WO2000007973A1 - Procede pour la preparation d'acide sorbique et d'esters d'acide sorbique ou de leurs derives - Google Patents

Procede pour la preparation d'acide sorbique et d'esters d'acide sorbique ou de leurs derives Download PDF

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Publication number
WO2000007973A1
WO2000007973A1 PCT/EP1999/005167 EP9905167W WO0007973A1 WO 2000007973 A1 WO2000007973 A1 WO 2000007973A1 EP 9905167 W EP9905167 W EP 9905167W WO 0007973 A1 WO0007973 A1 WO 0007973A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
sorbic acid
propyne
triphenylphosphine
acrylate
Prior art date
Application number
PCT/EP1999/005167
Other languages
German (de)
English (en)
Inventor
Thomas Barth
Norbert Rieber
Klaus Breuer
Martin Schäfer
Justin Wolf
Helmut Werner
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP99938299A priority Critical patent/EP1102740A1/fr
Priority to AU52856/99A priority patent/AU5285699A/en
Priority to CA002339736A priority patent/CA2339736A1/fr
Priority to JP2000563608A priority patent/JP2002522408A/ja
Publication of WO2000007973A1 publication Critical patent/WO2000007973A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to a process for the preparation of sorbic acid and sorbic acid esters or their derivatives.
  • Sorbic acid is currently produced on an industrial scale by reacting crotonaldehyde and ketene (DE 1 042 573, DE 1 059 899).
  • crotonaldehyde and ketene DE 1 042 573, DE 1 059 899.
  • the manufacture and handling of ketene is complex and requires complicated process engineering.
  • DE-OS 25 54 403 discloses a process for the catalytic coupling of allyl compounds to substituted olefins, with which sorbic acid esters from allyl alcohol and acrylic acid esters or acrylate and propene (but only "in traces", see Example 5) are producible.
  • EP 55 936 discloses a process by which sorbic acid can be prepared from butadiene and acetic acid via an intermediate (acetoxyhexenoic acid).
  • phenylacetylene can be reacted with inactivated olefins such as methyl 4-pentenoate or 4-pentenoate nitrile over a ruthenium catalyst, conjugated dienes being formed, but not with the carboxyl group conjugated alkadiene system such as sorbic acid and its esters.
  • inactivated olefins such as methyl 4-pentenoate or 4-pentenoate nitrile
  • conjugated dienes being formed, but not with the carboxyl group conjugated alkadiene system such as sorbic acid and its esters.
  • the object of the present invention was to provide a process for the preparation of sorbic acid and its esters or their derivatives from easily accessible starting materials To provide, which does not have the disadvantages of the prior art and provides the end product in high yields with respect to the acrylic compound reacted.
  • the process product is a compound of formula I.
  • R 1 and R 2 can have the meanings given above.
  • the alkyl or alkylene groups R 1 and R 2 can be straight-chain or branched.
  • the transition metal catalyst system preferably consists of a transition metal compound and a phosphine ligand.
  • a phosphonium salt is additionally added to the catalyst system.
  • an acid can be added to excess phosphine ligand.
  • the transition metal is preferably rhodium.
  • Suitable catalysts are, for example, rhodium, ruthenium or nickel complexes in combination with monodentate or bidentate phosphine ligands in a range from 0.1 to 10.0 mol% (the mol percentages given in each case relate to the compound of the formula used II.).
  • Rhodiumtris riarylphosphin chloride
  • Hydridodichlororhodium- bis triarylphosphine
  • Alkyldichlororhodiumbis triarylphosphine
  • Vinyldichlororhodiumbis triarylphosphine
  • cyclopentadienyl rutheniumbis triarylphosphine
  • Nickeldicarbonyl- bis triarylphosphine
  • Rhodiumtris triphenylphosphine
  • hydridodichlororhodium bis triphenylphosphine
  • R 1 OOCCHR 2 -CH 2 dichlororhodium bis (triphenylphosphine)
  • C 3 H 5 dichlororhodium bis (triphenylphosphine)
  • cyclopentadienyl ruthenium bis triphenylphosphine
  • the ligands occurring in the complexes are added to the reaction solution in the range from 0.4 to 40 mol%, particularly preferably 1 to 10 mol%. Mixtures of the ligands occurring in the complexes (0.4 to 40 mol%, particularly preferably 1 to 10 mol%) and further monodentate or bidentate phosphine ligands in the range from 0.1 to 10.0 mol% can also be used. %, very particularly preferably 1 to 10 mol%, are used.
  • ligands e.g.
  • multidentate ligands e.g. Bis (diphenylphosphino) methane, ethane or propane or 1,1,1-tris (diphenylphosphinomethyl) ethane used.
  • phosphonium salts e.g. Trialkylphosphonium chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate or triaryl phosphonium chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate used in the range from 0.001 to 40 mol%. Triphenylphosphonium chloride or triphenylphosphonium bromide in the range from 0.01 to 20 mol% are particularly preferred.
  • an organic or inorganic acid is added to a phosphine. Hydrogen chloride, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, tetrafluoroboric acid, trifluoromethanesulfonic acid or acetic acid are particularly preferred.
  • the process according to the invention is preferably carried out in an organic solvent.
  • Suitable solvents are ethers, hydrocarbons, cyclic amides, lactones or alcohols. Tetrahydrofuran, dioxane, ethylene glycol diethyl ether, benzene, toluene, xylene, gasoline, cyclohexane, N-methylpyrrolidone, ⁇ -butyrolactone, methanol, ethanol, propanol or butanol are particularly preferred.
  • acrylates used, propyne in condensed form or mixtures thereof can be used as solvents.
  • the process is preferably carried out at 20 to 200 ° C, particularly preferably at 40 to 120 ° C, and a pressure of 1 to 60 bar, preferably 1 to 20 bar, particularly preferably 1 to 5 bar.
  • the sorbic acid or the sorbic acid esters or their derivatives are obtained as trans-trans and cis-trans isomer mixtures.
  • the propyne and / or propadiene can be used in the process according to the invention in a mixture with other hydrocarbons.
  • This mixture can e.g. the propyne-containing fraction of the cracking gas treatment of a steam cracker or a propyne-propadiene mixture (MAPD).
  • mixtures of this type can also be used because these mixtures represent a favorable starting product base and lead to the desired product without a further refining step.
  • the addition of the propyne to the compound II surprisingly leads directly to the hexadiene system of the compound I.
  • triphenylphosphine hydrobromide triphenylphosphonium bromide, PPh 3 • HBr
  • a propyne stream (2 l / h) was introduced into this mixture at 80 ° C. for 20 hours.
  • the reaction discharge was then analyzed by GC analysis. With an acrylate conversion of 2%, a methyl sorbate selectivity of 18% was determined. Acrylate determined.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour la préparation de composés de la formule (I) dans laquelle R1 = H, alkyle C¿1?-C6, alcényle C1-C6, cycloalkyle C3-C6 ou bien phényle, et R?2¿ = H ou alkyle alkyle C¿1?-C3. Dans ce procédé, on fait réagir du propyne avec un composé de la formule (II), dans laquelle R?1 et R2¿ ont les significations précitées, en présence d'un système catalyseur à métal de transition.
PCT/EP1999/005167 1998-08-07 1999-07-20 Procede pour la preparation d'acide sorbique et d'esters d'acide sorbique ou de leurs derives WO2000007973A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99938299A EP1102740A1 (fr) 1998-08-07 1999-07-20 Procede pour la preparation d'acide sorbique et d'esters d'acide sorbique ou de leurs derives
AU52856/99A AU5285699A (en) 1998-08-07 1999-07-20 Method for producing sorbic acid and sorbic acid esters or derivatives thereof
CA002339736A CA2339736A1 (fr) 1998-08-07 1999-07-20 Procede pour la preparation d'acide sorbique et d'esters d'acide sorbique ou de leurs derives
JP2000563608A JP2002522408A (ja) 1998-08-07 1999-07-20 ソルビン酸およびソルビン酸エステルまたはその誘導体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998135783 DE19835783A1 (de) 1998-08-07 1998-08-07 Verfahren zur Herstellung von Sorbinsäure und Sorbinsäureestern oder deren Derivaten
DE19835783.4 1998-08-07

Publications (1)

Publication Number Publication Date
WO2000007973A1 true WO2000007973A1 (fr) 2000-02-17

Family

ID=7876819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/005167 WO2000007973A1 (fr) 1998-08-07 1999-07-20 Procede pour la preparation d'acide sorbique et d'esters d'acide sorbique ou de leurs derives

Country Status (6)

Country Link
EP (1) EP1102740A1 (fr)
JP (1) JP2002522408A (fr)
AU (1) AU5285699A (fr)
CA (1) CA2339736A1 (fr)
DE (1) DE19835783A1 (fr)
WO (1) WO2000007973A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781207A (zh) * 2010-03-11 2010-07-21 朱小刚 山梨酸正丁酯的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10004911A1 (de) * 2000-02-04 2001-08-09 Basf Ag Verfahren zur Herstellung von Sorbinsäure und Sorbinsäureestern oder deren Derivaten
CN102338779B (zh) * 2010-07-28 2013-05-08 内蒙古蒙牛乳业（集团）股份有限公司 检测奶酪中山梨酸含量的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737663A1 (fr) * 1995-04-12 1996-10-16 BASF Aktiengesellschaft Procédé pour la préparation de composés acétyléniquement insaturés

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737663A1 (fr) * 1995-04-12 1996-10-16 BASF Aktiengesellschaft Procédé pour la préparation de composés acétyléniquement insaturés

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781207A (zh) * 2010-03-11 2010-07-21 朱小刚 山梨酸正丁酯的制备方法
CN101781207B (zh) * 2010-03-11 2012-11-07 朱小刚 山梨酸正丁酯的制备方法

Also Published As

Publication number Publication date
JP2002522408A (ja) 2002-07-23
AU5285699A (en) 2000-02-28
DE19835783A1 (de) 2000-02-17
EP1102740A1 (fr) 2001-05-30
CA2339736A1 (fr) 2000-02-17

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