US3855255A - Process for the production of higher, polyunsaturated carboxylic acid ester and free acids - Google Patents

Process for the production of higher, polyunsaturated carboxylic acid ester and free acids Download PDF

Info

Publication number
US3855255A
US3855255A US00146780A US14678071A US3855255A US 3855255 A US3855255 A US 3855255A US 00146780 A US00146780 A US 00146780A US 14678071 A US14678071 A US 14678071A US 3855255 A US3855255 A US 3855255A
Authority
US
United States
Prior art keywords
carboxylic acid
electron donor
organo
polyunsaturated carboxylic
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00146780A
Other languages
English (en)
Inventor
M Dohr
H Singer
W Umbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Application granted granted Critical
Publication of US3855255A publication Critical patent/US3855255A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones

Definitions

  • ABSTRACT A process for the preparation of higher, polyunsaturated carboxylic acid esters consisting essentially of the steps of reacting a conjugated diolefin with an alkyl ester of methacrylic acid in a ratio of at least 4 mols of diolefin per mol of methacrylic acid ester, in the presence of an organo-metal complex of zerovalent nickel and of an electron donor selected from the group consisting of phosphorous acid triamides, heterocyclic N-bases, aliphatic and aromatic amines, nitriles, sulfides, sulfoxides and triaryl compounds of arsenic and antimony, and recovering said higher, polyunsaturated carboxylic acid ester having more than 19 carbon atoms in the acid moiety.
  • the reaction products are co-oligomerizates of four molecules of conjugated dienes and one molecule of methacrylic acid ester.
  • the ester may be saponified to obtain the free carboxylic acid having more than 19 carbon 12 Claims, N0 Drawings PROCESS FOR THE PRODUCTION OF HIGHER, POLYUNSATURATED CARBOXYLIC ACID ESTER AND FREE ACIDS THE PRIOR ART
  • diolefins with conjugated double bonds can be reacted with mono-olefinic compounds in the presence of an organo-metal complex of the iron group, and optionally a substance serving as an electron-donor, to form cooligomers.
  • Suitable catalysts include the zero-valent complexes of the metals of the iron group, which are added either in a pure form to the reaction mixture or are formed in situ by reduction of suitable salts of the said metals with organo-metal compounds or hydrides in the presence of electron donors, or of substances which form structures with isolated pairs of electrons and can act in this form as electron donors.
  • suitable salts of the said metals with organo-metal compounds or hydrides in the presence of electron donors, or of substances which form structures with isolated pairs of electrons and can act in this form as electron donors.
  • thioethers sulfoxides, sulfones and mercaptans may be mentioned as electron donors.
  • olefins especially polyolefins, and acetylenic compounds belong to substances which form structures with isolated pairs of electrons and, therefore, may also act as electron donors, while the diene used in the co-oligomerization process may also serve as electron donor in this sense.
  • the co-oligomerization process is carried out with dienes and mono-olefmic compounds which are activated by a carboxyl group, as for example, derivatives of acrylic and methacrylic acids, then, according to the French patent, a complex compound of zero-valent cobalt is particularly suitable as a catalyst.
  • Carboxylic acid esters or carboxylic acids witha relatively high carbon content namely, reaction products of butadiene and acrylic acid compounds in the molar ratio of 2:1 are obtained according to DDR Pat. No. 54,688 when the reaction is carried out specifically in the presence of an organic complex of zero-valent nickel.
  • suitable organo-metal complexes of nickel are those which are obtained by reduction of a nickel compound in which the nickel is present in its usual valency, possibly in the presence of electron donors or of substances which are capable of forming structures with isolated pairs of electrons.
  • Suitable electron donors according to the DDR patent are all those compounds mentioned in the said French patent, thus alkyl and aryl phosphines, alkyl or aryl phosphites, arsines and stibines and the phosphines, phosphites, arsines and stibines named in the French Patent No.
  • 1,337,558, i.e., triphenylphosphine, tri-o-tolylphosphine, tri-a-naphthylphosphine, tris- (trimethylphenyl)-phosphine, triphenylarsine, tri-otolyl-arsine, tri-o-tolylstibine and triphenylstibine, are denoted as particularly advantageous.
  • the diene to be reacted may serve as the electron donor, as in the above-mentioned patent.
  • the reaction between diene and acrylic or methacrylic acid esters is effected exclusively in the molar ratio of 2:1.
  • An object of the present invention is the preration of higher, polyunsaturated carboxylic acid esters and carboxylic acids having at least 19 carbon atoms in the acid moiety in a one step co-oligomerization reaction.
  • Another object of the present invention is the development of a process for the preparation of higher, polyunsaturated carboxylic acid esters consisting essentially of the steps of reacting a conjugated diolefin with an alkyl ester of methacrylic acid in a ratio of at least 4 mols of diolefin per mol of methacrylic acid ester, in the presence of an organo-metal complex of zerovalent nickel and of an electron donor selected from the group consisting of phosphorous acid triamides, heterocyclic N-bases, aliphatic and aromatic amines, nitriles, sulfides, sulfoxides and triaryl compounds of arsenic and antimony, and recovering said higher, polyunsaturated carboxylic acid ester having more than 19 carbon atoms in the acid moiety.
  • the present invention therefore, provides a process for the preparation of higher, polyunsaturated carboxylic acid esters and carboxylic acids, comprising reacting a conjugated diolefin with a methacrylic acid ester in a proportion of at least 4 mols of diolefin per mol of methacrylic acid ester, in the presence of an organometal complex of zero-valent nickel and of an electron donor from the class of phosphorous acid triamides, heterocyclic N-bases, aliphatic and aromatic amines, nitriles, sulfides, sulfoxides and triaryl compounds of arsenic and antimony, isolating the ester obtained from the reaction mixture and, if desired, converting said ester into the free carboxylic acid.
  • Suitable examples of substances from the said classes which can be used as electron donors according to the invention include phosphorous acid triamides such as phosphorous acid trimorpholide, phosphorous acid tri- N-methylanilide, tri-N,N-dialkylamides of phorphorous acid; aliphatic and aromatic amines, which may be primary, secondary, or tertiary, such as hexylamine, dibutylamine, triethylamine, morpholine, N- methylmorpholine, piperidine, triphenylamine, pyridine, the picolines, collidine, quinoline, pyrrole, diphenylamine, benzylamine, dimethylaniline, toluidine; nitriles such as acetonitrile or benzonitrile; aliphatic and aromatic sulfides and sulfoxides such as diethylsulfide, di-tert.-butylsulfide, didodecylsulfide
  • Electron donors from the classes of the heterocyclic N-bases, aliphatic and aromatic amines, sulfides, triarylarsines and triarylstibines are preferred.
  • the preparation of the organo-metal complex of the zero-valent nickel may be carried out in the usual way. Any nickel salt or nickel complex may be used, since insoluble salts in the system also gradually go into solution during the subsequent reduction and give an active catalyst solution.
  • anhydrous organic nickel salts, of aliphatic or aromatic carboxylic acids such as, for example, nickel laurate, nickel palmitate or nickel benzoate and chelate complexes, such as nickel-( Il)-acetylacetonate or nickel salicylate, are preferred for the preparation of the catalyst solutions.
  • reducing agents are those of the said types of compounds which enable the operation to be effected in a homogeneous phase, as for example, trialkylaluminum compounds, dialkylaluminum hydrides, trialkylboron compounds, alkylmagnesium bromides and iodides, dialkyl zinc and alkyl lithium compounds.
  • the relative proportion between the nickel compound to be reduced and the reducing agent is advantageously chosen so that the oxidation equivalent to the reduction equivalent is 1:0.5 to 1:10.
  • the complex of active catalyst with zero-valent nickel can advantageously be made in the mixture of compounds which is itself to be reacted.
  • a nickel compound in which nickel is present in a usual stage of valency, the electron donor and a part of the diene to be reacted are introduced into a solvent and then the reducing agent is added.
  • Solvents suitable for this reduction process and the subsequent co-oligomerization reaction are those which are inert under the operating conditions.
  • saturated aliphatic hydrocarbons such as hexane, heptane, or octane
  • saturated cycloaliphatic or aromatic hydrocarbons such as cyclohexane, benzene or toluene
  • lower alkyl ethers such as diethyl ether or diisopropyl ether
  • non-reactive cyclic ethers such as tetrahydrofuran or dioxan
  • halogenated hydrocarbons for example, methylene chloride or chlorobenzene.
  • the relative proportion between the catalyst and the methacrylic acid ester to be reacted is advantageously chosen so that 50 to 200 mols of methacrylic acid ester are used to 1 gram-atom of zero-valent nickel, i.e., the catalyst concentration, based on the sum of the monomers used, amounts to less than 4%.
  • the catalyst concentration i.e., the catalyst concentration
  • the methyl ester is of primary importance.
  • esters of methacrylic acid with other alkanols as for example, with n-, sec., or tert.-butanol or longer-chain, straightchain and branched-chain alcohols, may be used also in the reaction.
  • the preferred use of the methyl esters is of importance especially when the higher carboxylic acid esters prepared in the process of the invention are to be subsequently saponified to the corresponding acids.
  • butadiene, isoprene or 1,3-pentadiene are preferred as the conjugated diolefins to be reacted, butadienel ,3 being the especially preferred starting material.
  • the process according to the invention may be carried out continuously or discontinuously.
  • the reaction is effected at a temperature of from 20 to C under normal or increased pressure.
  • the relative proportions of diolefin and methacrylic acid ester are advantageously chosen so that a small excess of diolefin over the stoichiometrically required amount of 4 mols of diolefin per mol of methacrylate is present. This excess should amount to about 5 to 10% of the theoretical amount of diolefin required.
  • the separation of the products from the reaction mixture may be effected in the usual way, for example, by fractional distillation.
  • the active catalyst is suitably destroyed by passing air into the reaction mixture or by addition of a mineral acid.
  • acetonate trimorpholide 3 do.
  • morpholine 30 48 77 95 4 ca. 4 do. didodecyll 20 78 93 6 ca. 10
  • isomerization may again occur if the saponification of the ester obtained is carried out, in which less stable isomers are rearranged into a more stable form.
  • esters and acids prepared in the process of the invention are valuable intermediate products fororganic syntheses. They may be converted into the corresponding saturated esters and acids by hydrogenation, and polyfunctional substances may be obtained, by oxidative fission or hydroxylation of the double bonds, which are valuable, for example, as raw materials for polycondensation reactions. Further, as in analogy with drying oils, they may be used in suitable paints.
  • EXAMPLE 1 2 gm (7.8 mMol) of dry nickel (Il) acetylacetonate were dissolved in 100 ml of benzene under an atmosphere of nitrogen. 0.63 ml (7.8 mMol) of pyridine and about 10 gm of butadiene were added thereto. Then 2.2 ml (16 mMol) of triethylaluminum were slowly dropped into the reaction mixture. 39 gm (390 mMol) I ing over at about 135C under a pressure of about 0.1
  • mm Hg was collected. lt amounted to 1 15 gm and consisted of 96% of a C ester mixture. The yield of C esters, based on methacrylate used, was therefore 89%. The distillation residue obtained was 5%, based on methacrylate used, and the yield, based on methacrylate reacted, was therefore 95%. About 10% of the butadiene used had been trimerized to cyclododecatriene-l ,5,9.
  • the pr ocess of claim 1 including the further steps of saponifying said higher, polyunsaturated carboxylic acid ester and recovering a higher, polyunsaturated carboxylic acid having more than 19 carbon atoms.
  • organo-metal complex of zero-valent nickel is formed in situ in the presence of part of said conjugated diene and said electron donor by the reduction of an anhydrous organodonor is triaryl-stibine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00146780A 1970-05-27 1971-05-25 Process for the production of higher, polyunsaturated carboxylic acid ester and free acids Expired - Lifetime US3855255A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702025830 DE2025830A1 (de) 1970-05-27 1970-05-27 Verfahren zur Herstellung von höheren, mehrfach ungesättigten Carbonsäureestern und Carbonsäuren

Publications (1)

Publication Number Publication Date
US3855255A true US3855255A (en) 1974-12-17

Family

ID=5772199

Family Applications (1)

Application Number Title Priority Date Filing Date
US00146780A Expired - Lifetime US3855255A (en) 1970-05-27 1971-05-25 Process for the production of higher, polyunsaturated carboxylic acid ester and free acids

Country Status (6)

Country Link
US (1) US3855255A (enExample)
BE (1) BE767546A (enExample)
DE (1) DE2025830A1 (enExample)
FR (1) FR2093812A5 (enExample)
GB (1) GB1332971A (enExample)
NL (1) NL7105912A (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133890A (en) * 1977-01-05 1979-01-09 The Dow Chemical Company Hypolipidemic compositions and method employing derivatives of 4-(((1,3-benzodioxol-5-yl)methyl)amino)benzoic acid
US5066829A (en) * 1990-04-17 1991-11-19 Shell Oil Company Preparation of carboxylic acid esters
US5166409A (en) * 1991-11-25 1992-11-24 Shell Oil Company Preparation of carboxylic acid esters
US5166408A (en) * 1991-11-25 1992-11-24 Shell Oil Company Preparation of carboxylic acid esters
US5166410A (en) * 1991-11-25 1992-11-24 Shell Oil Company Preparation of carboxylic acid esters
US5227562A (en) * 1992-02-10 1993-07-13 Phillips Petroleum Company Ethylene dimerization

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660440A (en) * 1968-09-27 1972-05-02 Studiengesellschaft Kohle Mbh Nonadecapenta - 1 6 9 13 18-ene-10-methyl carboxylate and the production thereof
US3780074A (en) * 1969-03-19 1973-12-18 Exxon Research Engineering Co Preparation of alkadienoic acid esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660440A (en) * 1968-09-27 1972-05-02 Studiengesellschaft Kohle Mbh Nonadecapenta - 1 6 9 13 18-ene-10-methyl carboxylate and the production thereof
US3780074A (en) * 1969-03-19 1973-12-18 Exxon Research Engineering Co Preparation of alkadienoic acid esters

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133890A (en) * 1977-01-05 1979-01-09 The Dow Chemical Company Hypolipidemic compositions and method employing derivatives of 4-(((1,3-benzodioxol-5-yl)methyl)amino)benzoic acid
US5066829A (en) * 1990-04-17 1991-11-19 Shell Oil Company Preparation of carboxylic acid esters
US5166409A (en) * 1991-11-25 1992-11-24 Shell Oil Company Preparation of carboxylic acid esters
US5166408A (en) * 1991-11-25 1992-11-24 Shell Oil Company Preparation of carboxylic acid esters
US5166410A (en) * 1991-11-25 1992-11-24 Shell Oil Company Preparation of carboxylic acid esters
US5227562A (en) * 1992-02-10 1993-07-13 Phillips Petroleum Company Ethylene dimerization

Also Published As

Publication number Publication date
DE2025830A1 (de) 1971-12-09
FR2093812A5 (enExample) 1972-01-28
NL7105912A (enExample) 1971-11-30
BE767546A (fr) 1971-11-24
GB1332971A (en) 1973-10-10

Similar Documents

Publication Publication Date Title
US3780074A (en) Preparation of alkadienoic acid esters
US3635937A (en) Ethylene polymerization
Sustmann et al. Reactions of organic halides with olefins under Nio-catalysis. Formal addition of hydrocarbons to CC-double bonds
US4234454A (en) Diolefin dimerization catalyst and method for producing nitrosyl halides of iron triad metals
US3085102A (en) Process for producing alkyl tin halide compounds
EP1625109A1 (en) Process for the carbonylation of a conjugated diene
CN85109193A (zh) 以烯烃为原料制备二聚产物的方法
US3855255A (en) Process for the production of higher, polyunsaturated carboxylic acid ester and free acids
US3980683A (en) Process for carboxylation of olefins
EP0105704B1 (en) Process for the production of carboxylic acid esters and/or carboxylic acid
GB1600525A (en) Process for preparing unsaturated aliphatic acids or esters from aliphatic dienes
US4144278A (en) Diolefin dimerization using nitrosyl halides of iron triad metals
JPS63283756A (ja) オレフイン複分解用の活性持続改良触媒系
US3790607A (en) Carbonylation of fluorocarbon iodides
US4181707A (en) Diolefin dimerization catalyst and method for producing nitrosyl halides of iron triad metals
US3660440A (en) Nonadecapenta - 1 6 9 13 18-ene-10-methyl carboxylate and the production thereof
JPH0155284B2 (enExample)
US4071575A (en) Process for producing 2,6-dimethyl-1,3,6-octatriene
JP4118508B2 (ja) ルテニウム錯体の製造
US3855278A (en) Polybasic unsaturated carboxylic acid esters
US3641120A (en) Process for the production of long chain esters
US4169845A (en) Method of preparing transition metal-olefin complex compounds and alkali metal-transition metal-olefin complex compounds
US3238239A (en) Production of acrylic acid esters and amides
US3168581A (en) Production of cyclic dienes
US3364273A (en) Cyclooligomerization using nickel (0) polydentate ligand