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Process of Hydrocyanation of Unsaturated Carboxylic Acid Derivatives

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Process of Hydrocyanation of Unsaturated Carboxylic Acid Derivatives (19) TZZ ZZ T (11) EP 2 295 400 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 16.03.2011 Bulletin 2011/11 C07C 227/28 (2006.01) C07C 229/08 (2006.01) C07C 253/10 (2006.01) C07C 255/19 (2006.01) (21) Application number: 10175248.3 (22) Date of filing: 08.09.2004 (84) Designated Contracting States: • Lenges, Christian Peter BE DE FR NL Wilmington, DE 19810 (US) (30) Priority: 11.09.2003 US 501927 P (74) Representative: Carpmaels & Ransford One Southampton Row (62) Document number(s) of the earlier application(s) in London accordance with Art. 76 EPC: WC1B 5HA (GB) 09001657.7 / 2 058 298 04783415.5 / 1 663 957 Remarks: This application was filed on 03-09-2010 as a (71) Applicant: Invista Technologies S.à.r.l. divisional application to the application mentioned 8001 Zurich (CH) under INID code 62. (72) Inventors: • Allgeier, Alan Martin Oak Park, CA 91377 (US) (54) Process of hydrocyanation of unsaturated carboxylic acid derivatives (57) The present invention is directed to a process obtained by the above hydrocyanation to produce amine for the hydrocyanation of a naturally occurring oil. A meth- containing carboxylic acids is also disclosed. od of hydrogenating the nitrile containing carboxylic acids EP 2 295 400 A2 Printed by Jouve, 75001 PARIS (FR) EP 2 295 400 A2 Description FIELD OF THE INVENTION 5 [0001] This invention is related to the field of hydrocyanation of olefins and in particular, hydrocyanation of unsaturated carboxylic acids, fatty acids and oils comprising these acids. BACKGROUND OF THE INVENTION 10 [0002] Unsaturated fatty acids and oils comprising unsaturated carboxylic acids are attractive substrates for a variety of applications such as monomers for polymeric materials, as ingredients in composites, as lubricants or as fine chemicals. These materials are especially attractive since they are based on natural sources and therefore offer an environmentally and ecologically responsible route to useful chemicals. Significant effort has been devoted toward further transformations of these long chain unsaturated fatty acids to arrive at new, functional materials. 15 [0003] Towards this end the current invention provides a process of hydrocyanation of unsaturated and/or poly- unsaturated carboxylic acids, especially fatty acids and/or oils comprising these fatty acids to form the corresponding fatty acid/oil nitrile products. In case of the oils, typical examples are natural occurring oils, for example soybean oil. The products can be mononitriles, dinitriles and/or polynitriles. Furthermore these nitriles can be converted to the corre- sponding methylene-amines via a hydrogenation reaction. 20 [0004] Unsaturated carboxylic acids, and especially fatty acids and their derivatives containing nitrile groups are of interest as lubricants, surfactants or precursors to a variety of useful molecules. Typical examples of unsaturated fatty acids, which are naturally occurring, include mono- or polyunsaturated carboxylic acids, such as oleic acid, lauroleic acid, myristoleic acid, palmitoleic acid, linoleic acid, and arachidonic acid. Naturally occurring oils, for example soybean oil, comprise glycerin esters of these unsaturated fatty acids. Other typical useful unsaturated carboxylic acids are, for 25 example, 3-pentenoic acid or 4-pentenoic acid. [0005] Goertz et al. in Chem. Commun., 1521 (1997) disclosed a hydrocyanation reaction of unsaturated fatty acid esters (i.e. containing a terminal olefin) using nickel phosphine catalysts. The reported yields are undesirable for com- mercial application. Additionally, it is known in the art that internal olefins, such as those in many naturally occurring fatty acids and esters, are more difficult to react in a hydrocyanation process than terminal olefins, such as those found 30 in ω-unsaturated fatty acid esters. [0006] WO 99 06358 A1 disclosed the Hydrocyanation of monoethylenically unsaturated ester compounds to provide linear terminal nitrile molecules but did not disclose the hydrocyanation of carboxylic acids. Acidic compounds are known to deactivate catalysts and degrade typical hydrocyanation ligands. [0007] Prior to the present invention, it was not known that unsaturated fatty acids or naturally occurring oils with 35 olefinic unsaturation could be converted selectively in a hydrocyanation process to the corresponding fatty acid derivatives with nitrile groups in high yields. It was also not known that the so formed derivatives of fatty acids containing nitrile groups could be converted selectively in a hydrogenation process to the fatty acid derivatives with the corresponding amine groups. There is a need to access fatty acid derivatives, which have one or more additional functional groups, such as nitriles, amines, alcohols or carboxylic acids. In particular, derivatives of plant oils like soybean oil, which contain 40 one or more additional functional groups are of interest. [0008] Therefore, there remains a need for specific nitrile derivatives of unsaturated carboxylic acids, especially un- saturated fatty acids and/or oils of unsaturated fatty acids and a method to produce these compounds in general. There is also a need for derivatives of unsaturated fatty acids, which contain amine groups and for a method to produce such derivatives, which contain amine groups. These needs are met by the present invention. 45 SUMMARY OF THE INVENTION [0009] The present invention is directed to compositions of specific carboxylic acid, fatty acid or oil derivatives containing nitrile groups and methods of their preparation. The preparation involves a hydrocyanation reaction. A method of hy- 50 drogenating the nitrile containing carboxylic acid acids obtained by above hydrocyanation to produce amine containing carboxylic acids is also disclosed in this invention. [0010] The present invention is, therefore, a composition of matter of structural formula III: 55 2 EP 2 295 400 A2 5 and a composition of matter of structural formula V: 10 15 20 25 wherein: each A is independently a group comprising one or more hydrocarbon fragments comprising -(CH2)w-, alkene containing fragments comprising -CH=CH-, or nitrile containing fragment comprising -(CH2CHCN)- or -(CH(CN) 30 CH2)-, or a combination of two or more of these fragments in any order; each B is independently A’-H, wherein A’ is a group comprising one or more hydrocarbon fragment comprising -(CH2)w-, alkene containing fragment comprising -CH=CH-, or a nitrile containing fragment comprising- (CH2CHCN)- or -(CH(CN)CH2)-, or a combination of two or more of these fragments in any order; and wherein, w is independently 0 or a positive integer, preferably between 0 and 20. 35 [0011] Also disclosed is a hydrocyanation process, said process comprising converting a starting carboxylic acid in the presence of a catalyst to produce a derivative of carboxylic acid comprising one or more compounds of formula (I): 40 45 wherein: A is a group comprising one or more hydrocarbon fragments comprising -(CH2)w-, alkene containing fragments comprising -CH=CH-, or nitrile containing fragment comprisings -(CH2CHCN)- or -(CH(CN)CH2)-, or a combination 50 of two or more of these fragments in any order; B is A’-H, wherein A’ is group comprising one or more hydrocarbon fragment comprising -(CH2)w-, alkene containing fragment comprising -CH=CH-, or a nitrile containing fragment comprising -(CH2CHCN)- or -(CH(CN)CH2)-, or a combination of two or more of these fragments in any order; and R is H or a glycerol derivative; and 55 wherein, w is 0 or a positive integer, preferably between 0 and 20. [0012] Also disclosed is a process of hydrogenation comprising hydrogenating the carboxylic acid derivative to produce acid amine compounds of structural formula (II): 3 EP 2 295 400 A2 5 wherein 10 C is a group comprising one or more hydrocarbon fragments comprising -(CH2)x-, alkene containing fragments comprising -CH=CH-, nitrile containing fragments comprising -(CH2CHCN)- or -(CH(CN)CH2)-, or amine containing fragments comprising -(CH2CH(CH2NH2)- or -(CH(CH2NH2)CH2)-, or a combination of one or more of these frag- ments in any order; 15 D is H or C’-H wherein C’ is a group comprising one or more hydrocarbon fragments comprising -(CH2)x-, alkene containing fragments comprising -CH=CH-, nitrile containing fragments comprising -(CH2CHCN)- or -(CH(CN)CH2)-, or amine containing fragments comprising -(CH2CH(CH2NH2)- or -(CH(CH2NH2)CH2)-, or a combination of two or more of these fragments in any order; R is H or a glycerol derivative; and 20 x is 0 or a positive integer, preferably between 0 and 20, wherein x is independently chosen each time it is utilized in the structure. [0013] Notable for this invention is the use of oleic acid as the substrate to provide a nitrile derivative or a mixture of nitrile derivatives. While this invention may provide a variety of isomers described by (I), the process shows preference 25 for the terminal nitrile, (III): 30 35 [0014] Additionally, notable is amine derivative (IV) of corresponding structure. 40 45 [0015] Glycerol tri-esters with olefinic unsaturation, comprising naturally occurring plant and/or animal oils, are impor- tant feedstocks within the scope of the present invention. These glycerol tri-esters may be constructed of fatty acid fragments. Products derived from them according to the present invention can be described by formula (V) and/or (VI): 50 55 4 EP 2 295 400 A2 5 10 15 wherein, A, B, C and D are defined as above and are of independent identity each time utilized in the structure. [0016] These compounds are useful as organic synthesis precursors or as lubricants or in surfactant applications. [0017] Natural glyceridic oils may also contain different degrees of unsaturation, which deviate from the stoichiometry 20 suggested by the oleic acid derivative. Other oils useful for this invention include unsaturated plant oils such as tung oil, mono-, di-, and tri-glyceride oils such as oils from soybeans, oil seed rape, linseed, olive oil, castor oil, mustard seed oil, ground nut oil, coconut oil, corn oil, cottonseed oil, palm oil, peanut oil, safflower oil and phenolic oils such as cashew nut shell liquid.
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