WO2002014257A2 - SYNTHESE DE Α,Ω-DIESTERS - Google Patents

SYNTHESE DE Α,Ω-DIESTERS Download PDF

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Publication number
WO2002014257A2
WO2002014257A2 PCT/EP2001/009241 EP0109241W WO0214257A2 WO 2002014257 A2 WO2002014257 A2 WO 2002014257A2 EP 0109241 W EP0109241 W EP 0109241W WO 0214257 A2 WO0214257 A2 WO 0214257A2
Authority
WO
WIPO (PCT)
Prior art keywords
process according
reaction
diesters
ketone
mols
Prior art date
Application number
PCT/EP2001/009241
Other languages
English (en)
Other versions
WO2002014257A3 (fr
Inventor
Pietro Tundo
Sofia Memoli
Maurizio Selva
Original Assignee
Consorzio Interuniversitario Nazionale La Chimica Per L'ambiente
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 Consorzio Interuniversitario Nazionale La Chimica Per L'ambiente filed Critical Consorzio Interuniversitario Nazionale La Chimica Per L'ambiente
Priority to AU2001284002A priority Critical patent/AU2001284002A1/en
Publication of WO2002014257A2 publication Critical patent/WO2002014257A2/fr
Publication of WO2002014257A3 publication Critical patent/WO2002014257A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

Definitions

  • the present invention relates to the transformation of alicyclic ketones with an ⁇ -hydrogen into the corresponding ⁇ , ⁇ -diesters (also known as ⁇ , ⁇ -dicarboxylic acid diesters), by the reaction with organic carbonates.
  • ⁇ , ⁇ -dicarboxylic acid diesters are important intermediates for the preparation of dicarboxylic acids which are used in huge amounts in the industrial synthesis of polyesters and poly amides.
  • Adipic acid the starting material in the synthesis of nylon-6,6, is produced by catalytic oxidation of cyclohexanone with nitric acid, a process which generates N 2 0 as a byproduct. This production alone, causes a 10% of the annual increase of in N 2 0 levels with consequences on the ozone layer and on the greenhouse effect.
  • US5453535 and US5786502 describe a process for preparing ⁇ , ⁇ - dicarboxylic acid diesters by reaction of cycloalkanones with carbonic diesters in the presence of nitrogen bases and strongly basic agents, respectively.
  • R 1? R 2 and R 3 which can be the same or different, are hydrogen, linear or branched C ⁇ -C 8 -alkyl, alkenyl or aryl groups; R 4 is a C r C 2 alkyl group, benzyl or phenyl; n can vary from 1 to 20; where n>l, R2 and R3 are independently bonded to each carbon atom.
  • the reaction with an asymmetrical carbonate gives the corresponding products structurally similar to III.
  • phase transfer agents such as phosphonium salts, ammonium salts, crown ethers or preferably polyethylene glycols (PEGs), at temperatures of 100 to 250°C, for 1 to 24 hours.
  • the reaction is preferably carried out under N 2 . Even though PEG S having different molecular weight can be used as phase transfer agents, PEG
  • PEG is preferably used in 0.05-1.0 wt ratio with respect to the ketone, preferably of 0.1 - 0.6 and even more preferably of about 0.2.
  • the molar ratio between dialkylcarbonate and ketone may be from 1 : 1 to 30:1 preferably about 20: 1.
  • Cesium and potassium carbonates are used in amounts of 0.01-3 moles per mole of ketone.
  • a ratio of 0.1 - 2.0 is advantageus, preferably of about 0.2 mols/mole ketone. It has been moreover surprisingly found that the reaction takes place in a particularly favourable way if an alcohol (R 4 OH) is used as a co-solvent, in amount of 1 - 50 mols per mole of ketone, preferably 2-20 mols per mole of ketone and even more preferably of about 5 mols per mole of ketone.
  • ⁇ , ⁇ -diesters alkylated in position 2 or in positions 2 and ( ⁇ -1) are formed in a variable amount.
  • the presence of such intermediates may possibly be desired in the industrial synthesis of polyesters and polyamides.
  • the synthesis of ⁇ , ⁇ -diesters can be carried out starting from the ⁇ -ketoesters IV, as shown in the following scheme 2:
  • ⁇ -ketoesters IV are reacted with an alcohol R 4 OH, where R4 is as above defined, in a 2-20 molar excess with respect to IV, in the presence of cesium or potassium carbonates as catalyst and of a phase-transfer agent, in the conditions indicated above, yielding III.
  • 1,6-hexanedioic acid 2 methyl- 1,6-hexanedioic 2,5-dimethyl-l,6-hexanedioic dimethylester acid dimethylester acid dimethylester
  • Cyclohexanone (0.6 g, 0.006 mols), dimethylcarbonate (11.8 g, 0.12 mols), cesium carbonate (3.9 g, 0.012 mols), PEG 250 (0.6 g, 100% weight) and methanol (3.7 g, 0.12 mols) are reacted in autoclave at 200°C for 6 hours, under magnetical stirring.
  • the reaction mixture is dried under vacuum and analysed by GC with the usual procedures. Unreacted cyclohexanone was 23%; 1,7-heptanedioic acid dimethylester (dimethylpimelate) was 41% and 2-methyl- 1,7-heptanedioic acid dimethylester was 3%.
  • Cyclopentanone (0.5 g, 0.006 mols), dimethylcarbonate (11.8 g, 0.12 mols), potassium carbonate (0.08 g, 0.0006 mols), PEG 250 (0.25 g, 50% weight), and methanol (3.7 g, 0.12 mols) are reacted in autoclave at 220°C for 4 hours, under magnetical stirring.
  • the reaction mixture is dried under vacuum and analysed by GC with the usual procedures.
  • the ⁇ -ketoester 2-methoxycarbonyl cyclopentanone (1.5 g, 0.01 mols) is reacted with Cs 2 C0 3 (0.16 g, 0.0005 mols), PEG250 (0.33 g, 20% weight) and methanol (6.2 g, 0.2 mols), at 200°C for 6 hours, under N 2 .
  • the reaction mixture is dried under vacuum and analysed by GC with the usual procedures. Conversion was 100%; 1,6-hexanedioic acid dimethylester (dimethyladipate) formation was 98%.
  • the ⁇ -ketoester 2-methoxycarbonyl cyclohexanone (1.6 g, 0.01 mols) is reacted with Cs 2 C0 3 (0.16 g, 0.0005 mols), PEG 250 (0.33 g, 20% weight) and methanol (6.2 g, 0.2 mols), at 200°C for 6 hours, under N 2 .
  • the reaction mixture is dried under vacuum and analysed by GC with the usual procedures. Conversion was 100%; 1,7-heptanedioic acid dimethylester (dimethylpimelate) formation was 98%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne la transformation de cétones alicycliques comportant un α-hydrogène en α,Ω-diesters correspondants, par réaction avec des carbonates organiques.
PCT/EP2001/009241 2000-08-11 2001-08-10 SYNTHESE DE Α,Ω-DIESTERS WO2002014257A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001284002A AU2001284002A1 (en) 2000-08-11 2001-08-10 Synthesis of alpha,omega-diesters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22435300P 2000-08-11 2000-08-11
US60/224,353 2000-08-11

Publications (2)

Publication Number Publication Date
WO2002014257A2 true WO2002014257A2 (fr) 2002-02-21
WO2002014257A3 WO2002014257A3 (fr) 2002-09-12

Family

ID=22840297

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/009241 WO2002014257A2 (fr) 2000-08-11 2001-08-10 SYNTHESE DE Α,Ω-DIESTERS

Country Status (2)

Country Link
AU (1) AU2001284002A1 (fr)
WO (1) WO2002014257A2 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1540209A (fr) * 1966-10-10 1968-09-20 Techni Chem Co The Procédé perfectionné de préparation d'alkanes alpha, oméga-disubstitués
EP0632010A1 (fr) * 1993-07-01 1995-01-04 BASF Aktiengesellschaft Procédé de préparation de diesters d'acides alpha, oméga-dicarboxyliques
EP0643036A1 (fr) * 1993-09-13 1995-03-15 Hüls Aktiengesellschaft Procédé de préparation d'esters d'acide pimélique
EP0812817A1 (fr) * 1996-06-13 1997-12-17 Hüls Aktiengesellschaft Procédé pour la préparation de hauts-esters d'acides alpha, omega-dicarboxyliques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1540209A (fr) * 1966-10-10 1968-09-20 Techni Chem Co The Procédé perfectionné de préparation d'alkanes alpha, oméga-disubstitués
EP0632010A1 (fr) * 1993-07-01 1995-01-04 BASF Aktiengesellschaft Procédé de préparation de diesters d'acides alpha, oméga-dicarboxyliques
EP0643036A1 (fr) * 1993-09-13 1995-03-15 Hüls Aktiengesellschaft Procédé de préparation d'esters d'acide pimélique
EP0812817A1 (fr) * 1996-06-13 1997-12-17 Hüls Aktiengesellschaft Procédé pour la préparation de hauts-esters d'acides alpha, omega-dicarboxyliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. SELVA ET AL: "The addition reaction of dialkyl carbonates to ketones" GAZZETTA CHIMICA ITALIANA, vol. 123, no. 9, September 1993 (1993-09), pages 515-518, XP008002145 cited in the application *

Also Published As

Publication number Publication date
AU2001284002A1 (en) 2002-02-25
WO2002014257A3 (fr) 2002-09-12

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