CN1795164A - Process for the carbonylation of a conjugated diene - Google Patents

Abstract

A process for the carbonylation of a conjugated diene, comprising reacting a conjugated diene with carbon monoxide and a co-reactant having active hydrogen atoms in the presence of a catalyst system, wherein the catalyst system comprises: a palladium source; and (b) a bidentate diphosphine ligand of formula (II): r¹R²＞P¹R³ _m－R－R⁴ _n－P²＜R⁵R⁶In which P is¹And P²Represents a phosphorus atom; r¹、R²、R⁵And R⁶Independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which each group is attached to the phosphorus atom; r³And R⁴Independently represent the same or different optionally substituted methylene groups; r represents a divalent bridging group C¹－C²Wherein R is connected to R through said divalent bridging group³And R⁴The above step (1); m and n independently represent a natural number of 0 to 4, wherein the carbon atom C surrounding the bridging group is at a temperature in the range of 0 to 250 DEG C¹－C²Is restricted from rotating, and wherein, by C¹、C²And in P¹Directionally directly connected to C¹The plane occupied by the triatomic sequence of atoms of and a group consisting of C¹、C²And in P²Directionally directly connected to C²The dihedral angle between the planes occupied by the three atomic sequences of atoms is in the range of 0-120 degrees; and a source of anions.

Description

The carbonylation method of conjugated diolefine

The present invention relates to the carbonylation method of conjugated diolefine.The carbonylation reaction of conjugated diolefine is well-known in the art.In this manual, term " carbonylation " is meant in the presence of carbon monoxide and co-reactant, the reaction that the catalysis of conjugated diolefine by transition metal complex takes place.In the method, carbon monoxide and co-reactant join in the diolefine, described in WO-A-03/031457.

Be generally used under the condition of carbonylation, conjugated diolefine also may form dipolymer and/or telomer, and for example WO-A-03/040065 is described.This side reaction is extremely undesirable, because it can reduce the yield of target carbonylation product.Selectivity to carbonylation product is better than also being called as chemo-selective in this article to telomerizing product selectivity.

Except needs reached high as far as possible chemo-selective, also wishing to realize had extra high selectivity to a kind of in the some kinds of possible isomery carbonylation products, and this also is called as regioselectivity in this article.Carbonylation for conjugated diolefine, often wish regioselectivity to linear product, promptly the reaction that takes place had regioselectivity on primary carbon atom, because branched product does not have industrial use usually, linear product then is important intermediate, for example is used for the synthetic hexanodioic acid derivative that is used in polymeric amide.

WO-A-03/031457 discloses a kind of carbonylation method of conjugated diolefine, wherein, conjugated diolefine and carbon monoxide and have the compound of active hydrogen (mobile hydrogen) atom such as hydrogen, water, alkohol and amine react in the presence of catalyst system, wherein said catalyst system is based on (a) palladium cationic source, (b) phosphorus-containing ligand of formula (I):

Q ¹＞P-(CH ₂) _n-PQ ²Q ³ (I)

Wherein, Q ¹Be divalent group, it represents 2-phospha-adamantane group or derivatives thereof unsubstituted or that replace with the phosphorus atom that it connected, and one of them or several carbon atom are substituted Q by heteroatoms ²And Q ³Expression has the univalent perssad of 1-20 atom or jointly represents to have the divalent group of 2-20 atom independently, and n is 4 or 5 and its mixture.

Although show generally speaking high activity, the catalyzer of describing among the WO-A-03/031457 only provides limited chemo-selective and low yield.Disclosed carbonylation reaction generates some kinds of possible isomerized products mixtures, therefore not open regioselectivity of reacting in WO-A-03/031457.In addition, described method need use a large amount of palladiums and part reaching gratifying at least turnover number (turnover numbers), and this makes this method running cost height.In addition, the product mixtures that obtains need carry out suitable purification and/or will realize by product and the separating of part residuum, and this is undesirable in Industrial processes.

Therefore, also need to provide a kind of catalyst system, it can have higher chemo-selective and the higher regioselectivity for linear carbonylation product concurrently, can also obtain high turnover number and yield simultaneously, and can use more a spot of palladium to increase the total efficiency of method.This combination also will be avoided having to product mixtures is carried out suitable purifying, to remove the operation that telomerizes with polymeric by-products and nonlinearity product.

Have been found that now that in the presence of the different catalyst system of the following stated above-mentioned conjugated diolefine of mentioning and the carbonylation method that has between the co-reactant of at least one active hydrogen atom can carry out very effectively.

Summary of the invention

Therefore, the invention provides a kind of carbonylation method of conjugated diolefine, it comprises that the co-reactant that makes conjugated diolefine and carbon monoxide and have active hydrogen atom reacts in the presence of a kind of catalyst system, and wherein said catalyst system comprises:

(a) palladium source; With

(b) the bidentate diphosphine part of formula (II):

R ¹R ²＞P ¹-R ³ _m-R-R ⁴ _n-P ²＜R ⁵R ⁶ (II)

Wherein:

P ¹And P ²The expression phosphorus atom;

R ¹, R ², R ⁵And R ⁶Represent the organic group that includes tertiary carbon atom of identical or different optional replacement independently, wherein each group is connected on the phosphorus atom by described tertiary carbon atom;

R ³And R ⁴The methylene group of representing identical or different optional replacement independently;

R represents to comprise bivalent bridging group C ¹-C ²Organic group, wherein, R is connected to R by described bivalent bridging group ³And R ⁴On;

M and n represent the natural number of 0-3 independently,

Wherein, in 0-250 ℃ temperature range, around the carbon atom C of bridging group ¹-C ²Between the rotation of key be restricted and wherein, by C ¹, C ²With at P ¹Be directly connected to C on the direction ¹On the occupied plane of three atomic serieses formed of atom, and by C ¹, C ²With at P ²Be directly connected to C on the direction ²On the occupied plane of three atomic serieses formed of atom between interfacial angle in 0-120 degree scope; With

(c) negative ion source.

In the method according to the invention, the palladium source of suitable component (a) comprises metallic palladium and its title complex or compound, as palladium salt, such as the salt of palladium and hydracid, nitric acid, sulfuric acid or sulfonic acid; Palladium complex, as with the title complex of carbon monoxide or acetylacetonate, perhaps with the palladium of solid material such as ion-exchanger combination.Preferably, use the salt of palladium and carboxylic acid, suitable is to have carboxylic acid such as acetate, propionic acid and butyro-salt, the perhaps salt of carboxylic acid of Qu Daiing such as trichoroacetic acid(TCA) and trifluoroacetic acid up to 12 carbon atoms.Very suitable palladium source is acid chloride (II), or corresponding to the palladium salt (II) of the acid of diene substrate carbonylation product as being under the situation of substrate at 1,3-butadiene, be pentenoic acid palladium (II).

Bidentate diphosphine part (b) has the structure of formula (II), wherein in range of reaction temperature, around C ¹And C ²Between the rotation of key be restricted and wherein, by C ¹, C ²With at P ¹Be directly connected to C on the direction ¹On the occupied plane of three atomic serieses formed of atom, and by C ¹, C ²With at P ²Be directly connected to C on the direction ²On the occupied plane of three atomic serieses formed of atom between interfacial angle in 0-120 degree scope.

The definition of term " key " and " rotation " is referring to the organic chemistry of Hendrickson, Cram and Hammond, the third edition,, 175-201 page or leaf in 1970.According to the present invention, the rotation meaning refers to be connected respectively to C ¹And C ²On atom around C ¹And C ²Between the central shaft rotation of key.

When spinning obstacle is so low so that can not observe different forms in the time range of experiment the time, be known as " freedom " around the rotation of a key.Key group on every side can be observed above-mentioned phenomenon owing to existing abundant big spinning obstacle to make in the experimental period scope, this group to the rotation inhibition be known as be obstructed the rotation or restricted rotation (as IUPACCompendium of Chemical Terminology, second edition (1997), definition in 68,2209).

Suitable experiment can be ¹The H-NMR-experiment, referring to for example Hendrickson, the organic chemistry of Cram and Hammond, the 3rd edition, 1970, the nuclear magnetic resonance spectrometry of 265-281 page or leaf and F.A.Bovey, (New York, academic press, 1969), described in the 1-20 page or leaf, condition is to have hydrogen atom in part, and they will be owing to being subjected to C ¹And C ²Between key influence and show suitable displacement.

According to the present invention, in the temperature range of carrying out the inventive method, around C ¹And C ²Between key do not exist freely and rotate.Described temperature range can be 0 ℃-250 ℃ usually, but preferably present method is carried out in 10 ℃ of-200 ℃ of scopes, also more preferably at 15-150 ℃, even more preferably 18-130 ℃.

Therefore, in the temperature range of the inventive method, around the C of bitooth ligand ¹-C ²The rotation of key is hindered or is limited.Suitable is to measure described rotation at ambient temperature.

Bridging group R comprises two optional carbon atom C that replace ¹And C ²Chain.These two carbon atom C ¹And C ²Form R ¹R ²P ¹-R ³ _m-with-R ⁴ _n-P ²R ⁵R ⁶Between direct cross structure, thereby make phosphorus atom P ¹And P ²And the optional methylene group R that replaces ³And R ⁴By described bridging group C ¹-C ²Be connected to form diphosphine ligand (b).

Although have many different limited forms for part of the present invention, we find that specific interfacial angle is very important for the activity of catalyst system.Interfacial angle is generally defined as the angle that formed by two intersecting planes.The method according to this invention, interfacial angle are that four atomic serieses are (at P ¹Be directly connected to C on the direction ¹On atom)-C ¹-C ²-(at P ²Be directly connected to C on the direction ²On atom) in by following two angles that the plane forms, that is, and by three atom C ², C ¹With at P ¹Be directly connected to C on the direction ¹On the occupied plane of three atomic serieses formed of atom, and by three atomic series C ¹, C ²With at P ²Be directly connected to C on the direction ²On the angle that forms, the occupied plane of atom, it is in 0-120 degree scope.Herein " at P ¹Or P ²On the direction " looking like is meant that relevant atom is positioned at and connects C respectively ¹-P ¹Or C ²-P ²The part chain in that part.

For example, equal at m and n under 1 the situation, interfacial angle is four atomic series R ³-C ¹-C ²-R ⁴In by three atomic series R ³-C ¹-C ²Occupied plane is with four atomic series R ³-C ¹-C ²-R ⁴In other three atom C ¹-C ²-R ⁴Angle between the occupied plane.Each plane all is understood that by the central point of atom separately.

M and n should equal under 0 the situation in formula (II), and four atomic serieses will correspondingly be P ¹-C ¹-C ²-P ², two planes will be defined as P ¹-C ¹-C ²And C ¹-C ²-P ²

In the part according to the inventive method, interfacial angle is in 0-120 degree scope as defined above.Because can therefore obtain the catalytic activity of higher catalyst system, so interfacial angle is preferably in 0-70 degree scope, also more preferably in 0-15 degree scope, most preferably in 0-5 degree scope.

Do not wish to be entangled in any specific theory, believe, make around C ¹-C ²Between key rotation part not too can with palladium in be formed centrally the bidentate complex of stable configuration.Therefore, bidentate complex may be competed with the monomer title complex, thereby is reduced in the steric strain on the metal complexes, and therefore reduces the catalytic activity of title complex.

The where the shoe pinches that obtains stablizing bidentate complex also shows, for a large amount of catalytic activity title complex that obtains suiting need increase the amount of part and under reaction conditions the unstable of part higher.

As existing in or the aromatic substance unsaturated, at C at olefinic ¹And C ²Between the key that forms can be saturated or unsaturated link(age).Connect C at saturated bond ¹And C ²Situation under, R can be expressed as C ¹R ' R " C ²R R " ", therefore, bidentate diphosphine part according to the present invention has the feature of formula III aptly:

R ¹R ²P ¹-R ³ _m-C ¹R′R″-C ²RR″″-R ⁴ _n-P ²R ⁵R ⁶ (III)

Have only one to be hydrogen among in this embodiment, R ' and the R ", and the organic group of R and R " " expression hydrogen or identical or different optional replacement, condition is R ' and R " in have only one and R and R " ".If C ¹And C ²Connect by ethylenical unsaturated double bonds, then C ¹And C ²Can't rotate freely.In this case, R can be expressed as C ¹R '=C ²R ", therefore, bidentate diphosphine part according to the present invention has the feature of formula IV aptly:

R ¹R ²P ¹-R ³ _m-C ¹R′＝C ²R″-R ⁴ _n-P ²R ⁵R ⁶ (IV)

If C ¹And C ²Between key be ethylenic unsaturated bond, then pass through C ¹And C ²Connect P ¹And P ²The part chain can have two kinds of isomeric form, transconfiguration and cis-configurations in principle.According to above-mentioned definition, in transconfiguration, interfacial angle is about 180 degree, and in cis-configuration, interfacial angle is about 0 degree.

Substituent R among formula III or the IV ' to R " " itself can be an independent substituent, therefore only by carbon atom C ¹And C ²Be connected to each other, or preferably also have a connection at least.Described substituting group may further include carbon atom and/or heteroatoms.

The restriction of freely rotating is normally passed through to form at ambient temperature,, hinder around C under preferred 15-150 ℃ the temperature range more preferably at 0-250 ℃ ¹-C ²The bridging group C of the part of the molecular structure of key rotation ¹-C ²Realize.This molecular structure can be usually, for example, a) ethylenical unsaturated double bonds, wherein rotation is subjected to π favourable aspect energy-key eclipsed obstruction, and/or b) cyclic hydrocarbon group structure, wherein rotation because substituent R ' to the steric interaction of R " " or owing to the steric strain that ring texture caused that forms together to R " " by R ', or by the combination of above-mentioned factor, such as in aromatics or non-aromatics ring texture and be restricted.Structural stability and the rigidity that therefore produces also can be passed through c) realize, that is, if substituent R ' and R ", and/or R and R " " even if character feasiblely be not connected to each other, they also can hinder around C ¹-C ²The rotation of key for example hinders around C by strong steric interaction ¹-C ²The words of the rotation of key.In order to reach this purpose, preferred, in formula III or IV, R ' is a hydrogen to the middle none of R " ".

The preferably optional cyclic hydrocarbon group structure that is replaced by heteroatoms of R, also more preferably aliphatics or aromatic hydrocarbyl structure.This structure can be the part of the optional saturated or unsaturated polynuclear plane that further replaces, and it is also chosen wantonly can comprise heteroatoms such as nitrogen, sulphur, silicon or Sauerstoffatom.

Suitable structure R comprises, for example cyclohexane of Qu Daiing, tetrahydrobenzene, cyclohexadiene, and the pentamethylene of replacement, cyclopentenes or cyclopentadiene, all these can be chosen wantonly and comprise heteroatoms such as nitrogen, sulphur, silicon or Sauerstoffatom, and prerequisite is around C ¹-C ²The rotation of key is restricted, and interfacial angle and does not exist around by C within 0-120 degree scope ¹And C ²The rotation of the key that forms is a situation about being caused by conformational change, for example at height-limited ethylidene ether structure as 2,2-dimethyl-1 is in the 3-dioxolane.

In an especially preferred embodiment, R represents divalence multi-ring alkyl ring texture.Why preferred especially this many cyclic groups are, is because it has the structural stability of height, therefore, and around C ¹And C ²Between key freely rotate the restriction that has been subjected to height.The example of this particularly preferred hydrocarbyl group comprises norcamphyl, the norbornadiene base, different norcamphyl, dicyclopentadienyl, octahydro-4,7-methylene-1H-indenes methyl, α-and β-pinyl and 1,8-volatile oil extracted from eucalyptus' leaves or twigs alcohol radical, all these can be chosen wantonly and be substituted, or comprise heteroatoms as defined above.

May have at bitooth ligand under the situation of chiral centre, might be R, R-, S, S-or R, any in the S-meso-form, or its mixture.Meso-form and racemic mixture can use for two kinds, and condition is that interfacial angle is within 0-120 degree scope.

In the diphosphine of formula II, R preferably represents the optional divalent aryl that replaces, and it passes through radicals R ³And R ⁴Be connected on the phosphorus atom.

Because the rigidity of this aromatics ring texture and its interfacial angle in 0-5 degree scope, are preferred therefore generally.

Described aryl can be a monocyclic groups, for example phenyl, or many cyclic groups, for example naphthyl, anthryl or indyl.Preferably, aryl R only comprises carbon atom, but R can represent that also wherein carbochain is by one or more heteroatomss, such as the aryl of nitrogen, sulphur or Sauerstoffatom interruption, as pyridine, pyrroles, furans, thiophene, oxazole or thiazolyl group.Most preferably aryl R represents phenyl or naphthylidene group.

Optional, described aryl replaces.Suitable substituting group comprises and contains heteroatomic group, such as halogen, and sulphur, phosphorus, oxygen and nitrogen.This examples of groups comprises muriate, bromide, the group of iodide and following formula :-O-H ,-O-X ,-CO-X ,-CO-O-X ,-S-H ,-S-X ,-CO-S-X ,-NH ₂,-NHX ,-NO ₂,-CN ,-CO-NH ₂,-CO-NHX ,-CO-NX ₂With-CI ₃, wherein X represents the alkyl of 1-4 carbon atom independently, as methyl, and ethyl, propyl group, sec.-propyl and normal-butyl.

When aryl was replacement, it was preferably replaced by one or more aryl, alkyl or cycloalkyl groups that preferably have 1-10 carbon atom.Suitable group comprises methyl, ethyl, trimethylammonium, sec.-propyl, tetramethyl-and isobutyl-, phenyl and cyclohexyl.

But most preferably, described aryl is non-replacement, and only is connected to the R that is connected with phosphorus atom ³And R ⁴On the group.Preferably, on the consecutive position of aryl for example 1 with 2 on be connected alkylidene group.

Symbol m among formula II, III and the IV and n can represent the natural number in the 0-3 scope independently.If m and n are 0, phosphorus atom P so ¹And P ²Be directly connected to by carbon atom C ¹And C ²On the bridge that forms.If one among m or the n equals 0, so or C ¹, perhaps C ²To be directly connected to P ¹Or P ²On.Do not wish to be entangled in any specific theory, we believe, by C ¹And C ²The effect that this ad hoc structure of formed center bridge produces phosphorus atom, and the influence that therefore catalyst complexes is produced will be owing to the radicals R that has greater number ³And/or R ⁴And water down.Simultaneously, we believe, if m and n both equal 0, the distance between the phosphorus atom can be quite short so, thereby part is attached on the palladium central atom of catalyst complexes not too doughtily.

Therefore, because general good catalyst activity that this part produced, m preferably equals 0 or 1, and n is preferably in the scope of 1-3, more preferably 1-2, most preferably 1.

If the value of m and/or n is greater than 1, the radicals R of so some optional replacements ³And R ⁴With P ¹And P ²Be connected on the R.These may be identical or independent different groups.Therefore, R ³And/or R ⁴Lower alkylene groups (so-called lower alkylene groups is meant the alkylidene group that comprises 1-4 carbon atom) preferably.These alkylidene groups can replace, for example replaced by alkyl or heteroatoms, or unsubstituted, and can for example represent methylene radical, ethylidene, trimethylene, isopropylidene, tetramethylene, isobutylene and uncle's butylidene perhaps can be represented methoxyl group, oxyethyl group and similar group.Most preferably, R ³And/or R ⁴In at least one is a methylene group.

Suitable especially aromatic group comprises aromatic yl group, such as alkyl phenyl group such as the tolyl and the xylyl group of dibasic phenyl or naphthyl group and replacement.Because easily synthetic utilizability and the institute's good solvability of the catalyst complexes that forms in reaction medium, preferably tolyl and xylyl group, wherein the methylene radical substituting group on methylene radical substituting group or the aromatic nucleus plays radicals R ³And/or R ⁴Effect.Most preferably, C ¹And C ²Be the part of aromatic nucleus, and R ³And/or R ⁴In have at least an expression to be connected to annular atoms C ¹And C ²On methylene group.

Therefore, according to the present invention, particularly preferred part family is C wherein ¹And C ²It is the part of phenyl ring; M is 0 or 1; N is 1, R ³And R ⁴Be those parts of methylene group.In another particularly preferred part family, because easily synthetic utilizability, m and n equal 1.Therefore, this based on 1, the part of 2-two (phosphine methyl) benzene or 1-P-phosphino--2-(phosphine methyl)-phenyl group is particularly suitable for method of the present invention, and reason is the height rigidity of aromatics skeleton, synthesize utilizability easily and can obtain good result with resulting catalyst system.

Except skeleton structure, selectivity and activity that the direct part environment of phosphorus atom also is found for the inventive method have strong effect.Be used for the inventive method part, R ¹, R ², R ⁵And R ⁶Can represent the organic group that includes tertiary carbon atom of identical or different optional replacement independently, wherein each group is connected on the phosphorus atom by described tertiary carbon atom.

For the purposes of the present invention, term " organic group " expression unsubstituted or replacement, that have 1-30 carbon atom aliphatics, aromatics or araliphatic group, it is connected on the phosphorus atom by tertiary carbon atom, that is, carbon atom is linked on phosphorus and three dehydrogenations substituting group in addition by key.

Organic group R ¹, R ², R ⁵And R ⁶Can be univalent perssad, perhaps R independently of one another ¹And R ²Together and/or R ⁵And R ⁶Can be divalent group together.Described group can further comprise one or more heteroatomss such as oxygen, nitrogen, sulphur or phosphorus, and/or is replaced by one or more functional groups, comprises for example oxygen, nitrogen, and sulphur and/or halogen are for example replaced by fluorine, chlorine, bromine, iodine and/or cyano group.

Organic group R ¹, R ², R ⁵And R ⁶Can only be connected to each other, and preferably have 4-20 carbon atom, also more preferably 4-8 carbon atom by phosphorus atom.

Each group can be replaced by aliphatics, cyclic aliphatic or aromatic substituent by the described tertiary carbon atom that it is connected on the phosphorus atom, perhaps can form the part of the saturated of replacement or unsaturated aliphatic ring texture, all these can comprise heteroatoms, 1-adamantyl or derivatives thereof for example, wherein the carbon atom in the structure is substituted by Sauerstoffatom.Preferably, tertiary carbon atom is replaced by alkyl, thereby makes tertiary carbon atom become the part of tertiary alkyl groups, or is replaced by ether group.The example of suitable organic group is: the tertiary butyl, 2-(2-methyl) butyl, 2-(2-ethyl) butyl, 2-(2-phenyl) butyl, 2-(2-methyl) amyl group, 2-(2-ethyl) amyl group, 2-(2-methyl-4-phenyl) amyl group, 1-(1-methyl) cyclohexyl and 1-adamantyl group.

Although radicals R ¹, R ², R ⁵And R ⁶Can be different organic groups independently of one another, but owing in synthetic, use more a spot of different raw material, so radicals R ¹, R ², R ⁵And R ⁶The identical uncle's organic group of preferred expression.Also more preferably, radicals R ¹, R ², R ⁵And R ⁶The expression tertiary butyl or 1-adamantyl most preferably are tertiary butyl groups.Therefore, the present invention relates to such method, wherein R ¹, R ², R ⁵And R ⁶Represent tertiary butyl groups separately.Therefore, particularly preferred bidentate diphosphine is 1,2-two (two tert-butyl phosphine methyl) benzene (also being described to two [two ((tertiary butyl) phosphino-]-o-Xylol or dtbx part) and 2,3-two (di-t-butyl phosphine methyl) naphthalene.

Although use wherein radicals R ¹, R ², R ⁵And R ⁶Represent identical tertiary alkyl groups, obtained good result as the part of tertiary butyl groups, still, these parts obtain so be difficult to technical scale owing to need to use organometallics such as Grignard reaction thing.

Similarly, use wherein R ¹And R ²Together and/or R ⁵And R ⁶Represent that together the diphosphine ligand that is directly connected to the divalent group on the phosphorus atom by 2 tertiary carbon atoms has also obtained excellent results.This divalent group can have monocycle or polynuclear plane.The diphosphine that comprises inferior phosphorus atom that has this divalent group has following benefit, that is, they can obtain by relate to the different synthetic route that phosphine reacts under the condition of gentleness, and this makes their easier extensive acquisitions.Therefore, R ¹And R ²Together and/or R ⁵And R ⁶Also can represent the optional divalence cycloaliphatic groups that replaces together, wherein said cycloaliphatic groups is connected on the phosphorus atom by 2 tertiary carbon atoms.R ¹And R ²Together, and/or R ⁵And R ⁶Together, under each situation, all preferably the side chain cyclic, do not replaced or by divalent alkyl its replacement, that in alkylidene chain, contain 4-10 atom, wherein CH by heteroatoms ₂-group also can be by heteroatoms group, as-CO-,-O-,-SiR ₂-or-NR-substitutes, and wherein one or more hydrogen atoms can be substituted base, and for example aryl substitutes.

The example of preferred divalent group is C unsubstituted or that replace ₄-C ₃₀-alkylidene group, wherein, CH ₂-group can by heteroatoms group as-O-substitutes, it comprises 1,1,4,4-tetramethyl--Ding-1,4-two bases-, 1,4-dimethyl-1,4-dimethoxy-Ding-1,4-two bases-, 1,1,5,5-tetramethyl--penta-1,5-two bases-, 1,5-dimethyl-1,5-dimethoxy-penta-1,5-two bases-, 3-oxa--1,5-dimethoxy-penta-1,5-two bases-, 3-oxa--1,1,5,5-tetramethyl--penta-1,5-two bases-, 3-oxa--1,5-dimethyl-1,5-dimethoxy-penta-1,5-two bases-and similar divalent group.

The suitable especially R that comprises ¹And R ²Together, and/or R ⁵And R ⁶Single ring architecture together is, for example optional by heteroatoms replace 2,2,6, the quaternary phosphinan-4-ketone of 6-or-4-thioketones structure.The part that comprises this structure can obtain under mild conditions usually, referring to Welcher and Day, and Journal of Organic Chemistry, J.Am.Chem.Soc., 27 (1962), 1824-1827.

For example, has identical organic group R ¹, R ², R ⁵And R ⁶Bidentate diphosphine usually can be by making compound

H ₂P-(R ³) _m-C ¹R′R″-C ²RR″″-(R ⁴) _n-PH ₂

With compound

(Z ¹Z ²C)＝(CZ ³)-(C＝Y)-(CZ ⁴)＝(CZ ⁵Z ⁶)

Reaction obtains, wherein, and Z ¹, Z ², Z ⁵And Z ⁶The optional organic group that is replaced by heteroatoms of expression, Z ³And Z ⁴Optional organic group or the hydrogen that is replaced by heteroatoms of expression, and wherein Y represents oxygen or sulphur.An example of this compound is 2,6-dimethyl-2,5-heptadiene-4-ketone (also claim phorone, or sym.-diisopropylideneacetone).If use a plurality of compounds, then formation has the R of comprising ¹And R ²And comprise R ⁵And R ⁶Not isoplastic part.

Comprise R ¹And R ², and/or R ⁵And R ⁶Suitable polynuclear plane be for example on 1,3 and 5, to be substituted and (thereby to form tertiary carbon atom, by this atom, described group is connected on the inferior phosphorus atom) 2-phospha-three ring [3.3.1.1{3,7}] decyl group, or wherein one or more carbon atoms are by its derivative of heteroatoms alternate.Three ring [3.3.1.1{3,7}] decane more are commonly referred to as the systematic name of the compound of diamantane.Therefore, in whole specification sheets, 1,3,5-is trisubstituted-and 2-phospha-three ring [3.3.1.1{3,7}] decyl group or derivatives thereof will be called as " 2-PA " group (as 2-phospha-adamantane base group).

The 2-PA group is 1,3, on the one or more positions in 5, and optional also on 7 by 1-20 atom, preferred 1-10 carbon atom, also more preferably any monovalent organic radical of 1-6 carbon atom is rolled into a ball R ⁷Replace.R ⁷Example comprise methyl, ethyl, propyl group and phenyl.

More preferably, the 2-PA group is 1,3,5 with each position of 7 on all aptly by identical radicals R ⁷, more preferably by methyl substituted.The 2-PA group also preferably comprises other heteroatoms except that the 2-phosphorus atom at its skeleton.Suitable heteroatoms is oxygen and sulphur atom.Preferably is that these heteroatomss are on 6,9 and 10.Therefore, most preferred divalent group is a 2-phospha-1,3,5,7-tetramethyl--6,9,10-trioxa adamantyl group.

The bitooth ligand that is used for the inventive method can prepare described in WO01/68583 or following article: Chem.Commun., 2001,1476-1477 page or leaf (people such as Robert I.Pugh).Therefore, method of the present invention also relates to a kind of like this method, wherein, in the formula (II), R ¹And R ²Together and/or R ⁵And R ⁶Together for optional by heteroatoms replace 1,3, the part of the trisubstituted 2-phospha-adamantane structure of 5-, perhaps for optional by heteroatoms replace 2,2,6,6-is quaternary-part of phosphinan-4-ketone, perhaps for optional by heteroatoms replace 2,2,6,6-is quaternary-part of phosphinan-4-thioketones.

Described bitooth ligand can be made into meso and racemic form, and all these is fit to.

According to the present invention, particularly preferred diphosphine ligand is the compound according to formula (II), wherein R ¹And R ²Together, and R ⁵And R ⁶Together and phosphorus atom P separately ¹And P ²Form 2-phospha-1,3,5 together, 7-tetramethyl--6,9,10-trioxa adamantyl group, or 2,2,6,6-tetramethyl--phosphinan-4-ketone, and skeleton structure R wherein ³-C ¹-C ²-R ⁴Be α-phosphine tolyl, 1,2-xylyl or 2,3-naphthyl structure, that is, wherein, R ³, R ⁴Be methylene group, m is 1, and n is 0 or 1, C ¹-C ²Key is the part of phenyl ring, and is why preferred especially, and reason is can obtain good result with these parts; Most preferably the part in this embodiment is n and m those parts of equaling 1 wherein.

The bidentate diphosphine part that can be common in the inventive method is for example disclosing in the following file: WO-A-96/19434, WO-A-98/42717, WO-A-01/68583 and WO-A-01/72697, and comprise highly preferred ligand 1,2-P, P '-two (2-phospha-1,3,5,7-tetramethyl--6,9,10-trioxa three ring [3.3.1.1{3.7) decyl)-methylene radical-benzene (also is called 1 sometimes, 2-P, P '-two (2-phospha-1,3,5,7-tetramethyl--6,9,10-trioxa three rings [the 3.3.1.1{3.7} decyl)-o-Xylol) and 1,2-P, P '-two (2-phospha-1,3,5,7-tetraethyl--6,9,10-trioxa three ring [3.3.1.1{3.7} decyl]-methylene radical-benzene.

In WO-A-01/68583, a kind of method that is used to have the carbonylation of ethylenically unsaturated compounds of 3 or above carbon atom is disclosed, it be by making carbon monoxide and hydroxyl compound comprise catalyst system as described below in the presence of reaction realize:

(a) palladium source;

(b) as applied bidentate diphosphine in the inventive method and

(c) be not more than the negative ion source that 3 acid obtains by pKa value when in the aqueous solution, measuring under 18 ℃;

Described method is to carry out in the presence of aprotic solvent.According to WO-A-01/68583, preferred hydroxy-containing compounds is water and alkanol.It should be noted that the carbonylation of in this document, not mentioning conjugated diolefine.

Do not wish to be entangled in any specific theory, we believe, are not the alefinically unsaturated compounds and the conjugated diolefines of conjugated diolefine, the intermediate title complex at can experience in carbonylation reaction diverse and catalyst metal center.Conjugated diolefine according to the inventive method is considered to form π-allyl group-title complex with the metal center of catalyst complexes, and this intermediate title complex can further react.Rather than the alefinically unsaturated compounds of conjugated diolefine then can not form this π-allyl group-title complex.

Therefore, those of ordinary skill can not be diverted to the result who finds the carbonylation of conjugated diolefine in the carbonylation of the alefinically unsaturated compounds that does not have conjugated double bond, particularly just reactive, the regioselectivity of the chemo-selective and/or the product that forms.

Opposite with the above part that characterizes out, disclosed part does not have according to of the present invention the restricted rotation around the key that connects phosphorus atom among the WO-A-03/31457.Because the C of these parts ₄-and C ₅-alkylidene group skeleton, they will at room temperature show freely rotating around the dihedral axle, because exist the hydrogen substituting group to be considered to can between different possible forms, not produce big energy difference on the bridging atom, rotate under the condition of carbonylation reaction being generally used for to prevent part.

Palladium positively charged ion with respect to every mole, i.e. catalyst component (a), bidentate diphosphine, promptly the mol ratio of catalyst component (b) in the scope of 0.5-10, preferred 0.8-8, more preferably 1-5.

With wherein, R ¹And R ²Be only to pass through phosphorus atom organic group connected to one another independently of one another, and R ⁵And R ⁶Represent that together the bidentate diphosphine part that is connected to the divalent organic group on second phosphorus atom by two tertiary carbon atoms has also obtained good result.

This part that carries out asymmetric replacement on two phosphorus atom also had not been described before, and also nobody uses it in the catalyst composition of carbonylation reaction.Therefore, the invention still further relates to the bidentate diphosphine part of a kind of formula II,

R ¹R ²P ¹-(R ³) _m-R-(R ⁴) _n-P ²R ⁵R ⁶ (II)

Wherein,

P ¹And P ²The expression phosphorus atom;

R ¹And R ²The organic radical of representing optional replacement identical or different, that contain tertiary carbon atom independently, wherein each group is connected on the phosphorus atom by described tertiary carbon atom, and these groups are only by phosphorus atom P ¹Be connected to each other;

R ⁵And R ⁶Represent together to be connected to phosphorus atom P by tertiary carbon atom ²On organic divalent group;

R ³And R ⁴The organic group of representing identical or different optional replacement independently;

M and n represent the natural number of 0-3 independently.

Preferably, R ³And R ⁴It is the methylene group that replaces.

The present invention further provides the catalyst composition that comprises the following stated component: (a) group VIII source metal and (b) the bidentate diphosphine part of novel formula II, wherein P ¹And P ²The expression phosphorus atom; R ¹And R ²The organic group of representing optional replacement identical or different, that contain tertiary carbon atom independently, wherein each group is connected on the phosphorus atom by described tertiary carbon atom, and these groups are only by phosphorus atom P ¹Be connected to each other; R ⁵And R ⁶Represent together to be connected to phosphorus atom P by tertiary carbon atom ²On organic divalent group; R ³And R ⁴The organic group of representing hydrogen or identical or different optional replacement independently; M and n represent the natural number in the 0-3 scope independently.

Suitable group VIII metal comprises Pd, Pt and Rh, and preferred Pd and Pt, most preferably Pd is used for the carbonylation of conjugated diolefine.

All obtained excellent results with good grounds part of the present invention, if this proof is R ¹, R ²And R ⁵And R ⁶Be connected on separately the phosphorus atom by tertiary carbon atom, just can realize this total inventive concept of extra high reactivity and selectivity.

Although these novel parts can be used for several different methods, for example be used for alefinically unsaturated compounds, or preferably conjugated diolefine is carried out in the catalyst composition of carbonylation reaction,, as implied above, this purposes requires part should be cis-configuration.

Therefore, the invention still further relates to novel bidentate diphosphine part as implied above purposes at the catalyst system that is used for carbonylation of conjugated dienes, wherein, in described part, around C ¹And C ²Between the rotation of key be restricted at ambient temperature and wherein, by C ², C ¹With at P ¹Be directly connected to C on the direction ¹On the occupied plane of three atomic serieses formed of atom, and by C ¹, C ²With at P ²Be directly connected to C on the direction ²On the occupied plane of three atomic serieses formed of atom between interfacial angle in 0-120 degree scope.

This part is, 1-P-1 for example, 3,5,7-tetramethyl--1,3,5-trimethylammonium-6,9,10-trioxa-2-phospha three ring [3.3.1.1{3,7}] decyl-2-(di-t-butyl phosphine methyl) benzene.

Bidentate diphosphine, promptly catalyst component (b) is with respect to every mole of palladium, and promptly the mol ratio of catalyst component (a) is not crucial.Preferably, its in the 0.1-100 scope, more preferably 0.5-10.

But for preferred catalyzer, active substance is considered to based on the bidentate diphosphine part with respect to every mole of palladium equimolar amount.Therefore, with respect to the molar weight of every mole of palladium bidentate diphosphine part preferably in the 1-3 scope, more preferably 1-2, even more preferably 1-1.5.In the presence of oxygen, bigger a little amount may be useful.

Method of the present invention allows conjugated diolefine and carbon monoxide and co-reactant reaction.Conj ugated diene reactant has at least 4 carbon atoms.Preferably, diolefine has 4-20, more preferably 4-14 carbon atom.But in different preferred embodiments, described method also goes for those in its molecular structure, as comprise the molecule of conjugated double bond in such as elastomeric polymer chain.

Conjugated diolefine can be that replace or unsubstituted.Preferably, described conjugated diolefine is unsubstituted diolefine.The example of useful conjugated diolefine is a 1,3-butadiene, the conjugated pentadiene, and conjugated hexadiene, cyclopentadiene and cyclohexadiene, all these can replace.What have special commercial benefits is 1,3-butadiene and 2-methyl isophthalic acid, 3-divinyl (isoprene).

The raw material that comprises the diolefine reactant not necessarily must not contain the mixture with alkene, because carbonylation reaction of the present invention especially has selectivity for the diolefine raw material.Even, and up to 30mol%, preferably be in the raw material and also can stand up to the mixture of the alkynes of 5mol% based on the diolefine reactant.

The ratio of diolefine and co-reactant (v/v) can change in very wide scope in the raw material, and suits 1: 0.1-1: in 500 scopes.

According to the present invention, co-reactant can be any compound that has active hydrogen atom and can react under catalysis as nucleophilic reagent and diolefine.The character of co-reactant is determining the type of formed product to a great extent.Suitable co-reactant is a water, carboxylic acid, alcohol, ammonia or amine, mercaptan, or its combination.Because co-reactant is a water, so the product that obtains will be an ethylenically unsaturated carboxylic acids.When co-reactant is carboxylic acid, just obtain the ethylenic unsaturated acid acid anhydride.For pure co-reactant, carbonylation product is an ester.Similarly, use ammonia (NH ₃) or uncle or secondary amine RNH ₂" NH will generate acid amides to or R ' R, and use mercaptan RSH will generate thioesters.In the co-reactant of above definition, R, R ' and/or R " optional organic radical, preferred alkyl, thiazolinyl or the aryl that is replaced by heteroatoms of expression.When using ammonia or amine, the sub-fraction of these co-reactants will with the acid-respons that exists, form acid amides and water.Therefore, under the situation of ammonia or amine-co-reactant, always have water and exist.

Preferably, carboxylic acid co-reactant has with the diolefine reactant and adds 1 identical carbonatoms.

Preferred pure co-reactant is that per molecule has 1-20, and more preferably the alkanol of 1-6 carbon atom and per molecule have 2-20, more preferably the alkanediol of 2-6 carbon atom.Alkanol can be aliphatic, cyclic aliphatic or aromatics.In the method for the invention, suitable alkanol comprises methyl alcohol, ethanol, ethylene glycol, n-propyl alcohol, 1, ammediol, Virahol, the 1-butanols, 2-butanols (second month in a season-butanols), 2-methyl isophthalic acid-propyl alcohol (isopropylcarbinol), 2-methyl-2-propyl alcohol (trimethyl carbinol), the 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols (primary isoamyl alcohol), 2-methyl-2-butanols (tertiary amyl alcohol), n-hexyl alcohol, 2-hexanol, 4-methyl-2-amylalcohol, 3,3-dimethyl-2-butanols, 1-enanthol, the 1-octanol, 1 nonyl alcohol, 1-decanol, 1 and 1, ammediol, wherein owing to can obtain high turnover number and because the special purposes of the product that forms, most preferably methyl alcohol.

Preferred amine per molecule has 1-20, more preferably 1-6 carbon atom, and it is individual that the diamines per molecule has 2-20, more preferably 2-6 carbon atom.Described amine can be aliphatic, cyclic aliphatic or aromatics.Owing to can obtain high turnover number, therefore, more preferably ammonia and primary amine.Negatively charged ion in catalyst system (c) is under the situation of acid, and preferred, the amount of ammonia or amine is lower than the chemical equivalent based on the amine functionality.Unintentionally, when being primary amine when co-reactant is ammonia and under a few cases, the acid of existence will be reacted and be formed acid amides, discharge water outlet.Therefore, also have the acid that is formed by conjugated diolefine, carbon monoxide and water on a small quantity all the time, this acid replaces being converted into by aforesaid direct reaction the acid of acid amides subsequently.

Described mercaptan co-reactant can be aliphatic, cyclic aliphatic or aromatics.Preferred mercaptan co-reactant is that per molecule has 1-20, and more preferably the aliphatics mercaptan of 1-6 carbon atom and per molecule have 2-20, more preferably aliphatics two mercaptan of 2-6 carbon atom.

Negative ion source (c) can be any negative ion source that is suitable for this reaction of catalysis.But described negative ion source is acid preferably, more preferably carboxylic acid, and it both can play the effect of promoter component (c), can be used as reaction solvent again.Again, more preferably, described negative ion source is that the pKa value is higher than the acid of 2.0 (measuring) under 18 ℃ in the aqueous solution, and also more preferably catalyst component (c) is that the pKa value is higher than 3.0 acid, even more preferably the pKa value is higher than 3.6.

The example of preferred acid comprises acetate, propionic acid, and butyric acid, valeric acid, pentenoic acid and n-nonanoic acid, back three is highly preferred, because we find that their low polarity and high pKa value can increase the reactivity of catalyst system.Be to use to be equivalent to react the acid of target product extremely easily as catalyst component (c).In conjugated diolefine is under the situation of 1,3-butadiene, preferred especially pentenoic acid.Catalyst component (c) also can be carboxylic ion exchange resin.This helps simplifying the purifying of product mixture.

Negative ion source and palladium, promptly catalyst component (c) and mol ratio (b) are not crucial.But because the activity of enhanced catalyst system, it suits 2: 1-10 ⁷: between 1, more preferably 10 ²: 1-10 ⁶: 1, also more preferably 10 ²: 1-10 ⁵: 1, most preferably 10 ²: 1-10 ⁴: 1.Therefore, if co-reactant will with the acid-respons that plays the negative ion source effect, the selection of acid and the amount of co-reactant will make and have an amount of free acid so.Usually, owing to can improve speed of reaction, therefore preferred, the acid amount is superfluous greatly with respect to co-reactant.

The consumption of catalyst system is not crucial completely, and can change in very wide scope.Usually, use for every mole of conjugated diolefine, consumption is 10 ^-8-10 ^-1, preferred 10 ^-7-10 ^-2The palladium atom of mole is preferably at every mole 10 ^-5-10 ^-2In the grammeatom scope.This method can be chosen wantonly in the presence of solvent and carry out, but preferred, and the described acid of playing component (c) effect is used as solvent and promotor.

According to the present invention, carbonylation reaction carries out under moderate moisture and pressure.Suitable temperature of reaction is 0-250 ℃, more preferably 50-200 ℃, and also more preferably 80-150 ℃.

Reaction pressure is at least normal atmosphere usually.Suitable pressure is 0.1-15 MPa (1-150 crust), preferred 0.5-8.5MPa (5-85 crust).Preferably, the branch of carbon monoxide is pressed in 0.1-8MPa (1-80 crust) scope, is limited to 4-8MPa on more preferably.High pressure need provide specialized apparatus.

In the method according to this invention, carbon monoxide can use with pure form, perhaps uses such as the rare gas element of nitrogen, carbonic acid gas or such as the rare gas element of argon gas or such as the coreaction gas dilution of ammonia.

In addition, add limited amount hydrogen,, can promote carbonylation reaction as the 3-20mol% of used CO content.But, use more substantial hydrogen then to tend to take place the hydrogenation of undesirable diolefine reactant and/or unsaturated carboxylic acid product.

Method of the present invention has additional advantage,, except the reaction of wherein using ammonia or amine co-reactant or halogen-containing co-reactant, does not need nitrogenous compound or halogen contained compound that is.Therefore, the product that obtains is substantially free of nitrogenous impurity or halogen-containing impurity.

In addition, only comprise in the dicarboxylic acid product composition a spot of side chain dicarboxylic acid product isomer (as, under the situation of hexanodioic acid product composition, Alpha-Methyl pentanedioic acid and/or α-ethyl succinic acid), the halogen-containing impurity that preferably is lower than the nitrogenous impurity of 1.5ppmw and is lower than 1.5ppmw, also more preferably nitrogenous impurity is lower than 0.1ppmw, most preferably is lower than 1ppbw and halogen-containing impurity is lower than 1ppbw.When 1, when the 3-divinyl takes place to transform, described hexanodioic acid product composition can be advantageously used in the synthesizing polyamides product, reason is that it comprises the pentanedioic acid that is lower than 1.5ppmw and/or each in the Succinic Acid really, with because astoundingly, the a small amount of Alpha-Methyl pentanedioic acid that exists in the product composition and/or α-ethyl succinic acid can not produce tangible problem in manufacturing processed, and may advantageously reduce the melt temperature of polymkeric substance and its other physicals is not caused passive influence.Therefore, the hexanodioic acid product preferably comprises the pentanedioic acid that is lower than 0.1ppmw and/or each in the Succinic Acid, more preferably less than the pentanedioic acid of 1ppbw and/or each in the Succinic Acid.Therefore, the present invention also preferably relates to can be by the carbonylation product composition of method acquisition of the present invention, wherein said product composition comprises Alpha-Methyl pentanedioic acid and/or α-ethyl succinic acid and is lower than the nitrogenous impurity of 1.5ppmw, is lower than the halogen-containing impurity of 1.5ppmw and is lower than the pentanedioic acid of 1.5ppmw and/or each in the Succinic Acid.

The present invention will describe by following indefiniteness embodiment.

Embodiment 1:1-P-(1,3,5,7-tetramethyl--6,9,10-trioxa-2-phospha three ring [3.3.1.1{3,7}] decyls)-2-[di-t-butyl-phosphine methyl] preparation of benzene part

8.25 gram (33 mmole) the 2-bromobenzyl bromide and 5 gram (34.2 mmole) the di-t-butyl phosphines that will be in 40 milliliters of degassing acetonitriles are metered in 100 milliliters of glass reactors that are under the inert atmosphere, stir at ambient temperature then 12 hours.Afterwards, the vacuum removal acetonitrile adds 30 milliliters of degassed toluenes, 30 milliliters of de aerated waters and 7.5 milliliters of triethylamines.Adding 10 milliliters of ethanol in this mixture is separated with improvement.When being separated, isolate the upper strata and the evaporate to dryness that contain toluene.Residuum is 9 gram (28.6 mmoles, 87%) (2-benzyl bromide) (di-t-butyl) phosphines, light yellow oil, ³¹Be presented among the P NMR+resonance peak at 34.16ppm place.

2-benzyl bromide-(di-t-butyl) phosphine that 2.5 grams (7.9 mmole) obtain like this, 2.24 gram DABCO (20 mmole), 1.94 grams 1,3,5-trimethylammonium-4,6,9-trioxa-2-phospha three ring-[3.3.1.1{3,7}] decane (9 mmole) and 0.23 gram Pd (PPh ₃) ₄(0.2 mmole) and 10 milliliters of toluene join in 250 milliliters of Glass Containerss that are in the inert atmosphere, and the content in the container under agitation is heated to 140 ℃, heat 12 hours.Make reaction mixture be cooled to 100 ℃, filter then.With the filtrate cool to room temperature, add 30 ml methanol then, and mixture cooling 12 hours to-35 ℃, isolate 1-P-(1,3,5,7-tetramethyl--6,9,10-trioxa-2-phospha three ring [3.3.1.1{3,7}] decyls)-2-[di-t-butyl-phosphine methyl] benzene, yellow crystals (2.2 grams, 4.9 mmole, 62%), can pass through ³¹Among the P NMR+38.08 and-38.96ppm place shows two distinct resonance signals and obtains sign.This part also will be called as α-dtb-2-pa-tolyl part in the present invention, and expression meets the part of formula II, R=aryl wherein, and m=0, n=1, its interfacial angle are approximately 0 degree.

The carbonylation reaction at intermittence of embodiment 2-18 and comparative example A-D-divinyl and water

In 250 milliliters that make by HASTELLOY C (HASTELLOY C the is a trade mark) autoclaves that magnetic agitation arranged, the acid of packing into continuously and measuring shown in the Table I down, 5 ml waters, 0.1 mmole acid chloride, part separately, wherein (unit is a mmole) shown in the following Table I of amount of ligand.

In embodiment 2-13 and embodiment 18, part is 1, two (di-t-butyl phosphine methyl) benzene of 2-(also be called as dtbx, meet formula (II), wherein R equals benzene, and m=n=1, interfacial angle are about 0 degree); In embodiment 14, part is 2, two (di-t-butyl-phosphine methyl) naphthalenes of 3-(also be called as dtbn, meet formula (II), wherein R equals naphthalene, and m=n=1, interfacial angle are about 0 degree); In embodiment 15, part is 1-P-(1,3,5,7-tetramethyl--6,9,10-trioxa-2-phospha-three ring [3.3.1.1{3,7}] decyl)-2-[di-t-butyl phosphine methyl] benzene (α that in embodiment 1, obtains-pa-2-dtb-tolyl part; Meet formula (II), wherein R equals benzene, and m=0, n=1, interfacial angle are about 0 degree); In embodiment 16 and 17, part is 1,2-pair (P, P '-(1,3,5,7-tetramethyl--6,9,10-(2-phospha trioxa three ring [3.3.1.1{3,7}] decyls) toluene (also is called as 1,2-bpa-o-Xylol ylidene ligands; Meet formula (II), wherein R equals benzene, and m=n=1, interfacial angle are about 0 degree).In embodiment 18, substrate is 2-methyl butadiene (isoprene) rather than divinyl.

In the comparative example A, part is that 3-(di-t-butyl phosphine)-2-(di-t-butyl phosphine methyl)-1-propylene (does not meet requirement of the present invention; Around C ¹-C ²The rotation of key is not restricted); In Comparative Examples B, part is 1, and 2-two (9-phospha dicyclo [3.3.1] nonyl) ethane (does not meet requirement of the present invention; Around C ¹-C ²The rotation of key is not restricted, and does not have uncle's substituting group on the phosphorus atom); In Comparative Examples C, part is 1, and two (di-t-butyl phosphine) acetone of 3-(do not meet requirement of the present invention; Around C ¹-C ²The rotation of key is not restricted); In Comparative Examples D, part is 1, and two (dicyclo-hexyl phosphine methyl) benzene of 2-(do not meet requirement of the present invention; Do not have uncle's substituting group on the phosphorus atom).

Then, with autoclave sealing and find time, pump into 20 milliliters of divinyl.With autoclave H ₂And/or CO pressurization, the dividing potential drop that reaches as shown in Table I, sealing is heated to 135 ℃ and kept 10 hours under this temperature.At last, with the autoclave cooling, use the GLC analyze reaction mixture.

Find, in embodiment 2-18, in fact, in 10 little the reaction times, there is 100% initial substrate (divinyl) to be converted into pentenoic acid (in embodiment 18, isoprene is converted into the methylpent olefin(e) acid), and in comparative example A-D, transformation efficiency does not reach the level greater than 15%.

Initial carbonylation rate in this periodical operation (the moles/mole palladium/hour), as shown in Table I, concerning embodiment 2-18, be defined as the mean rate (pressure drop) that when beginning most to consume 30% substrate, consumes carbon monoxide.Do not reach comparative example A-D of 40% for base consumption, initial carbonylation rate is defined as and is starting the mean rate that CO consumes in two hours.

Table I

Embodiment	Part	Substrate	Solvent	H 2Dividing potential drop	The CO dividing potential drop	Initial carbonylation rate
											Mpa	Mpa	Mol/mol Pd/hr
2	dtbx [0.25]	Divinyl	Diglyme/3-pentenoic acid [25/25ml]	-	4.0	400
							3	dtbx [0.25]	Divinyl	Caproic acid [40ml]	-	4.0	460
4	dtbx [0.25]	Divinyl	N-nonanoic acid [40ml]	-	4.0	700
							5	dtbx [0.25]	Divinyl	Propionic acid [40ml]	-	4.0	400
6	dtbx [0.25]	Divinyl	3-pentenoic acid [40ml]	-	4.0	280
							7	dtbx [0.25]	Divinyl	Caproic acid [40ml]	1.0	4.0	740
8	dtbx [0.25]	Divinyl	Caproic acid [40ml]	0.5	4.0	780
							9	dtbx [0.25]	Divinyl	Caproic acid [40ml]	-	4.0	460
10	dtbx [0.25]	Divinyl	Caproic acid [40ml]	0.2	4.0	560
							11	dtbx [0.25]	Divinyl	Caproic acid [40ml]	-	6.0	880
12	dtbx [0.25]	Divinyl	Caproic acid [40ml]	0.5	6.0	1020
							13	dtbx [0.2]	Divinyl	3-pentenoic acid [40ml]	-	6.0	240
14	dtbx [0.2]	Divinyl	3-pentenoic acid [40ml]	-	6.0	400
							15	α-pa-2-dtb-tolyl [0.5]	Divinyl	N-nonanoic acid [35ml]	-	6.5	350
16	1,2-bpa-o-xylyl [0.2]	Divinyl	N-nonanoic acid [35ml]	-	6.0	225
							17	1,2-bpa-o-xylyl [0.5]	Divinyl	3-pentenoic acid [35ml]	-	6.0	450
18	Dtbx [0.25]	Isoprene	Caproic acid [40ml]	-	6.0	1200
							A	3-(di-t-butyl phosphine)-2-(di-t-butyl phosphine methyl)-1-propylene [0.5mmol]	Divinyl	Caproic acid [40ml]	-	4.0	30
B	1,2-pair-(9-phospha dicyclo [3.3.1] nonyl)-ethane [0.5mmol]	Divinyl	Caproic acid [40ml]	-	4.0	5
							C	1,3-pair-(di-t-butyl phosphine) acetone [0.5mmol]	Divinyl	Caproic acid [40ml]	-	4.0	45
D	1, two (dicyclohexylphosphontetrafluoroborate methyl) benzene [0.5mmol] of 3-	Divinyl	Caproic acid [40ml]	-	4.0	10

Embodiment 19 and Comparative Examples E and F-divinyl and carbonylation of methanol form the rhythmic reaction of pentenoate

The acid chloride (0.1 mmole) of in 250 milliliters of autoclaves that magnetic agitation arranged, packing into continuously, 20 ml methanol, 40 milliliters of pentenoic acids and 0.5 mmole part.

In embodiment 19, the part of use is identical with embodiment 1-13, and in Comparative Examples E, the part of use is identical with Comparative Examples B.

Then, with autoclave sealing and find time, use nitrogen purging, pump into 20 milliliters of divinyl then.Autoclave is pressurized to 6MPa with CO, and sealing is heated to 135 ℃ and kept 10 hours under this temperature.In Comparative Examples E and F, do not observed carbon monoxide consumption, have an appointment 30% divinyl and 4 vinyl cyclohexene and butadiene polymer react.

Table II: with the reaction of methyl alcohol

Embodiment	Part	Solvent	The CO dividing potential drop	Initial carbonylation rate	Butadiene conversion
									Mpa	Mol/mol Pd/hr
19	dtbx [0.5mmol]	3-pentenoic acid [40ml]	6.0	1200	100％
						E	1,2-pair-(9-phospha dicyclo [3.3.1] nonyl)-ethane [0.5mmol]	3-pentenoic acid [40ml]	6.0	-	30％ *
F	1,4-(diphenylphosphine)-butane [0.5mmol]	3-pentenoic acid [40ml]	6.0	-	30％ *

^*Divinyl is converted into the mixture of 4 vinyl cyclohexene and butadiene polymer

Embodiment 20-21 and Comparative Examples G-divinyl carry out the rhythmic reaction that carbonylation forms pentenoic acid with acid via acid anhydrides

The 20 milliliters of acetate of in 250 milliliters of autoclaves that magnetic agitation arranged, packing into continuously, 40 milliliters of diglymes, acid chloride (being 0.25 mmole among the embodiment 20, is 0.1 mmole among embodiment 21 and the Comparative Examples G) and 0.5 mmole part separately.In embodiment 20 and 21, the part of use is identical with embodiment 1-13, and in Comparative Examples G, the part of use is identical with the comparative example A.

With autoclave sealing and find time, pump into 10 milliliters of divinyl then.

Autoclave is pressurized to 4MPa with CO, and sealing is heated to 135 ℃ and kept 10 hours under this temperature.After the cooling, use the GLC contents analysed.

The definition of initial carbonylation rate such as embodiment 1-18 and comparative example A-D.

In embodiment 20, divinyl is to transformation efficiency＞90% of pentenoic acid, and acetate has 35% the diacetyl oxide that is converted into.Initial carbonylation rate is 400 moles/mole Pd/ hours.

In embodiment 21, the transformation efficiency of mensuration is identical with embodiment 20, but speed of reaction is 900 moles/mole Pd/ hours.

In Comparative Examples G, divinyl is 15% to the transformation efficiency of pentenoic acid, and acetate has 5% the diacetyl oxide that is converted into.Speed of reaction is 60 moles/mole Pd/ hours.

Embodiment 22-is prepared the semicontinuous reaction of pentenoic acid by divinyl

In 1.2 liters of churned mechanically autoclaves, pack into 150 milliliters of n-nonanoic acids and 5 ml waters.Autoclave is outgased three times with CO under 3.0MPa.Then, autoclave is pressurized to 5.0MPa, adds 20 milliliters of divinyl subsequently with CO.Next, inject the catalyzer that two (the di-t-butyl phosphine methyl) benzene of 2-are formed by the 0.1 mmole acid chloride and 0.5 mmole 1 that are dissolved in 10 gram n-nonanoic acids.Syringe washes with 10 other gram n-nonanoic acids.

Afterwards, respectively with the 40-50 mmole/hour speed continuously divinyl and water are joined in the reactor, reactor is at 30 minutes internal heating to 130 ℃.When reaching this temperature, pressure is adjusted to 8.0MPa.These conditions kept 68 hours.After the cooling, mixture is distilled under 70-80 ℃ and 10Pa, obtains 304 gram mixtures, analyze by GLC and have following composition:

Table III

The pentenoic acid butenyl esters	6.1wt％
		The n-nonanoic acid butenyl esters	1.4wt％
Suitable/anti-3-pentenoic acid	84.0wt％
		2-and 4-pentenoic acid	1.4wt％
N-nonanoic acid	6.9wt％

The carbonylation rate of this semi continuous operation is defined as the moles butadiene that every mole of palladium per hour reacts, and total turnover number is defined as the moles butadiene/mole Pd of reaction.Based on above result, in 68 hours operating process, average carbonylation rate is 390, and total turnover number is 26000.

The mix products batch of material of embodiment 23-26-embodiment 20 is converted into the further carbonylation of hexanodioic acid

With 4 batches each more than 30 milliliters the mixing product of distillation of illustrated embodiment 21 further carry out following reaction with CO and water.

In 250 milliliters that make by the HASTELLOY C autoclaves that magnetic agitation arranged, the product of distillation of shown in following Table III, pack into water and 30 milliliters of embodiment 21.Then, add 0.1 mole of acetic acid palladium and 0.5 mole of ligand 1, two (di-t-butyl phosphine the methyl)-benzene of 2-, and with the autoclave sealing with find time.Autoclave H ₂And/or CO is pressurized to dividing potential drop as shown in Table III, and sealing is heated to 135 ℃ and kept 15 hours under this temperature.At last, with the autoclave cooling, use the GLC analyze reaction mixture.

Reaction mixture almost completely is made up of solid adipic acid.Add THF to form the slurries of hexanodioic acid in THF.Analyze the THF phase by GLC, calculate the transformation efficiency of pentenoic acid by the pentenoic acid of remnants.In all experiments, the transformation efficiency of pentenoic acid all is higher than 90%.Selectivity＞95% for hexanodioic acid.

Initial carbonylation rate in this periodical operation (the moles/mole palladium/hour), as shown in Table III, be defined as the mean rate (pressure drop) that when beginning most to consume 30% substrate, consumes carbon monoxide.

Table IV

Embodiment	Amount of water	Induction time	H 2Dividing potential drop	The CO dividing potential drop	Initial carbonylation rate
								Hr**	Mpa	Mpa	Mol/mol Pd/hr
23	5ml	6	10	40	610
						24	5ml	5	-	60	700
25	7ml	10	-	65	730
						26	2+5ml *	＜1	-	65	880

* react after 1 hour and add 5 milliliters

The * induction time causes that by the pentenoic acid butenyl esters that exists in the raw material (is 6.1wt% according to Table II) it is converted into pentenoic acid and divinyl at first.When initial water concentration hangs down in embodiment 17, reach this transformation efficiency soon.

Embodiment 27 and 28-divinyl are to the direct carbonylation of hexanodioic acid

In the first step, the 35 milliliters of pentenoic acids of in 250 milliliters that make by the HASTELLOY C autoclaves that magnetic agitation arranged, packing into continuously, 5 ml waters, 0.1 mmole acid chloride and 0.5 mmole ligand 1, two (the di-t-butyl phosphine methyl) benzene of 2-.With autoclave sealing and find time, pump into 20 milliliters of divinyl then.Autoclave is pressurized to 6MPa with CO, is heated to 135 ℃ and kept under this temperature 10 hours.After the cooling, open autoclave, take out sample, analyze with the THF pulp and with GLC.Find that in fact in 10 little the reaction times, 100% initial substrate (divinyl) all is converted into (amylene) acid.

In second step, after the cooling, 7 ml waters are joined in the autoclave, and with CO autoclave is pressurized to 6MPa once more, be heated to 135 ℃ and under this temperature, kept again 10 hours.After the cooling,, and analyze with GLC with content THF pulp.Find that divinyl and pentenoic acid are converted into the transformation efficiency of hexanodioic acid greater than 95%.By filtered and recycled 69 gram products.

In these two steps, the initial carbonylation rate of this periodical operation (moles/mole palladium/hour) all is defined as the mean rate (pressure drop) that consumes carbon monoxide when beginning most to consume 30% substrate.The speed of the first step is 400 moles/mole Pd/ hours.The speed in second step is 550 moles/mole Pd/ hours.

Embodiment 29-B-B-divinyl raw mix is converted into the direct carbonylation of hexanodioic acid

In the first step, in 250 milliliters that make by the HASTELLOY C autoclaves that magnetic agitation arranged, pack the catalyst composition that two (the di-t-butyl phosphine methyl) benzene of 2-are formed continuously into by product mixture (wherein 84wt%'s is pentenoic acid), 5 ml waters, 0.1 mmole acid chloride and the 0.5 mmole ligand 1 of 35 milliliters of embodiment 21.With autoclave sealing and find time, pump into B-B-divinyl raw material that 31 grams have following composition then.

Component Mol%

Acetylene 0.03

Propane 0.01

Propylene 0.03

Butane 3.35

Propine/anti-2-butylene 6.54

Along 2-butylene 5.37

2-methylpropane 0.91

1-butylene 8.72

Iso-butylene 28.13

1,3-butadiene 45.44

Pentane/1 0.4

2-methyl-2-butene 0.77

3-methyl-1-butene 0.05

2-methyl-1-butene alkene 0.17

C ₆₊Hydrocarbon 0.03

Autoclave is pressurized to 6MPa with CO, and sealing is heated to 135 ℃ and kept 10 hours under this temperature.After the cooling, open autoclave, take out sample, analyze with the THF pulp and with GLC.Find that in fact in 10 little the reaction times, 100% initial substrate (divinyl) all is converted into (amylene) acid, and butene conversion does not reach 2%.

In second step, add 2 ml waters and seal autoclave once more and find time and be pressurized to 6MPa with CO again, and be heated to 135 ℃ to remove any residual alkene that comes from the BBB raw mix.2.5 after hour, inject 5 other ml waters (using the CO of 8MPa), pressure and temperature kept 8 hours in addition.After the cooling, solids content is gone out reactor with the THF pulp, and recrystallization, 43 gram solids obtained, when passing through ¹When H NMR (solvent is d-DMSO) analyzes, prove＞99% pure hexanodioic acid.In these two steps, the initial carbonylation rate of this periodical operation (moles/mole palladium/hour) all is defined as the mean rate (pressure drop) that consumes carbon monoxide when beginning most to consume 30% substrate.

The speed of the first step is 1150 moles/mole Pd/ hours.

The speed in second step is 200 moles/mole Pd/ hours.

Embodiment 30-is prepared the semicontinuous reaction of hexanodioic acid by divinyl

In 1.2 liters of churned mechanically autoclaves, pack into 150 milliliters of n-nonanoic acids and 5 ml waters.Autoclave is outgased three times with CO under 3.0MPa.Then, autoclave is pressurized to 5.0MPa, adds 20 milliliters of divinyl subsequently with CO.Next, inject the catalyzer that two (the di-t-butyl phosphine methyl) benzene of 2-are formed by the 0.1 mmole acid chloride and 0.5 mmole 1 that are dissolved in 10 gram n-nonanoic acids.Syringe washes with 10 other gram n-nonanoic acids.

Afterwards, respectively with the 40-50 mmole/hour speed continuously divinyl and water are joined in the reactor, reactor is at 30 minutes internal heating to 130 ℃.When reaching this temperature, pressure is adjusted to 8.0MPa.These conditions were kept about 10 hours, at regular intervals just sampling.In case reach TON is 30,000 moles of pentenoic acid/mol catalysts, is about 97% for the selectivity of pentenoic acid, just stops butadiene feed, and makes remaining divinyl reaction.Add entry then, the concentration of water is about 10%w/w with respect to reactor mixture, transforms fully up to pentenoic acid continuing reaction down with described identical condition before (8.0MPa CO pressure and 135 ℃).

Behind cooling and the relief pressure,, and analyze with GLC with the pulp in THF of the content in the autoclave.Find that pentenoic acid has been converted into hexanodioic acid, selectivity is greater than 97%, and beginning to the overall selectivity of hexanodioic acid from divinyl is 94%.The TON of second reaction is 10,000 moles of hexanodioic acid/mol catalysts.The hexanodioic acid of preparation comprises the nitrogenous impurity that is lower than 1.5ppmw in this reaction, is lower than the halogen-containing impurity of 1.5ppmw, and is lower than 0, the pentanedioic acid of 1ppmw and Succinic Acid.

The amidation of embodiment 31-divinyl

(HASTELLOY is Haynes International by HASTELLOY C at 250 milliliters, Inc. registered trademark) pack in the autoclave of making 0.1 mmole acid chloride and 0.5 mmole ligand 1, two [two (tertiary butyl) phosphine methyl] benzene of 2-, 0.1 mmole acid chloride (II) and 34 milliliters of pentenoic acids.Then, use NH ₃Autoclave is pressurized to 0.2MPa (2 crust).Subsequently, 10 milliliters of 1,3-butadienes are pumped in the reactor, with carbon monoxide reactor are pressurized to 6MPa (60 crust) then.After the autoclave sealing, its content is heated under 135 ℃ the temperature and under this temperature, kept 7 hours.

After the cooling, sampling and analyze from the content of autoclave by gas liquid chromatography.1,3-butadiene and ammonia have transformed 100%, are about 99% for the selectivity of 2-and 3-amylene acid amides, and residuum comprises the pentenoic acid anhydride of trace.

More than experiment shows that the carbonylation method of conjugated diolefine carries out under high turnover ratio at height, reaches completely to transform always, have high overall selectivity for linear product, by the way, it does not also comprise halogen-containing impurity, and after amidated products, also do not contain nitrogenous impurity.

In addition, also described Novel Ligands and its preparation method, it can provide the alternative catalyst system that is easy to utilize.

Claims (18)

1. the carbonylation method of a conjugated diolefine comprises that the co-reactant that makes conjugated diolefine and carbon monoxide and have active hydrogen atom reacts in the presence of a kind of catalyst system, and wherein said catalyst system comprises:

(a) palladium source; With

(b) the bidentate diphosphine part of formula (II):

R ¹R ²＞P ¹-R ³ _m-R-R ⁴ _n-P ²＜R ⁵R ⁶ (II)

Wherein:

P ¹And P ²The expression phosphorus atom;

R ¹, R ², R ⁵And R ⁶Represent the organic group that includes tertiary carbon atom of identical or different optional replacement independently, wherein each group is connected on the phosphorus atom by described tertiary carbon atom;

R ³And R ⁴The methylene group of representing identical or different optional replacement independently;

R represents to comprise bivalent bridging group C ¹-C ²Organic group, wherein, R is connected to R by described bivalent bridging group ³And R ⁴On;

M and n represent the natural number of 0-4 independently,

Wherein, in 0-250 ℃ temperature range, around the carbon atom C of bridging group ¹-C ²Between the rotation of key be restricted and wherein, by C ¹, C ²With at P ¹Be directly connected to C on the direction ¹On the occupied plane of three atomic serieses formed of atom, and by C ¹, C ²With at P ²Be directly connected to C on the direction ²On the occupied plane of three atomic serieses formed of atom between interfacial angle in 0-120 degree scope; With

(c) negative ion source.

2. according to the process of claim 1 wherein that negative ion source (c) is the pKa value measured greater than 3 acid in the aqueous solution under 18 ℃.

3. according to any one method in claim 1 or the claim 2, wherein around carbon atom C ¹-C ²Between the rotation of key be restricted at ambient temperature.

4. according to any one method of claim 1-3, wherein R is the optional aryl that replaces.

5. according to any one method of claim 1-4, wherein n is 1, and m is 0 or 1.

6. according to any one method of claim 1-5, wherein R ³And R ⁴The expression methylene group.

7. as any one method among the claim 1-6, wherein with respect to carbon monoxide, add the hydrogen of 3-20mol%.

8. according to any one method of claim 1-7, wherein R ¹, R ², R ⁵And R ⁶Represent tertiary butyl groups separately.

9. according to any one method of claim 1-8, wherein R ¹And R ²Together and/or R ⁵And R ⁶Together, be the part of 2-phospha-adamantane structure, phosphinan-4-ketone structure or phosphinan-4-thioketones structure.

10. according to any one method of claim 1-9, wherein conjugated diolefine is 1,3-butadiene or 2-methyl isophthalic acid, the 3-divinyl.

11. according to any one method of claim 1-10, wherein the catalyst component of Cun Zaiing (c) and the molar ratio of catalyst component (b) palladium are 10 ²: 1-10 ⁴: in 1 the scope.

12. according to any one method of claim 1-11, wherein, diolefine and carbon monoxide and the co-reactant that is selected from water and carboxylic acid react comprising in the presence of the catalyst system of following component:

(a) palladium source;

(b) the bidentate diphosphine part of formula (II):

R ¹R ²＞P ¹-R ³-R-R ⁴-P ²＜R ⁵R ⁶ (II)

Wherein:

P represents phosphorus atom; R ¹, R ², R ⁵And R ⁶Represent the organic group that contains tertiary carbon atom of identical or different optional replacement independently, wherein each group is connected on the phosphorus atom by described tertiary carbon atom; R ³And R ⁴The alkylidene group that replaces is chosen in expression wantonly independently; R represents the optional aromatic group that replaces;

(c) by under 18 ℃, in the aqueous solution, surveying the negative ion source that the acid of periodic pKa value greater than 3 obtains.

13. as any one method among the claim 1-12, wherein, temperature of reaction is in 50-250 ℃ of scope, reaction pressure is in the 0.1-15MPa scope, and carbon monoxide pressure of tension is in the 0.1-6.5MPa scope.

14. a bidentate diphosphine part that is used for the catalyst composition of each described method of claim 1-13 is characterized in that being represented by formula II:

R ¹R ²＞P ¹-R ³ _m-R-R ⁴ _n-P ²＜R ⁵R ⁶ (II)

Wherein, P ¹And P ²The expression phosphorus atom; R ³And R ⁴The organic group of representing identical or different optional replacement independently; R represents to comprise bivalent bridging group C ¹-C ²Organic group, R is connected to R by described bivalent bridging group ³And R ⁴On; M and n represent the natural number of 0-4 independently; Wherein, R ¹And R ²Together or R ⁵And R ⁶The optional organic group that comprises tertiary carbon atom that replaces of a pair of expression independently together, wherein each group is connected on the phosphorus atom by described tertiary carbon atom, and these groups are only by phosphorus atom P ¹Or P ²Be connected with each other; Wherein, R ⁵And R ⁶Together or R ¹And R ²Together another is connected to phosphorus atom P to expression by tertiary carbon atom ¹Or P ²On organic divalent group.

15. catalyst composition, it comprises: (a) group VIII source metal and (b) according to the bidentate diphosphine part of claim 14.

16. according to the catalyst composition of claim 15, wherein in the bidentate diphosphine part, by C ¹, C ²With at P ¹Be directly connected to C on the direction ¹On the occupied plane of three atomic serieses formed of atom, and by C ¹, C ²With at P ²Be directly connected to C on the direction ²On the occupied plane of three atomic serieses formed of atom between interfacial angle in 0-120 degree scope.

17. can be by the carbonylation product composition that obtains according to any one method of claim 1-13, wherein said product composition comprises the nitrogenous impurity that is lower than 1.5ppmw and is lower than the halogen-containing impurity of 1.5ppmw.

18. according to the carbonylation product composition of claim 17, wherein said product composition stems from 1,3-butadiene and comprises Alpha-Methyl pentanedioic acid and/or α-ethyl succinic acid; Comprise pentanedioic acid and/or the Succinic Acid that is lower than 1.5ppmw with wherein said product composition.