temperature alcohol oligomer byproduct corresponding to the 1,6-hexanediols being produced in the hydrocarbonylation process. Another appropriate recovery technique is solvent extraction or crystallization. Generally, it is preferred to remove the desired 1,6-hexanediol from the reaction mixture containing the catalyst under reduced pressure and at low temperatures in order to avoid possible degradation of the organophosphorus co-ordinator group and the reaction products. When an alpha-mono-olefin reagent is also employed, the alcohol derivative thereof can also be separated by the aforementioned methods.

More particularly, the distillation and separation of the desired diol product from the solution of the product containing the metal complex catalyst and coordinating group can be carried out at any desired appropriate temperature. It is generally recommended that this distillation be carried out at relatively low temperatures, such as less than 150 ° C and more preferably at a temperature within the range of about 50 ° C to about 130 ° C. It is also generally recommended that this distillation of the diol be carried out under reduced pressure, e.g. a total gas pressure that is considerably lower than the total gas pressure used during hydrocarbonation, when low boiling temperature alcohols (eg, 5 and 6 carbon atoms) are involved or under vacuum when high temperature alcohols are involved of boiling (vg of 7 carbon atoms or more). For example, a common practice is to subject the liquid reaction product medium removed from the hydrocarbonation reactor to a pressure reduction in order to volatilize a considerable portion of the unreacted gases dissolved in the liquid medium, which now contains a concentration of gae. of much lower presence than was present in the middle of the hydrocarbonation process to the distillation zone, eg the vaporizer / separator, where distills the desired alcohol product. In general, distillation pressures that range from vacuum pressures to total gas pressure of approximately 3.52 kilograms per square centimeter should be sufficient for most purposes. Although it is not desired to be bound to any specific reaction mechanism, it is believed that the total hydrocarbonylation reaction proceeds generally in one step, that is, one or more of the substituted or unsubstituted alkadienes (eg butadiene) become one. or more substituted or unsubstituted diols (eg 1,6-hexanediols either directly or through one or more intermediates (eg 3-penten-ol and / or 4-penten-1-ol) This invention is not intended to be limited in any way to any specific reaction mechanism but rather encompasses all the permissible reaction mechanisms involved in the hydrocarbonylation of one or more of the substituted or unsubstituted alkadienes and / or the more saturated alcohols, with carbon monoxide and hydrogen in the presence of a metal complex catalyst and coordinator group and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted 1, 6-hexanediols.

A one-step process involving the reductive hydroformylation of one or more substituted or unsubstituted alkadienes to produce one or more substituted or unsubstituted 1,6-hexanediols is disclosed in Copending US Patent Application Serial No. 60 / 016,287, filed April 24, 1996, the disclosure of which is incorporated herein by reference. Another process involving the reductive hydroformylation of one or more of the substituted or unsubstituted alkadienes to produce one or more substituted or unsubstituted 1, 6-hexanediols is disclosed in a copending US Patent Application Serial Number (D-17775). ), presented on the same date as this, the exhibition of which is incorporated herein by reference. One embodiment of this invention relates to a process for producing one or more substituted or unsubstituted 1, 6-hexanediols comprising: (a) subjecting one or more substituted or unsubstituted alkadienes e.g. butadiene, hydrocarbonation in the presence of a hydrocarbonate catalyst, v g a metal complex catalyst and organophosphorus coordinating group and a promoter and optionally a free coordinating group to produce one or more alcohols substituted or unsubstituted msaturates comprising 3-penten-1-oles, 4-penten-1-ol and / or 2-penten-1-oles; (b) optionally separating the 3-penten-l-oles, 4-penten-l-ol, and / or 2-penten-l-oles from the hydrocarbonylation catalyst; and (c) subjecting one or more unsaturated or substituted unsaturated alcohols comprising 3-penten-l-oles, 4-penten-l-ol and / or 2-penten-l-oles to hydrocarbonation in the presence of a hydrocarbonation catalyst. vg a metal complex catalyst and the organophosphorus coordinating group, and a promoter and optionally a free coordinating group to produce one or more substituted or unsubstituted 1, 6-hexanediols. The hydrocarbonation reaction conditions in steps (a) and (c) may be the same or different, and the hydrocarbonate catalysts in steps (a) and (c) may be the same or different. Still another embodiment of this invention relates to a process for producing one or more substituted or unsubstituted 1,6-hexanediols comprising (a) subjecting one or more substituted or unsubstituted alkadienes e.g. butadiene, to hydrocarbonylation in the presence of a hydrocarbonation catalyst, e.g. a metal complex catalyst and an organophosphorus coordinating group and a promoter and optionally a group free coordinator for producing one or more substituted or unsubstituted saturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1-ols; (b) optionally separating the 3-penten-l-oles, 4-penten-l-ol, and / or 2-penten-l-oles from the hydrocarbonylation catalyst; and (c) optionally submitting isomerization, the 2-penten-l-oles and / or 3-penten-l-oles in the presence of a heterogeneous or homogeneous define isomerization catalyst to partially or completely isomerize the 2-penten-1 -ols and / or 3-penten-l-oles in 3-penten-l-oles and / or 4-penten-l-ol; and (d) subjecting one or more of the substituted or unsubstituted saturated alcohols comprising 2-penten-l-oles, 3-penten-l-oles and / or 4-penten-l-ol to hydrocarbylation in the presence of a catalyst of hydrocarbonylation, eg a metal complex catalyst and an organophosphorus coordinating group, and a promoter and optionally a free coordinating group to produce one or more substituted or unsubstituted 1, 6-hexanediols. The hydrocarbonylation reaction conditions in steps (a) and (d) may be the same or different, and the hydrocarbonylation catalysts in steps (a) and (d) may be the same or different.

The olefin isomerization catalyst in step (c) can be any of a variety of catalysts based on homogeneous or heterogeneous transition metal (particularly Ni, Rh, Pd, Pt, Co, Ru or Ir), or it can be a Heterogeneous or homogeneous acidic catalyst (particularly any acidic zeolite), polymeca resin, or source of H +, any of which can be modified with one or more transition metals). These olefinic isomerization catalysts are known in the art and isomepzation can be carried out by conventional methods known in the art. As used herein the term "isomerization" is proposed as including, but not being limited to, all permissible isomerization processes that involve converting one or more of the 2-penten-1-ols and / or 3-penten-1. -alles substituted or unsubstituted to one or more substituted or unsubstituted 4-penten-1-oles. When the processes of this invention are carried out in two stages (ie, producing first 2-penten-1-oles, 3-penten-1-oles and / or 4-penten-2-ol under a set of conditions and producing then a 1,6-hexanediol of the 2-penten-l-oles, 3-penten-l-oles and / or 4-penten-1-ol (or the acetals) under another set of conditions), it is preferred to carry carried out the first stage at a temperature of 75 ° C to 110 ° C, and a total preeión of 17. 58 kilograms per square centimeter at 70.30 kilograms per square centimeter, and carry out the second stage at a temperature of 60 ° C to 100 ° C, and at a pressure of 7.03 kilograms per square centimeter at 35.15 kilograms per square centimeter. Equal or different catalysts can be used in the first and second stages. The other conditions may be the same or different in both stages. The 1, 6-hexanodols products have a wide scale of utilities and are well known in the art, e.g. they are useful as starting materials / intermediates in the production of polyesters. The 1,6-hexanediols may also be useful as starting materials / intermediates in the production of caprolactones and caprolactams.

CYCLING STEP The process of cyclization involves converting one or more substituted or unsubstituted 1, 6-hexanediols, eg, a 1,6-hexanediol, or a reaction mixture comprising one or more substituted 1,6-hexanediols or not. substituted to one or more substituted or unsubstituted epsilon caprolactones or a reaction mixture comprising one or more subtilized epsilon caprolactones or not replaced. As used herein, the term "cyclization" is intended to include all permissible cyclization processes that involve converting one or more of the substituted or unsubstituted 1, 6-hexanediols, eg, into 1, 6-hexanod ? ol, or a reaction mixture comprising one or more 1,6-hexanediols to one or more substituted or unsubstituted epsilon caprolactones or a reaction mixture comprising one or more substituted or unsubstituted epsilon caprolactones. As used herein, the term "epsilon caprolactone" is intended to include all substituted or unsubstituted epsilon epsilon caprolactones which can be derived from one or more of the substituted or unsubstituted 1, 6-hexanediols, eg , 1, 6-hexanedione, or a reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediolee. Illustrative of the 1, 6-hexanediols substituted or unsubstituted include, for example, 1,6-hexanedione or its acetals, and the like. The 1, 6-hexanodols useful in the cyclization process are known materials and can be prepared by conventional methods. For example, 1,6-hexanedione can be produced by the hydroformylation and hydrogenation steps described above or by other conventional processes. Reaction mixtures comprising 1,6-hexanediols can be useful in the present. The amount of 1,6-hexanediols used in the cyclization step is not narrowly critical and can be any amount sufficient to produce epsilon caprolactone, preferably at high selectivities. The specific cyclization reaction conditions are not narrowly critical and can be any of the effective cyclization procedures sufficient to produce epsilon caprolactone. The cyclization reaction can be carried out at a temperature from about 50 ° C to about 400 ° C for a period of about one hour or less to about 4 hours or more, with the longer time being used at a lower temperature, of preferably from about 100 ° C to about 350 ° C for about 1 hour or less, to about 2 hours or more, and especially preferably at a temperature of about 150 ° C to about 300 ° C for about 1 hour or less. The cyclization reaction can be carried out through a wide range of pressures ranging from about 1.05 kilograms per square centimeter to about 140.60 kilograms per square centimeter.

It is preferred to carry out the cyclization reaction at pressures of about 1.05 kilograms per square centimeter to about 70.30 kilograms per square centimeter. The cyclization reaction is preferably carried out in the liquid or vapor states or mixtures thereof. The cyclization reaction can be carried out using known catalysts in conventional amounts. Illustrative of the appropriate cyclization catalysts include, for example, copper chromium promoted by barium, chromium promoted with barium, manganese, copper, calcium, zinc, for example, copper chromium promoted by barium, silver on alumina, molybdenum oxide on alumina, copper / zinc oxides , whether supported on alumina or bulk oxides, platinum / tin on alumina, copper / chrome / barium, cobalt on alumina / silica. Preferred cyclization catalysts include copper chromium promoted by barium, and copper / zinc oxide on alumina, and the like. The specific catalyst used should be capable of transforming 1,6-hexanediol into epsilon caprolactone in a high yield under mild conditions. The catalyst can be homogeneous or heterogeneous. The appropriate coordinator or promoter groups can be incorporated into these catalysts to modify the activity of the catalyst, selectivity, duration or ease of operation. These coordinator and promoter groups are known materials and can be used in conventional amounts. The amount of the cyclization catalyst used depends on the specific cyclization catalyst employed and may vary from about 0.01 weight percent or less to about 10 weight percent or more of the total weight of the starting materials. These cyclization reactions can be carried out in any suitable solvent in any appropriate atmosphere, or in the gas phase. These solvents and atmospheres are selected to allow the most desirable operation of the catalyst. For example, the reactions can be carried out on a hydrogen gas in order to stabilize the catalyst of the decomposition reactions in non-productive catalysts. Suitable solvents include ethers, esters, lactones (such as epsilon caprolactone), ketones, aliphatic or aromatic hydrocarbons, fluorocarbons, silicones, polyethers, chlorinated hydrocarbons and the like. The epsilon caprolactone produced by the cyclization step of this invention can be separated by conventional techniques such as distillation, extraction, precipitation, crystallization, membrane separation or other appropriate means. For example, a crude reaction product may be subjected to distillation at atmospheric or reduced pressure through a packed distillation column. Reactive distillation can be useful to carry out the cyclization reaction step. Exemplary epsilon caprolactones which can be prepared by the processes of this invention include epsilon caprolactone and substituted epsilon caprolactones (e.g., epsilon caprolactones substituted with alpha, beta, gamma and delta). Illustrative of the appropriate substituted and unsubstituted epsilon caprolactones (including the epsilon caprolactone derivatives) include those permissible substituted and unsubstituted epsilon caprolactones described in the Kirk-Othmer Chemical Technology Encyclopedia, Third Edition, 1984, pertinent portions of which are incorporated herein by reference. The substituted or unsubstituted epsilon caprolactone has a broad scale of utilities that are well known in the art, e.g., they are useful as starting materials / intermediates in the production of epsilon caprolactam and polyesters. The hydrocarbonylation processes of this invention can be carried out using, for example, a fixed bed reactor, a fluid bed reactor, a continuous stirred tank reactor (CSTR) or a slurry reactor. The optimal size and shape of the catalysts will depend on the type of reactor used. In general, for the fluid bed reactors, a small spherical catalyst particle is preferred for easy fluidization. With fixed bed reactors, larger catalyst particles are preferred so that the back pressure within the reactor remains reasonably low. The hydrocarbonation processes of this invention can be carried out intermittently or continuously, with the recycling of unconsumed starting materials, if required. The reaction can be carried out in a single reaction zone or in a plurality of reaction zones, in series or in parallel or it can be carried out intermittently or continuously in an elongated tubular zone or a series of these zones. The materials of construction used must be inert to the materials present during the reaction and the manufacture of the equipment must be able to withstand the temperatures and pressures of the reaction. The means for introducing and / or adjusting the amount of starting materials or ingredients introduced intermittently or continuously into the reaction zone during the course of the reaction, they can be conveniently used in the processes especially to maintain the desired molar ratio of the starting materials. For example, hydrogen and carbon monoxide can be fed in appropriate molar ratios e.g. about 2: 1 in order to maintain the desired partial pressures. The reaction steps can be carried out by the incremental addition of one of the starting materials to the other. Also, the reaction steps can be combined by co-addition of the starting materials. When the complete conversion is not desired or is not able to be obtained, the starting materials can be separated from the product, for example by distillation, and the starting materials are then recycled back to the reaction zone. The hydrocarbonation processes can be carried out either in a glass-lined, stainless steel reaction equipment or a similar type. The reaction zone can be equipped with one or more internal and / or external heat exchangers in order to control undue temperature fluctuations or to prevent any of the possible "fugitive" reaction temperatures. The hydrocarbonylation processes of this invention can be carried out in one or more steps or stages. The exact number of steps or stages of reaction will be regulated by the best compromise between achieving high catalyst selectivity, activity, duration and ease of operation as well as the intrinsic reactivity of the starting materials in question, and the stability of the materials of starting and the desired reaction product with respect to the reaction conditions. The substituted and unsubstituted 6-hexanodols produced by the processes of this invention may undergo additional reaction (s) to provide the desired derivatives thereof. These permissible derivatization reactions can be carried out in accordance with conventional procedures known in the art. Exemplary derivatization reactions include, for example, cyclization, dehydration, cyclocarbonylation, carboesterification, hydrogenation, esterification, etherification, animation, quenching, dehydrogenation, reduction, acylation, condensation, carboxylation, carboylation, oxidation, silylation and the like, including allowable combinations. from the same. Preferred derivatization reactions and 1,6-hexanediol derivatives include, for example, animation to provide hexamethylenediamma, oxidation to provide acid adipic, oxidation and cyclization to provide epsilon caprolactone, and oxidation, cyclization and amination to provide epsilon caprolactam. This invention is not intended to be limited in any way by the permissible derivatization reactions or permissible derivatives of the substituted and unsubstituted 1, 6-hexanediols. For purposes of this invention, the term "hydrocarbon" is proposed as including all permissible compounds having at least hydrogen and a carbon atom. These allowable compounds may also have one or more heteroatoms. In a broad aspect, the permissible hydrocarbons include acyclic (with or without heteroatoms) and cyclic, branched and unbranched, carbocyclic and heterocyclic aromatic and non-aromatic compounds which can be substituted or unsubstituted. , the term "substituted" is intended to include all permissible substituents of the organic compounds unless otherwise indicated In a broad aspect, the permissible substituents include acyclic and branched and unbranched cyclic, carboxylic and heterocyclic, aromatic and cyclic substituents and non-aromatic, organic compounds.

Illustrative include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen, and the like wherein the number of carbon atoms may vary from 1 to about 20 or more, preferably from 1 to about 12. Permissible substituents may be one or more and may be the same or different for the appropriate organic compounds. This invention is not intended to be limited in any way by the permissible substituents of the organic compounds. For the purposes of this invention, the chemical elements that are identified in accordance with the Periodic Table of Elements reproduced in "Basic Inorganic QUi.m?" By F. Albert Cotton, Geoffrey Wiikinson and Paul L. Gaue, published by John Wiley and Sons, Inc. Third Edidon of 1995. Certain of the following examples are provided to further illustrate this invention.

Examples 1-19 In a high-pressure stirred high-pressure reactor 100 milliliters was charged 0.25 millimole rhodium of rhodium dicarbonyl acetylacetonate (I), 0.9 millimole of a trialkyl phosphine defined in Table A which is then presents 3 milliliters of butadiene, 26 milliliters of a solvent as defined in Table A and 1 milliliter of diglyme as an internal standard. The reactor was pressurized with from .352 to .703 kilogram per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1 and heated to the desired temperature indicated in Table A. At the desired temperature, the reactor was pressurized to the desired hydrogen / carbon monoxide ratio indicated in Table A, and gas absorption was monitored. After a decrease in pressure of 10 percent, the reactor is re-pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. Samples of the reaction mixture were taken in flasks cooled with dry ice through the sampling line at scheduled intervals and analyzed by gas chromatography. At the end of the 90 minute reaction period, the gases were discharged and the reaction mixture was drained. The additional details and results of the analyzes are shown in Table A.

Table A Ex Solvent / P: Temp No. ° C 1 Ethanol Triethylphosphine 60 2 Ethanol Tpethylphosphine 80 3 Ethanol Triethylphosphine 80 4 Ethanol Triethylphosphine 80 Octanol Trioctylphosphine 80 6 3-Pentenol Tpoctilfosfma 80 7 Hexane lol Tpoctilfosfina 80 8 Pirrol Trioctilfosfma 80 9 Ethanol Tributylphosphine 80 Phenol / THF Tpoctllfosfma 80 11 t-Butanol Tpetilfosfma 120 12 Ethanol Trimetilfosfma 120 13 Ethanol Diethyl-para-N, N- dimethylf emlf osf ma 80 14 Ethanol / Acetonitoplo Triethylphosphma 80 15 Ethanol / Tetraglyme Tethylphosphine 80 16 Diphenylamine Trioctylphosphine 80 17 Acetamide T ioctilfosfma 80 18 Metllacetamlda Trioctllfosfina 80 19 N-Met? Lformam Tpoctilfosfma 80 Table A (continued) Ex. H H22 // CCO0 C Coonnvveerrssiioon R Régéggiimmeenn Selectivi- No. ((kkgg // ccmm22)) of bbuuttaaddiieennoo ((mm // LL // hh)) given (%) of (%) 3 and 4 Pentenoles 1 2 211..0099 // 2211..0099 2 277 0 0..22 92 2 2 211..0099 // 2211..0099 9 900 1 1..66 87 3 3 355..1166 // 3355..1166 8 877 1 1..33 91 4 5 5..2244 // 55..2244 7 755 0 0..33 71 5 42.18 / 14,06 98 1.9 6 4 422 ... 1188 // 1144 .. .0066 8 899 nndd 90 7 2 211. .0099 // 2211 .. .0099 6 655 nndd 93 8 4 422 ... 1188 // 1144 .. .0066 9 900 1 1..44 88 9 2 211. .0099 // 2211 .. .0099 5 555 1 1..00 70 10 4 422 ... 1188 // 1144 .. .0066 8 844 2 2..00 55 11 1 177 .. .66 // 1177 .. .66 9 999 nndd 38 (15 man Runtime) 17. 6 /17.6 97 nndd 42 (2 hr. 13 17.6 /17.6 70 1.2 64 14 21.09 / 21.09 68 1.1 82 21.09 / 21.09 64 1.0 91 16 42.18 / 14.06 80 0.8 54 17 42 18 / 14.06 85 0.9 34 18 42.18 / 14.06 73 0.8 59 19 42.18 / 14.05 33 0.1 19 nd = not determined Examples 20-26 In an upper agitated high pressure reactor with a capacity of 100 milliliters, 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), 0.9 millimole of tpalkylphosphine defined in Table B below, was charged with 3 milliliters of butadiene, 26 milliliters ethanol and 1 milliliter of diglyme as the internal norm. The reactor was pressurized with from .352 to .703 kilogram per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1 and heated to 80 ° C. At the desired temperature, the reactor is pressurized to the desired hydrogen / carbon monoxide ratio indicated in Table B, and the gas absorption was monitored. After a decrease in pressure of 10 percent, the reactor was re-pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. Samples of the reaction mixture were taken in flasks cooled with dry ice through the sampling line at scheduled intervals and analyzed by gas chromatography. At the end of the 120 minute reaction period, the gases were discharged and the reaction mixture was drained. The additional details and results of the analyzes are shown in Table B.

Table B Ex. Fos ina H_ / CO Conver- Selective Regimen No. (kg / cm2) of (m / L / h) nity (< 4) of buta- 3 and 4 diene Pentenoles < *) 20 t-butyldiethyl 21.09 / 21.09 60 0.8 13 phosphine 21 t-butyldiethyl 56.24 / 14.06 69 1.1 19 phosphine 22 cyclohexyl- 21.09 / 21.09 76 _0.7 75 diethylphosphine 23 cyclohexyl- 56.24 / 14.06 82 1.4 80 diethyl phosphine 24 n-butyldiethyl- 21.09 / 21.09 77 '1.1 82 phosphine 25 diethylphenyl 14.06 / 56.24 53 0.9 77 phosphine 26 ethyldiphenyl- 14.06 / 56.24 38 0.6 27 phosphine Example 27 A magnetically stirred autoclave of 160 milliliter capacity was purged with 1: 1 H- / C0 and charged with a catalyst solution consisting of 0.1125 gram (0.44 millimole) of dicarbonyl acetylacetonate of rodlo (I), 0.3515 gram (2.94 millimoles) of P (CH¿CH2CH-OH) 3, and 44.1 grams of tetrahydrofuran. The autoclave was pressurized with 2.81 kilograms per square centimeter gauge of 1: 1 H2 / CO and heated to 80 ° C. 6 milliliters (3.73 grams) of 1,3-butadiene were charged with a regulated supply pump and the reactor was pressurized to 70.30 kilograms per square centimeter with 1: 1 H2 / CO. The reaction mixture was maintained at 80 ° C under 70.30 kilograms per square centimeter of 1: 1 H2 / CO. The samples of the reaction mixture that were taken after 90 minutes and 170 minutes gave the results indicated in Table C below: Table C Example 28 A magnetically stirred autoclave of 160 milliliter capacity was purged with 1: 1 H2 / CO and charged with a catalyst solution consisting of 0.1126 gram (0.44 millimole) of rhodium dicarbonyl acetylacetonate (I), 0.6120 gram (1.69 millimoles) of P (CH2CH2CH2OH) J and 39.9 grams of ethanol. The autoclave was pressurized with 2.81 kilograms per square centimeter gauge of 1: 1 H2 / CO and heated to 80 ° C. 6 milliliters (3.73 grams) of 1,3-butadiene were charged with a regulated supply pump and the reactor was pressurized at 70.30 kilograms per square centimeter gauge with 1: 1 H2 / CO. The reaction mixture was maintained at 80 ° C under a pressure of 70.30 kilograms per square centimeter of 1: 1 H2 / CO. The samples of the reaction mixture taken after 15 and 43 minutes gave the results indicated in Table D, which are presented below.

Table D Tlelppo (min.) (*) Example 29 A magnetically stirred autoclave with a capacity of 160 milliliters was purged with 1: 1 H / CO and charged with a catalyst solution consisting of 0.1125 gram (0.44 millimole) of rhodium dicarbonyl acetylacetonate (I), 0.3515 gram (2.94). millimoles) of P (CH2CH2CH2OH) 3 and 44.1 grams of tetrahydrofuran. The autoclave was pressurized with 2.81 kilograms per square centimeter gauge of 1: 1 H2 / CO and heated to 80 ° C. 6 milliliters (3.73 grams) of 1,3-butadiene were charged with a regulated supply pump and the reactor was pressurized at 70.30 kilograms per square centimeter gauge with 1: 1 H2 / CO. The reaction mixture was maintained at 80 ° C under 70.30 kilograms per square centimeter of 1: 1 H2 / CO. A sample of the reaction mixture taken after 90 minutes gave the results indicated in Table E, which are presented below.

Table E T ± focus H2 / C0 Conversion Rate Selectivity (%) 2 (min.) Kgkg / cra) of butadiene (m / L / H) of 1, 6 -Hexanodiol manometer) () 35.15 / 35.15 Example 30 A magnetically stirred autoclave with a capacity of 160 milliliters was purged with 1: 1 H / CO and loaded with a catalyst solution consisting of 0.1126 gram (0.44 millimole) of rhodium dicarbonyl acetylacetonate (I), 0.6120 gram (1.69 millimoles) ) of P (CH2CH2CH2OH) 3 and 39.9 grams of ethanol. The autoclave was pressurized with 2.81 kilograms per square centimeter gauge of 1: 1 H2 / CO and heated to 80 ° C. 6 milliliters (3.73 grams) of 1,3-butadiene were charged with a regulated supply pump and the reactor was pressurized at 70.30 kilograms per square centimeter gauge with 1: 1 H2 / CO. The reaction mixture was maintained at 80 ° C under 70.30 kilograms per square centimeter of 1: 1 H2 / CO. A sample of the reaction mixture taken after 60 minutes gave the results indicated in Table F, which are presented below.

Table F Examples 31 to 34 A stirred high-pressure reactor with a capacity of 100 milliliters was charged with 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), 0.9 millimole of tpalkylphosphine (as defined in Table G below), 3 milliliters of butadiene , 26 milliliters of ethanol and 1 milliliter of diglyme, as an internal standard. The reactor was pressurized with from .352 to .0703 kilogram per square centimeter of hydrogen / carbon monoxide in a ratio of 1/1, and heated to 80 ° C. At the desired temperature, the reactor was pressurized to a desired hydrogen / carbon monoxide ratio as indicated in Table G and the absorption of the gas was monitored. After a 10 percent drop in reactor pressure, the reactor was re-pressurized to the initial value with hydrogen / carbon monoxide in a ratio of 1/1. At the end of the 120 minute reaction period, the gases were discharged and the reaction mixture was drained and analyzed by gas chromatography. The details and additional results of the analyzes are shown in Table G.

Table G Ex. Trialquil H2 / CO ConverRime Selectivity to No. Phosphine (kg / cm2) of (m / L / h) buta1, 6-hexanod? Ol diene (* > (%) 31 cyclohexyl 21.09 / 21. .09 76 0.7 7.2 diethylphosphine 32 cyclohexyl 56.24 / 14.06 diethyl phosphine 33 n-butyl diethylphosphine 21.09 / 21.09 34 diethylphenylphosphine 14.06 / 56.24 53 Examples 35 to 52 The catalysts were prepared by mixing the rhodium (I), [C 2 (CO) β] and ethanol (30 milliliters) dicarbonyl acetylacetonate in a Schlenk flask under a blanket of nitrogen such that the individual metal concentrations were achieved from Table H. added triethylphosphine (the amount indicated in Table H) as a 1.0 molar solution in tetrahudrofuran together with a measured amount of diglyme, as the internal standard. The mixture was stirred for 5 to 10 minutes before being transferred to a stainless steel Parr autoclave with a capacity of 100 milliliters. The desired amount of butadiene was then added via syringe. The pump was then presiomzed with approximately 25 percent of the desired final carbon monoxide pressure and approximately 25 percent of the desired final hydrogen partial pressure before heating to the final desired reaction temperature, when carbon monoxide was added. and the hydrogen in an amount to achieve the desired final partial pressures (all indicated in Table H). The reaction was allowed to continue for a stated period of time. When the total pressure had decreased to 90 percent of the total desired pressure, 2.1 sytic gas (a mixture of hydrogen and carbon monoxide) was added to raise the total pressure back to 100 percent of that desired. The reactor was cooled to room temperature and discharged at atmospheric pressure and the content was analyzed by gas chromatography to provide the results indicated in Table I.

Table H Ej [[RRhh]] [[CCoo]] PPEEttjj BBuuttaa-- T Teemmpp P P ((CCOO)) P (H2) Time (ppm) (ppm) (millidiene CC) (kg / (kg / (min) mol) (milli- cm 2 cm 2 moles) _man) (man) 309 315 0.3 34.8 100 17.06 28.12 113 36 604 313 1.0 36.7 125 38.30 42.18 120 37 911 311 1.6 33.8 150 28.12 56.24 148 38 965 654 1.0 33.3 100 28.12 42.18 124 39 297 599 2.1 33.1 125 17.06 56.24 110 40 594 593 0.3 36.9 150 28.12 38.30 138 41 300 892 2.1 27.7 100 38.30 42.18 115 42 606 892 0.3 34.2 150 28.12 56.24 138 43 900 900 1.1 33.7 150 17.06 28.12 120 44 600 300 1.7 67.0 100 28.12 28.12 121 45 916 312 0.3 68.1 125 17.06 42.18 99 46 330 332 1.0 31.5 150 38.30 56.24 122 47 911 597 0.3 66.7 100 38.30 56.24 120 48 307 586"1.2 66.7 125 28.12 28.12 138 49 600 600 1.9 69.6 150 17.06 42.18 112 50 601 910 1.2 68.6 100 17.06 56.24 138 51 885 874 1.9 69.5 150 28.12 42.18 138 52 324 789 0.4 71.9 150 28.12 42.18 120 Cuad: ro I Example Penten-Penten- 6-Hydroxy-1, 6- 1-oles 1-oles hexanal Hexanodiol 1.7 68.7 2.0 3.7 36 0.0 29.4 0.0 - 8.7 37 3.8 3.3 0.0 0.0 38 0.0 79.3 0.0 7.5 39 0.0 62.5 0.9 8.5 40 4.6 0.0 1.6 2.4 41 2.5 13.0 0.0 0.0 42 6.1 0.0 1.8 0.0 43 0.0 0 0 0.0 9.8 44 0.0 74.8"0.7 5.2 45 1.9 0.0 2.5 1.0 46 0.0 4.4 0.6 10.2 47 0.0 42.0 0.6 7.8 48 0.0 53.1 1.0 7.3 49 0.0 1.3 0.4 9.5 50 0.4 79.2 0.9 5.4 51 0.0 54.8 0.6 8.5 52 5.8 1.0 0.0 0.0 Ej emplos 53 - 60 The catalysts were prepared by mixing rhodium acetylacetonate (I), (0 11 millimole), Pet3 (1.0 molar in tetrahydrofuran) and PhP (CH2CN) 2, diglyme (internal standard of gas chromatography: 1 milliliter) and ethanol ( 23 milliliters) in a Schlenk flask under a blanket of nitrogen such that the molar ratios of the coordinator / metal group of Table J presented below were achieved. The mixture was stirred for 5 to 10 minutes before being transferred to a 100 milliliter stainless steel Parr autoclave. The desired amount of butadiene was then added by means of a syringe. The pump is then pressurized with approximately 25 percent of the desired final carbon monoxide pressure and approximately 25 percent of the desired final hydrogen partial pressure before heating to the final desired reaction temperature., when carbon monoxide and hydrogen were added in an amount to achieve the desired final partial pressures (all indicated in Table J). The reaction was allowed to continue for the indicated time interval. When the total pressure had decreased 90 pet of the total desired pressure, 2: 1 of synthesis gas (a mixture of hydrogen and carbon monoxide) was added to raise the total pressure back to 100 pet of that desired . The reactor cooled to Room temperature was discharged at atmospheric pressure and the content was analyzed by gas chromatography to provide the results indicated in Table K below.

Picture J Ex PhP (CH2CN) 2 / Rh PEt3 / Rh Butadiene Temp P (CO) P (H2) Time (mil- (° C) (kg / cm2 (kg / cm2 (min) mmoolleess)) manom) manom) 53 2 1 - 58.1 70 56.25 10.55 138 54 2 5 100.6 70 14. 06 10.55 138 55 8 5 68.5 70 56.25 10.55 123 56 2 1 67.4 100 56.25 31.27 110 57 8 1 67.4 100 14.06 31.27 110 58 2 5 68.1 100 14. 06 31.27 127 59 8 5 68.1 100 56.25 31.27 128 60 5 3 68.4 85 35.15 21.09 127 Table K Ej Penten- 1-oles Penten-1-o 53 11. 0 74. 9 0.0 0.0 54 5 .2 70. 8 0.0 0.0 55 43. 4 47. 3 0.0 0.0 56 65.1 3. 4 0.0 0.0 57 71. 3 1. 4 0.0 0.0 58 0. 5 69.1 0.0 0.0 59 5. 4 68. 8 2.5 3.5 60 14. 9 49. 9 3.4 1.2 Examples 61-66 A stirred high-pressure reactor with a capacity of 100 milliliters was charged with 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), from 0.9 to 2.6 millimoles of a phosphine indicated in Table L below, 3 milliliters. of butadiene, 26 milliliters of the solvent indicated in Table L and 1 milliliter of diglyme, as the internal standard. The reactor was pressurized with from .352 to .0703 kilogram per square centimeter of 1/1 of -hydrogen / carbon monoxide and heated to desired temperature. At the desired temperature, the reactor was pressurized to the desired ratio and pressure with hydrogen and carbon monoxide, and gas absorption was monitored After absorption of 10 percent gas, the reactor was re-pressurized to the initial value with 1/1 hydrogen / carbon monoxide Samples of the reaction mixture they were collected in small flasks cooled with dry ice through the sampling line at scheduled intervals and analyzed by gas chromatography. At the end of the 90 minute reaction period, the gases were discharged and the reaction mixture was drained and stored. in storage bottles under a blanket of nitrogen Details and additional results are illustrated in Table L Table L Sol Solvent / Promoto: Phosphine Temp No (Phosphine Rh) ° C 61 Diphenylamine Tpoctylphosphine (4) 80 62 Ethanol Triethylphosphine (10 5) 100 63 Ethanol Triethylphosphine (3 5) 80 64 Acetamide Trioctylphosphine (4) 90 65 N-Methyl Cetamide Tpoctilfosfma (4) 90 66 Pirrol Trioctllfosfma (4) 80 Table L (continued) Ex. r / CO Conv. of Regime 1,6-No. (kg / cm2) butadiene (m / L / h) Hexanodiol (*) (%) 61 42.18 / 14. .06 80 0.6 6 62 21.09 / 21. .09 74 1.4 7 63 21.09 / 2-1. .09 71 1.0 5 64 42.18 / 14. .06 84 0.8 3 65 42.18 / 14. .06 73 0.5 8 66 42.18 / 14. .06 90 1.4 5 Examples 67 and 68 A stirred high-pressure reactor with a capacity of 100 milliliters was charged with 0.25 millimole of rhodium dicarbonyl acetylacetonate (I), 0.9 millimole of phosphine indicated in Table M below, 2 milliliters of the unsaturated substrate (pentenal or pentenol) indicated in Table M, 26 milliliters of the solvent indicated in Table M, and 1 milliliter of diglyme as the internal standard. The reactor was pressurized with 7.03 kilograms per square centimeter of 1/1 hydrogen / carbon monoxide, and heated to the desired temperature. At the desired temperature, the reactor was pressurized to the desired pressure with 1/1 of hydrogen in carbon monoxide and the reaction mixture is stirred for 2 to 4 hours. At the end of the reaction period, the gases were discharged and the reaction mixture was drained and analyzed by gas chromatography. The details and additional results are illustrated in Table M.

Table M E] Substrate Solvent / Phosphine Temp H / CO 1,6- Promoter. Phosphine Rh) (° C) (kg / cm2) Hexanediol (%) 67 4-Pentenol Ethanol Tpetll- fosfma (3 5) 120 21 09/21 09 69 68 4-Pentenal Pyrrole Trioctyl-fosiline (4) 120 21.09 / 21 09 59 Example 69 Reactor System The reaction system consisted of an oven Applied Test Systems, Inc. equipped with a quartz tube reaction zone of 9.53 millimeters by 55.88 centimeters. The tube was charged in the following order with a 2-centimeter glass wool plug, 3 centimeters of 2-millimeter lead-free glass beads, 12 centimeters of an Engelhard Cu-1186T granulated catalyst of 3.18 millimeters and 20 centimeters of glass beads free of lead of 2 millimeters. The quartz tube was placed in the furnace in order to center the catalyst inside the furnace. The tube was equipped with two thermoelectric cells, one in the upper part of the catalyst bed, one in the lower part of the catalyst bed. The system was equipped with regulated feeds of nitrogen gas and nitrogen gas. A cold trap was used to condense the product from the gas flow. The reactor was operated at atmospheric pressure. The reagents were fed into the system through a syringe pump and squeezed into the glass beads to vaporize.

Activation of the Catalyst A flow of nitrogen gas of 51 cubic centimeters per minute was initiated. The oven was heated to a temperature of 230 ° C. Once the temperature had stabilized, a flow of hydrogen gas of 5 cubic centimeters per minute was initiated. Over a period of two hours the flow of hydrogen gas was increased to 51 cubic centimeters per minute. An exothermic reaction associated with the reduction of the catalyst was observed by the upper thermoelectric cell. Activation of the catalyst was completed when a reaction was observed exothermic by the lower thermoelectric battery and subsists. The temperature of the catalyst bed was raised to 260 ° C. A diethylene glycol feed of 0.012 millimeter per minute was started and allowed to continue for 24 hours. The produced condensed material was sampled after 24 hours and analyzed by gas chromatography. The analysis showed a conversion of > 90 percent and a selectivity to 1, -dioxanone of diethylene glycol. The dehydrogenation of diethylene glycol was carried out to determine if the catalyst was active.

Dehydrogenation of 1,6-Hexanediol The feed of the reagent was stopped, the hydrogen feed was stopped, and the syringe pump, feed lines and the receptacle for the product were cleaned. The syringe pump was filled with a solution of 75 grams of glyme and 50 grams of 1,6-hexanediol. The hydrogen feed was started and maintained at 51 cubic centimeters per minute. The nitrogen feed was maintained at 51 cubic centimeters per minute. the feed of 1,6-hexanediol was started at 0.024 milliliter per minute. The temperature of the upper thermoelectric cell was 264 ° C. The temperature of the catalyst bed was maintained at approximately 260 ° C (as measured by the upper thermoelectric battery) during the rest of the test. The reactor was operated under these conditions for 24 hours. The products and the unreacted feed were condensed from the gas stream through an air-cooled condenser. After 24 hours of reaction time, the reactor was switched on and 5.0 grams of the crude product of the condenser collecting the product were removed. The crude product was analyzed by gas chromatography. Analysis of the crude product showed 13.2 percent glima, 25.0 percent 1,6-hexanedione, 30.9 percent caprolactone, and several other unidentified by-products that make up the rest of the sample. Gas chromatography was not calibrated and the results are the percentage of the area of analysis. The product of caprolactone was confirmed through gas chromatography / infra-red analysis / mass spectrography. Even though the invention has been illustrated by certain of the foregoing examples, it should not be construed as being limited thereby; rather, the invention encompasses the generic area as disclosed in the foregoing. Different modifications and modalities can be made without deviating from the spirit and scope of the same.

Claims (20)

R E I V I N D I C A C I O N E S-

1. A process for producing one or more substituted or unsubstituted 1,6-hexanediols, which comprises reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen, in the presence of a complex metal catalyst and a coordinating group and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted 1, 6-hexanediols.

2. A process for producing one or more substituted or unsubstituted 1,6-hexanediols comprising reacting one or more pentanels substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted 1,6-hexanediols.

3. A process for producing one or more substituted or unsubstituted 1,6-hexanediols comprising reacting one or more substituted or unsubstituted penten-1-ols with carbon monoxide and hydrogen, in the presence of a complex metal catalyst and a coordinating group and a promoter and optionally a group free coordinator, in order to produce one or more substituted or unsubstituted 1,6-hexanediols.

4. A process for producing one or more substituted or unsubstituted 1,6-hexanediols comprising: (a) reacting one or more substituted or unsubstituted alkadienes with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group and a promoter and optionally a free coordinating group, to produce one or more substituted or unsubstituted penten-1-ols and (b) to react one or more penten-1-ols substituted or unsubstituted with carbon monoxide and hydrogen, in the presence of a metal complex catalyst and a coordinating group, and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted 1, 6-hexanediols.

5. The process of claims 1 and 4, wherein the substituted or unsubstituted alkadiene comprises butadiene, the substituted or unsubstituted penten-1-oles comprise cis-3-penten-1-ol, trans-3-penten -l-ol, 4-penten-1-ol, c? s- -penten-l-ol and / or trans-2-penten-l-ol and substituted or unsubstituted 1,6-hexanod? ol comprises 1 , 6-hexanediol.

6. The process of claim 4, wherein the hydrocarbonation reaction conditions in the Steps (a) and (b) may be the same or different, and the hydrocarbonylation catalysts in steps (a) and (b) may be the same or different.

The process of claims 1, 2, 3 and 4 wherein the metal complex catalyst and the coordinator group comprises a metal selected from Group 8, 9 and 10 metal formed in complex with an organophosph coordinating group. which is selected from the coordinating group of mono-, tp- and poly- (organophosphine).

8. The process of claims 1, 2, 3 and 4, wherein the metal complex catalyst and the coordinating group comprises a metal which is selected from a Group 8, 9 and 10 metal formed in complex with an organophosphine coordinating group which is selected from a triorganophosphine coordinating group represented by formula: R1 / P - R1 \ 1 R wherein each R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical.

9. The process of claim 7, wherein the coordinating organophosph group has a basicity greater than or equal to the basicity of triphenylphosphine (pKb = 2.74) and a spherical volume less than or equal to a Tolman cone angle of 210 ° C.

10. The process of claims 1, 2, 3 and 4, wherein the promoter is incorporated into the structure of the coordinating group either as a complex metal catalyst and coordinating group or as a free coordinating group.

11. The process of claims 1, 2, 3 and 4, wherein the promoter has a pKa of about 1 to And it comprises a protic solvent, organic and inorganic acid, alcohol, water, phenol, thiol, selenol, nitroalkane, ketone, nithop, amine, amide or a mono-, di- or tp-alkylammonium salt or mixtures thereof.

12. The process of claims 1, 2, 3 and 4, which is carried out at a temperature of about 50 ° C to 150 ° C, and a total pressure of about 1.41 kilograms per square centimeter manometrica to about 210.90 kilograms per square centimeter manometpca.

The process of claim 1, 2, 3 and 4, wherein the process intermittently or continuously generates a reaction mixture comprising. (1) one or more substituted or unsubstituted 1, 6-hexanediols; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 6-hydroxyl hexanals; (4) optionally one or more substituted or unsubstituted 5-hydroxyspinals, and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted 4-hydroxysubstituted butanales, and / or the cyclic lactol derivatives thereof; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; (8) optionally one or more substituted or unsubstituted pentenales; (9) optionally one or more substituted or unsubstituted 1, 6-hexanediols; (10) optionally one or more substituted 1, 5-pentanediols; (11) optionally one or more substituted 1,4-butanediols; and (12) one or more substituted or unsubstituted butadienes; where the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9), ( 10) and (11) is greater than about 0.1; and the weight ratio of the component (12) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) ), (10) and 11, is from about 0 to about 100; or a reaction mixture comprising: (1) one or more substituted or unsubstituted 1,6-hexanediols; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 6-hydroxyl hexanals; (4) optionally one or more substituted or unsubstituted 5-hydroxyspinals, and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; and (8) optionally one or more substituted or unsubstituted pentenales; wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6) and (7) is greater than about 0.1; and the weight ratio of the component (8) to the sum of the components (1), (2), (3), (4), (5), (6) and (7) is from about 0 to about 100.; or a reaction mixture comprising: (1) one or more substituted or unsubstituted 1,6-hexanediols; (2) one or more substituted or unsubstituted penten-1-oles; (3) optionally one or more substituted or unsubstituted 6-hydroxyhexanals; (4) optionally one or more substituted or unsubstituted 5-hydroxyptanales, and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof; and (6) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4), (5) and (6) is greater than about 0.1; and the weight ratio of the component (2) to the sum of the components (1), (3), (4), (5) and (6) is from about 0 to about 100; or a reaction mixture comprising: (1) one or more substituted or unsubstituted 1,6-hexanediols; (2) optionally one or more substituted or unsubstituted penten-1-oles; (3) optionally one or more substituted or unsubstituted 6-hydroxyhexanals; (4) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; (8) optionally one or more substituted or unsubstituted pentenales; (9) optionally one or more substituted or unsubstituted 1, 6-hexanediols; (10) optionally one or more substituted 1, 5-pentanedioles; (11) optionally one or more substituted 1,4-butanediols; and (12) one or more substituted or unsubstituted butadienes; where the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9), ( 10) and (11), is greater than about 0.1; and the weight ratio of the component (12) to the sum of the components il), (2), (3), (4), (5), (6), (7), (8), (9) , (10) and (11) is from about 0 to about 100.

14. A process for producing a reaction mixture comprising one or more substituted or unsubstituted 1, 6-hexanediols, which process comprises the process of claims 1, 2, 3 and 4.

15. A composition produced by the process of Claims 1, 2, 3 and 4, comprising: (1) one or more substituted or unsubstituted 1, 6-hexanediols; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 6-hydroxyl hexanals; (4) optionally one or more substituted or unsubstituted 5-hldrox? Pentanales, and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; (8) optionally one or more substituted or unsubstituted pentenales; (9) optionally one or more substituted or unsubstituted 1, 6-hexanediols; (10) optionally one or more substituted 1, 5-pentanediols; (11) optionally one or more substituted 1,4-butanediols; and (12) one or more substituted or unsubstituted butadienes; where the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6), (7), (8), (9), ( 10) and (11) is greater than about 0.1; and the weight ratio of the component (12) to the sum of the components (1), (2), (3), (4), (5), (6), (7), (8), (9) ), (10) and 11, is from about 0 to about 100; or a composition comprising: (1) one or more substituted or unsubstituted 1, 6-hexanediols; (2) optionally one or more substituted or unsubstituted penten-1-ols; (3) optionally one or more substituted or unsubstituted 6-hydroxyhexanals; (4) optionally one or more substituted or unsubstituted 5-hydroxypentanals, and / or the cyclic lactol derivatives thereof; (5) optionally one or more substituted or unsubstituted 4-hydroxybutanales, and / or the cyclic lactol derivatives thereof; (6) optionally one or more substituted or unsubstituted pentan-1-oles; (7) optionally one or more substituted or unsubstituted valeraldehydes; and (8) optionally one or more substituted or unsubstituted pentenales; wherein the weight ratio of the component (1) to the sum of the components (2), (3), (4), (5), (6) and (7) is greater than about 0.1; and the weight ratio of component (8) to the sum of components (1), (2), (3), (4), (5), (6) and (7) is from about 0 to about 100; a composition comprising: (1) one or more substituted or unsubstituted 1, 6-hexanediols; (2) one or more substituted or unsubstituted penten-1-oles; (3) optionally one or more substituted or unsubstituted 6-hydroxyl hexanals; (4) optionally one or more substituted or unsubstituted 5-hydroxyspinals, and / or the cyclic lactol buffers thereof, (5) optionally one or more substituted or unsubstituted 4-hydroxysubstituted butanales, and / or the cyclic lactol derivatives thereof; and (6) optionally one or more substituted or unsubstituted valeraldehydes; wherein the weight ratio of the component (1) to the sum of the components (3), (4), (5) and (6) is greater than about 0.1; and the weight ratio of the component (2) to the sum of the components (1), (3), (4), (5) and (6) is from about 0 to about 100.

16, A process to produce one or more 1,6-hexanediols substituted or unsubstituted comprising. (a) subjecting one or more substituted or unsubstituted alkadienes to hydrocarbonylation, in the presence of a hydrocarbonylation catalyst and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted unsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1-ols; (b) optionally separating the 3-penten-1-oles, 4-penten-1-ol and / or 2-penten-1-oles from the hydrocarbonylation catalyst: and (c) subjecting one or more substituted or unsubstituted alcohols , unsaturated comprising 3-penten-l-oles, 4-penten-l-ol and / or 2-penten-l-oles to hydrocarbonylation, in the presence of a hydrocarbonylation catalyst and a promoter and optionally a coordinating group to produce one or more substituted or unsubstituted 1, 6-hexanediols.

17. a process for producing one or more substituted or unsubstituted 1,6-hexanediols, comprising: (a) subjecting one or more substituted or unsubstituted alkadienes to hydrocarbonylation, in the presence of a hydrocarbonylation catalyst and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted unsaturated alcohols comprising 3-penten -l-oles, 4-penten-l-ol and / or 2-penten-l-oles; (b) optionally removing the 3-penten-1-ols, 4-penten-1-ol and / or 2-penten-1-ols, from the hydrocarbonylation catalyst; (c) optionally subjecting the 2-penten-l-oles and / or 3-penten-l-oles to isomerization, in the presence of a homogeneous or heterogeneous olefin Isomerization catalyst to partially or completely isomerize the 2-penten-1- oles and / or 3-penten-l-oles in 3-penten-l-oles and / or 4-penten-1-ol; and (d) subjecting one or more of the substituted or unsubstituted unsaturated alcohols comprising 2-pen-1-ols, 3-penten-1-ols and / or 4-penten-1-ol to hydrocarbylation, in the presence of an hydrocarbonylation catalyst and a promoter and optionally a free coordinating group, in order to produce one or more substituted or unsubstituted 1,6-hexanediols.

18. A reaction mixture comprising one or more substituted or unsubstituted 1,6-hexanediols wherein the reaction mixture is prepared by the process of claims 1, 2, 3 and 4.

19. The process of claims 1 , 2, 3 and 4 which further comprises the step of deriving one or more of the substituted or unsubstituted 1, 6-hexanediols wherein the derivatization reaction comprises cyclization, dehydration, cyclocarbonylation, carboesterification, hydrogenation, esterification, etherification, amination , alkylation, dehydrogenation, reduction, acylation, condensation, carboxylation, carbonylation, oxidation, silylation and permissible combinations thereof.

20. A derivative of one or more of the substituted or unsubstituted 1,6-hexanediols of claim 19.