CA1242741A

CA1242741A - Preparation of 4-substituted but-3-ene-1-carboxylic acids and their esters

Info

Publication number: CA1242741A
Application number: CA000469893A
Authority: CA
Inventors: Walter Himmele; Werner Hoffmann; Lothar Janitschke
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1983-12-15
Filing date: 1984-12-12
Publication date: 1988-10-04
Also published as: JPS60152437A; DE3462484D1; EP0146859A3; EP0146859B1; EP0146859A2; DE3345375A1

Abstract

ABSTRACT OF THE DISCLOSURE:

The invention relates to a process for the preparation of a 4-substituted but-3-ene-1-carboxylic acid or its esters of the formula (I):
where R1 is an organic radical, R2 is hydrogen or an organic radical, and R1 and R2 may furthermore be bonded to one another to form a 5-membered to 20-membered ring and should be inert under the reaction conditions des-cribed below, and R3 is hydrogen or lower alkyl, by carbonylation of a derivative of allyl alcohol with the aid of a palladium halide, wherein an allyl alcohol (II):
(II) is carbonylated with carbon monoxide at 50 - 150°C and under 200 - 700 bar, a) together with an alcohol(III):

R3' -OH (III) where R3' is lower alkyl,if a predominant amount of an ester (I) is to be prepared, or b) without any alcohol of formula (III) where an acid(I)is to be prepared; in the presence of an effective amount of a complex of a palladium halide and a tertiary phosphine (IV):

Description

~.Z~ 7~

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o.z. oaso/36s60 Preparation of 4-substituted but-3-ene-1-carboxylic acids and their esters The present invention relates to a novel process for the preparation of 4-substituted but-3-ene-1-carboxy-lic acids or their esters of the general formula I

C=CH-CH2-Co-o-~3 (I) R2~
where R1 is an organic radical, R2 is hydrogen or an organic radical, and R1 and R2 may furthermore be bonded to one another to form a 5-membered to 20-membered ring and should be inert under the reaction condit;ons des-cribed below, and R3 is hydrogen or lower alkyl.
Tsuj; et al., in J. Am. Chem. Soc. 86 ~1964), 4350-4353, disclose that ethyl pent-3-ene-1-carboxylate (I, where R1 is Me, R2 ;s H and R3 is Et) can be pre-pared by carbonylation of but-1-en-3-ol with carbon mon-. . _ ox;de and ethanol in the presence of palladium chloride as a carbonylation catalyst. However, the yield of only 39~ ach;eved in this procedure is unsatisfactory for industrial purposes.
Furthermore, Bittler et al., in Angew. Chemie, 80 t1968), 352 - 359, disclose that allyl alcohol and methanol can be carbonylated using a palladium chloride/triphenyl-phosphine complex to give methyl but-3-enecarboxylate in 65~ yield. According to the authors (cf. loc cit, page 355), the carbonylation of the allyl alcohol takes place w;th retention of the double bond~ so that the ~-substi-tuted but-3-enecarboxylates have to be prepared usingf as starting materials, the allyl alcohols Rl~
C=CH-CH2-oH

which are difficult to obtain.

- 2 - O.Z. 0050/36~60 It is an object of the present invention to make the compounds I more readily accessible~ these compounds generally being important for organic syntheses, and some of them being directly useful as fragrance materials.
We have found, unexpectedly in view of the work by Bittler et al., that this object is achieved by a process for the preparation of the compounds (I) defined at the outset, by carbonylation of a derivative of allyl alcohol with the aid of a palladium halide, wherein an allyl alco-hol II

C-CH=~H2 R OH

is carbonylated with carbon mcnoxide at 50 - 150C and under 20û - 700 bar, a) together with an alcohol III

_ 15 R3 -OH (III) where R3 is lower alkyl, if a predominant amount of an ester I is to be prepared, or b) without any alcohol of formula (III) where an acid I is to be prepared, in the presence of an effective amount of a complex of a palladium halide and a tertiary phosphine ~IV).
The starting compounds II are obtainable in a simple manner from the corresponding carbonyl compounds R1-CO-R2 and vinyl magnesium halides. II can also be prepared from the carbonyl compounds and acetylides, such as sodium acetylide, with subsequent partial hydrogenation of the ethynyl group to the vinyl group.
On the basis of the very extensive investigations carried out to date, the nature of the compounds II, ie.
the type of organic radicals R1 and R2, is in principle unimportant ~ith regard to the novel process, provided 12~L~74~

- 3 - ~ O.Z. 0050/36860 that these radicals do not contain any substituents or groups which are reactive under the carbonylation condi-tions. Examples of such reactive radicals are alkenyl groups having terminal double bonds; if, on the other hand, the double bond is an internal one, it is as a rule v;rtu-ally never attacked under the reaction conditions.
Examples of suitable radicals R1 and R2 are aliphat;c radicals of 1 to 30 carbon atoms, cycloaliphatic radicals having 3 to 1Z ring members, aromatic radicals possessing from 1 to 3 isocyclic or heterocyclic arornatic rings, mixed radicals containing aliphatic and/or cycloaliphatic and/or aromatic groups in any sequence, and cyclic radicals which have from 3 to 20 ring members, are formed by 21 and R2 together and can in turn be substituted by the above radicals.
All of these radicals can furthermore contain sub-stituents such as halogen, eg. fluorine or chlarine, hydroxyl (which in general is virtually never attacked during the carbonylation according to the invention), sub-st;tuted amino, cyano, nitro, alkoxy, acyl, acyloxy, carbalkoxy, thiol, mercaptan, carboxamide or alkylsulfonyl.
Particularly important alcohols II are those whose mole-cule contains one or more isoprene skeletons; the compounds I derived from these are often typical fragrance mater;als.
Suitable alcohols III are mainly lower alcohols, such as methanol and ethanol, since the carbonylation pro-ceeds most rapidly with these. Higher alcohoLs of not more than about 6 carbon atoms can in principle also be used, although it is frequently more advantageous to introduce these into the molecule by transesterification of the methyl or ethyl esters I.
In general, it is preferable to use a molar excess of the alcohol III over the alcohol II. Usually, the molar ratio of III to II is from 2 1 to 6:1. If III is used as a solvent, this ratio may also be higher.
If the procedure is carried out in the absence of ~2~274~.

~ 4 - O.Z. 005~/3686~
a further reac~ant, ;e. w;thout an alcohol III, the acids I are obtained. Predominant amounts of acid are also generally obtained when a tertiary alcohol III, eg~ tert.-- butanol, is used.
The carbonylation catalysts are complexes of a palladium halide, eg. the bromide or in particular the chloride, and a tertiary organic phosphine (IV). Since formation of these complexes takes place directly under the reaction conditions, the said complexes are advantage-ously employed in the form of their components; however, it is of course also possible to start from the prepre-pared complexes, eg. Pd(Pph3)2Cl2 (Ph phenyl).
The tertiary phosphines IV are of the general formula IV
,R4 P-R5 (IV) ~R6 where R4, R5 and R6 are each an organic radical.
In particular, R4, R5 and R6 can each be alkyl of 4 to 18 carbon atoms, C1-C4-alkylphenyl or~ especially, phenyl. Two of these radicals may furthermore be bonded to one another to form a 5-membered to 8-membered ring, and it is of course also possible to use compounds possess-ing 2 or more tertiary phosphine groups, eg. 1,2-bis-(diphenylphosphino)-ethane.
The type of phosphines is in principle unimportant, so that it is in general preferable to use the cheapest member of this class of substances, ie. triphenylphosphine.
It is also advantageous to carry out the reaction in the presence of free phosphine, ie. phosphine which is not bonded in a complex~ The preferred molar ratio of phosphine to Pd is from 3:1 to 10:1.
It is not possible to state a particular value for the effective amount of the catalyst because the reaction takes place in principle with infinitely small amounts of Pd, but is of course then very slow, and because large ~2~274~1.

_ 5 _ O.z. 0050/36860 amounts have no adverse effect. Hence, the amount of Pd depends on the reactivity of the alcohol II and on the reaction time desired. In general, the amount of Pd is - from 0.1 to 5 9 per mole of II.
According to the general principLes of process engineering, the reaction takes place most read;ly and most rapidly in the substantially homogeneous liquid phase.
In general, homogeneity results automatically under the reaction conditions owing to the presence of the alcohol 10 III, so that an additionaL solvent need not be used. If, however, the alcohol II is sparingly soluble, it is advis-able to use a solvent, such as toluene, diethyl ether or tetrahydrofuran.
The pressure, which for the most part corresponds to the C0 partial pressure, is in general from lO0 to 650, in particular from 300 to oO0, bar, and the recommended temperature is from 50 to 150C, preferably from 90 to 110C. Under these conditions, and using the recommended amounts of catalyst, the reaction times are about 1 - 24 hours.
The novel process can be carried out continuously or batchwise, and the method used is identical to the con-ventional carbonylation technique, so that more detailed description of this can be dispensed wi~h~ The same applies to the working up of the reaction mixtures. Owing to the sensitivity of the phosphines to oxidation, it is advisable to carry out the procedure in the absence of atmospheric oxygen.
When the alcohol III is also used, the products obtained are mainly the esters I, the free acids 1 also resulting; tertiary alcohols III generally give larger amounts of the acid. The amount of by~products is low in every case, although it was expected that the alcohols II
would be dehydrated under the reaction conditions. The compounds I can be formed in the cis or trans form, pre~
dominant amounts of the trans isomer usually being obtaine~O

~2~2~4~.

- 6 - O~Z. 0050/36860 EXAMPLES
Various alcohols II were reacted with various alc~hols III, in each case in the absence of atnospheric oxygen, at 100C, in the presence of palladium chloride and triphenylphosphine (Pph3), to give the acids or esters I.
Details of the other reaction conditions and o~
the results of the experiments are shown in the Table below. About 98~ of the stated pressure is due to the C0 partial pressure~ Each of the reactions was terminated when scarcely any further C5 was consumed.
The products were identified by means of gas chromatographic, ~-NMR, 13C-NMR, mass spectroscopic and IR analysis. The yields were determined gravimetrically;
where separation into the acid and the ester presented difficulties, onLy the sum of the yields was determined.
Boiling points and melting points are stated wherever they were obtained directly from the experiments.

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Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the preparation of a 4-substituted but-3-ene-1-carboxyLic acid or its esters of the formuLa I
(I) where R1 is an organic radicaL, R2 is hydrogen or an organic radicaL, and R1 and R2 may furthermore be bonded to one another to form a 5-membered to 20-membered ring and shouLd be inert under the reaction conditions des-cribed beLow, and R3 is hydrogen or Lower aLkyL, by carbonyLation of a derivative of aLLyL aLcohoL with the aid of a paLLadium haLide, wherein an aLLyL aLcohoL II
(II) is carbonyLated with carbon monoxide at 50 - 150°C and under 200 - 700 bar, a) together with an aLcohoL III
R3'-OH (III) where R3' is Lower aLkyL, if a predominant amount of an ester (I) is to be prepared, or b) without any aLcohoL of formuLa (III) where an acid (I) is to be prepared, in the presence of an effective amount of a compLex of a paLLadium haLide and a tertiary phosphine (IV);

(IV) where R4, R5 and R6 are each organic radical.

2. A process for the preparation of a 4-substituted but-3-ene-1-carboxylic acid or its esters of the formula (I):
(I) wherein R1 is an aliphatic radical of 1 to 30 carbon atoms, a cycloaliphatic radical having from 3 to 12 ring members, an aromatic radical possessing from 1 to 3 isocyclic or heterocyclic aromatic rings, a mixed radical containing aliphatic and/or cycloaliphatic and/or aromatic groups in any sequence, unsubstituted or substituted by at least one radical selected in the group consisting of halogen atoms hydroxy radical, substituted amino radicals, cyano radical, nitro radical, alkoxy radical, acyl radical, acyloxy radical, carbalkoxy radical, thiol radical, mercaptan radical, car-boxamide radical or alkylsulfonyl radical, R2 is a hydrogen atom or is an aliphatic radical of 1 to 30 carbon atoms, a cycloaliphatic radical having from 3 to 12 ring members, an aromatic radical possessing from 1 to 3 isocyclic or heterocyclic aromatic rings, a mixed radical containing aliphatic and/or cycloaliphatic and/or aromatic groups in any sequence, unsubstituted or substituted by at least one radical selected in the group consisting of halogen atoms hydroxy radical, substituted amino radicals, cyano radical, nitro radical, alkoxy radical, acyl radical, acyloxy radical, carbalkoxy radical, thiol radical, mercaptan radical, car-boxamide radical or alkylsulfonyl radical, and R1 and R2 may furthermore be bonded to one another to form a 5-membered to 20-membered ring, and should be inert under the reaction conditions described below, and R3 is hydrogen or lower alkyl, by carbonylation of a derivative of allyl alcohol with the aid of a palladium halide, wherein an allyl alcohol (II):
(II) where R1 and R2 have the above identified meanings, is carbonylated with carbon monoxide at 50 - 150°C and under 200 - 700 bar, a) together with an alcohol (III):

R3'-OH (III) where R3' is lower alkyl, if a predominant amount of an ester (I) is to be prepared, or b) without any alcohol of formula (III) where an acid (I) is to be prepared, in the presence of an effective amount of a complex of a palladium halide and a tertiary phosphine (IV):
(IV) where R4, R5 and R6 are each an alkyl radical of 4 to 18 carbon atoms, a C1-C4-alkylphenyl radical or a phenyl radi-cal, or two of these radicals are bonded to one another to form a 5-membered to 8-membered ring.

3. A process according to claim 2, wherein the allyl alcohol of formula (II) is selected in the group con-sisting of pent-1-en-3-ol, hex-1-en-3-ol, hept-1-en-3-ol, oct-1-en-3-ol, 3-methylbut-1-en-3-ol, 3,7-dimethyloct-1-en-3-ol, 3,7-dimethylocta-1,6-dien-3-ol, 3,7,11-trimethyl-dodec-1-en-3-ol, 3,7,11-trimethyldodeca-1,6-dien-3-ol, 3,7,11-trimethyldodeca-1,6,10-trien-3-ol, 3,7,11,15-tetra-methylhexadec-1-en-3-ol, 5-(2,6,6-trimethylcyclohex-1-en-1-yl)-3-methylpent-1-en-3-ol, 5-(2,6,6-trimethylcyclohex-1-en-1-yl)-3-methylpenta-1,4-dien-3-ol, 3-ethylpent-1-en-3-ol, 4-vinylheptan-4-ol, 1-vinylcyclododecan-1-ol, 2-methyl-1-vinyl-cyclohexan-1-ol, 3-methyl-1-vinyl-cyclohexan-1-ol, 1-vinyl-cyclohexan-1-ol, 3,3-dimethyl-1-vinylcyclohexan-1-ol, 2,2,4-trimethyl-1-vinylcyclopentan-1-ol, 2,4,4-trimethyl-1-vinylcyclopentan-1-ol, 1-vinyl-1-hydroxy-1,2,3,4-tetrahy-dronaphtalene, 9-vinyl-9-hydroxyfluorene, 3,3-diphenylprop-1-en-3-ol, 3-phenylbut-1-en-3-ol, 3-(3,3-dimethylcyclo-hex-1-yl)-but-1-ene, 3-cyclopropylbut-1-en-3-ol, 3-methoxybut-1-en-3-ol, 3-methyl-4-phenylbut-1-en-3-ol, 1-vinyl-cyclo-heptan-l-ol, 3-(4-methoxyphenyl)-but-1-en-3-ol, 4-tert-butoxy-hex-1-en-3-ol, 3,2-methoxyphenyl)-but-1-en-3-ol, 2-benzyl-1-vinyl-cyclohexan-1-ol, 3-(tetrahydropyran-3-yl)prop-1-en-3-ol, bis-(4-chlorophenyl)-vinylcarbinol, bis-(4-fluoro-phenyl)-vinylcarbinol, 1-vinyl-2,3-6,7-dibenzocyclohept-4-en-1-ol, 1-vinyl-2,3-6,7-dibenzocycloheptan-1-ol and 3-(2-methoxyphenyl)-prop-1-en-3-ol.

4. A process according to claim 2, wherein the alcohol of formula (III) is selected in the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol and t-butanol.

5. A process according to claim 2, wherein the ter-tiary phosphine of formula (IV) is triphenylphosphine.

6. A process according to claim 2, wherein the palladium halide is PdCl2.

7. A process according to claim 2, wherein the allyl alcohol of formula (II) is selected in the group consisting of pent-1-en-3-ol, hex-1-en-3-ol, hept-1-en-3-ol, oct-1-en-3-ol, 3-methylbut-1-en-3-ol, 3,7-dimethyloct-1-en-3-ol, 3,7-dimethylocta-1,6-dien-3-ol, 3,7,11-trimethyldodec-1-en-3-ol, 3,7,11-trimethyldodeca-1,6-dien-3-ol, 3,7,11-tri-methyldodeca-1,6,10-trien-3-ol, 3,7,11,15-tetramethylhexa-dec-l-en-3-ol, 5-(2,6,6-trimethylcyclohex-1-en-1-yl)-3-methylpent-1-en-3-ol, 5-(2,6,6-trimethylcyclohex-1-en-1-yl)-3-methylpenta-1,4-dien-3-ol, 3-ethylpent-1-en-3-ol, 4-vinyl-heptan-4-ol, 1-vinylcyclododecan-1-ol, 2-methyl-1-vinyl-cyclohexan-1-ol, 3-methyl-1-vinylcyclohexan-1-ol, 1-vinyl-cyclohexan-1-ol, 3,3-dimethyl-1-vinylcyclohexan-1-ol, 2,2, 4-trimethyl-1-vinylcyclopentan-1-ol, 2,4,4-trimethyl-1-vinylcyclopentan-1-ol, 1-vinyl-1-hydroxy-1,2,3,4-tetrahydro-naphtalene, 9-vinyl-9-hydroxyfluorene, 3,3-diphenylprop-1-en-3-ol, 3-phenylbut-1-en-3-ol, 3-(3,3-dimethylcyclo-hex-1-yl)-but-1-ene, 3-cyclopropylbut-1-en-3-ol, 3-methoxybut-1-en-3-ol, 3-methyl-4-phenyl-but-1-en-3-ol, 1-vinyl-cyclo-heptan-1-ol, 3-(4-methoxyphenyl)-but-1-en-3-ol, 4-tert-butoxy-hex-1-en-3-ol, 3-(2-methoxyphenyl)-but-1-en-3-ol, 2-benzyl-1-vinyl-cyclohexan-1-ol, 3-(tetrahydropyran-3-yl)-prop-1-en-3-ol, bis-(4-chlorophenyl)-vinylcarbinol, bis-(4-fluoro-phenyl)-vinylcarbinol, 1-vinyl-2,3-6,7-dibenzocyclohept-4-en-l-ol, 1-vinyl-2,3-6,7-dibenzocycloheptan-1-ol and 3-(2-methoxyphenyl)-prop-1-en-3-ol; the alcohol of formula (III) is selected in the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol and t-butanol; the ter-tiary phosphine of formula (IV) is triphenylphosphine; and the palladium halide is PdCl2.