WO2005023749A2 - Procede de production d'esters carboniques asymetriques - Google Patents

Procede de production d'esters carboniques asymetriques Download PDF

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Publication number
WO2005023749A2
WO2005023749A2 PCT/EP2004/051990 EP2004051990W WO2005023749A2 WO 2005023749 A2 WO2005023749 A2 WO 2005023749A2 EP 2004051990 W EP2004051990 W EP 2004051990W WO 2005023749 A2 WO2005023749 A2 WO 2005023749A2
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WO
WIPO (PCT)
Prior art keywords
formula
glycol
reaction
alkyl
iii
Prior art date
Application number
PCT/EP2004/051990
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German (de)
English (en)
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WO2005023749A3 (fr
Inventor
Erich Dilk
Horst Surburg
Original Assignee
Symrise Gmbh & Co. Kg
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 Symrise Gmbh & Co. Kg filed Critical Symrise Gmbh & Co. Kg
Publication of WO2005023749A2 publication Critical patent/WO2005023749A2/fr
Publication of WO2005023749A3 publication Critical patent/WO2005023749A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a new process for producing asymmetrical carbonic acid esters by reacting monochloroformic acid esters with glycols.
  • the preferred route is via the monochloroformic acid esters.
  • the reaction of monochloroformic acid esters with alcohols takes place particularly advantageously in the presence of acid acceptors such as, for example, pyridine, quinoline, N, N-dimethylaniline or triethylamine.
  • acid acceptors such as, for example, pyridine, quinoline, N, N-dimethylaniline or triethylamine.
  • the reactions are carried out either in excess pyridine or in solvents such as dichloromethane, dichloroethane, ether, benzene or chlorobenzene (see U. Petersen in Houben-Weyl, Methods of Organic Chemistry, 4th edition, volume E4, page 68, H. Vernaleken in Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 14, page 591).
  • EP 21211 A1 describes the preparation of dimethyl carbonate in a two-phase system consisting of 45% aqueous sodium hydroxide solution and chlorobenzene.
  • the authors point out that, surprisingly, neither the dimethyl carbonate nor the particularly hydrolysis-susceptible methyl chloroformate are saponified under the alkaline conditions in this system and high product yields result (pages 9 and 10). A transfer of these conditions to the implementation of z.
  • B. Chloroformic acid menthyl ester with glycols delivered in its own experiments, however, the desired product only in the trace range. Presumably, insufficient mixing is achieved with the highly hydrophilic glycols and the chloroformic acid ester contained in the organic phase.
  • a base is used in order to partially or completely neutralize the HCl formed during the reaction
  • glycol of formula (II) and the chloroform ure ester of formula (III) are present in a homogeneous liquid phase during the reaction
  • R 1 C ⁇
  • R 2 , R 3 independently of one another hydrogen, C ⁇
  • X is a 2-valent aliphatic C ⁇
  • asymmetrical carbonic acid esters of the formula (I) sometimes have asymmetrical carbon atoms, so that optical isomerism can occur in them. Depending on the starting material used, they are therefore obtained as mixtures of the optical isomers or as pure isomers.
  • a polar aprotic compound in particular N-methyl-2-pyrrolidinone ()
  • N-methyl-2-pyrrolidinone is usually used as the solvent for the glycol of the formula (II), the chloroformate of the formula (III), the carbonic ester (I) and, if appropriate, the base, during the reaction NMP) or dimethylformamide (DMF) used; the use of N-methyl-2-pyrrolidinone is preferred.
  • a metal hydroxide dissolved in a suitable solvent is advantageously used as the base in the process according to the invention.
  • the use of an aqueous metal hydroxide is preferred; aqueous alkali hydroxide is preferably used. Potassium and sodium hydroxide in a more concentrated or dilute form are preferred as the alkali hydroxide solution aqueous solution is used, the use of equimolar amounts of alkali metal hydroxide, based on the chloroformate, being particularly preferred.
  • the glycol of the formula (II) is present in a molar excess over the chloroformate of the formula (III) during the entire reaction.
  • the molar ratio of the total glycol of formula (II) used to the total amount of chloroformate of formula (III) used is preferably in the range from 30: 1 to 1: 1, preferably in the range from 15: 1 to 2: 1. In this way it is almost completely prevented that both OH groups of the glycol used participate in the esterification reaction; the implementation is therefore essentially restricted to one OH group each.
  • the chloroformic acid ester and the base i.e. an aqueous alkali hydroxide solution
  • the proportion of base for example alkali metal hydroxide
  • the proportion of base is kept in molar deficiency with the chloroformic acid ester in the course of the metering in order to avoid hydrolysis of the chloroformic acid ester.
  • R 1 Ci-CiQ-Al yl, C2-C ⁇ alkenyl, optionally by one or more alkyl, alkenyl, alkynyl, hydroxy, amino, acetoxy, carboxy, carbalkoxy and / or carbamoyl groups substituted C5-Cg-cycloalkyl, C ⁇ -C ⁇ aryl or C7-C-
  • R 2 , R 3 independently of one another hydrogen, C- -C-iQ-alkyl, C2-C ⁇
  • Aralkyl which are optionally substituted by hydroxy, amino, acetoxy, carboxy, carbalkoxy, carbamoyl or interrupted by ether oxygen,
  • X is a divalent aliphatic CjC-iQ residue or araliphatic C7-
  • R 1 C-
  • R 2 , R 3 independently of one another are hydrogen or CjC-jrj-alkyl, which are optionally substituted by hydroxy,
  • R 1 C ⁇
  • the process according to the invention - preferably in one of its preferred embodiments - is suitable for synthesizing an asymmetrical carbonic acid ester according to one of the formulas below:
  • radicals R 1 , R 2 , R 3 , X and n are then selected in the starting materials so that the products mentioned are obtained.
  • the reaction of the chloroformate with the glycol is advantageously carried out at a temperature in the range from -20 to 80 ° C; Temperatures from 0 to 50 ° C are preferred.
  • Reaction mixture / product mixture After completion of the reaction, water is added, for example, and the phases are separated. After appropriate washes / extractions, the organic phase is usually concentrated and the crude product obtained is purified to the end product quality by suitable cleaning measures, such as thin-film evaporator distillation.
  • suitable cleaning measures such as thin-film evaporator distillation.
  • NMP as a solvent
  • water e.g. as a solvent for alkali hydroxide
  • a water / N MP / glycol phase is regularly obtained during processing. If the components of this water / NMP / glycol phase are to be reused, water and then NMP / glycol as a mixture are advantageously distilled off from this phase. The NMP / glycol mixture thus recovered is then used again in the desired manner.
  • NMP / ethylene glycol mixture 1030 g of water, 92 g of intermediate fraction and 1540 g of NMP / ethylene glycol mixture are distilled from the aqueous phase under reduced pressure.
  • the NMP / ethylene glycol mixture thus obtained which contains 683 g NMP and 858 g ethylene glycol, can be used again in a subsequent batch.

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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

L'invention concerne un procédé de production d'un ester carbonique asymétrique de formule (I), ce procédé consistant à faire réagir un glycol de formule (II) avec un chloroformiate de formule (III) pour obtenir l'ester carbonique (I). Avant ou pendant la réaction, une base est ajoutée pour neutraliser partiellement ou totalement le HCl produit. Pendant la réaction, le glycol de formule (II) et le chloroformiate de formule (III) se trouvent dans une phase liquide homogène.
PCT/EP2004/051990 2003-09-10 2004-09-01 Procede de production d'esters carboniques asymetriques WO2005023749A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10341699.4 2003-09-10
DE10341699A DE10341699A1 (de) 2003-09-10 2003-09-10 Verfahren zur Herstellung unsymmetrischer Kohlensäureester

Publications (2)

Publication Number Publication Date
WO2005023749A2 true WO2005023749A2 (fr) 2005-03-17
WO2005023749A3 WO2005023749A3 (fr) 2005-05-26

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PCT/EP2004/051990 WO2005023749A2 (fr) 2003-09-10 2004-09-01 Procede de production d'esters carboniques asymetriques

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DE (1) DE10341699A1 (fr)
WO (1) WO2005023749A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008145525A3 (fr) * 2007-05-25 2009-08-13 Hoffmann La Roche Procédé de préparation d'un dérivé de dibenzo [b,d]azépin-6-one
WO2009123355A2 (fr) * 2008-04-01 2009-10-08 Takasago International Corporation Composition d'agent de sensation de fraîcheur et composition d'agent de stimulation sensorielle
CN102625866A (zh) * 2009-04-01 2012-08-01 高露洁-棕榄公司 薄荷醇衍生化合物及其作为口腔和全身活性剂的用途
JP2012522771A (ja) * 2009-04-01 2012-09-27 コルゲート・パーモリブ・カンパニー 口腔ケア組成物における使用のための抗バイオフィルムカーボネート化合物
US9802885B2 (en) 2011-09-01 2017-10-31 Takasago International Corporation (Usa) Substituted cyclohexane compounds
WO2020030582A1 (fr) 2018-08-06 2020-02-13 Basf Se Procédé de production d'esters d'acide carbonique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419543A (en) * 1964-10-01 1968-12-31 Liggett & Myers Inc Carbonate esters of flavorants
EP0021211A1 (fr) * 1979-06-22 1981-01-07 Bayer Ag Procédé de préparation de carbonate de diméthyle
US4509537A (en) * 1983-04-04 1985-04-09 Philip Morris Incorporated Smoking compositions
EP0583651A1 (fr) * 1992-08-06 1994-02-23 Haarmann & Reimer Gmbh Compositions donnant une impression de fraicheur physiologique et composés actifs utilisables dans ces compositions
WO1999028288A1 (fr) * 1997-11-27 1999-06-10 Firmenich S.A. Nouveaux composes derives du menthol et leur utilisation en tant qu'agent rafraichissant
GB2401865A (en) * 2003-05-22 2004-11-24 Givaudan Sa Antibacterial and antifungal glycerol monocarbonates

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419543A (en) * 1964-10-01 1968-12-31 Liggett & Myers Inc Carbonate esters of flavorants
EP0021211A1 (fr) * 1979-06-22 1981-01-07 Bayer Ag Procédé de préparation de carbonate de diméthyle
US4509537A (en) * 1983-04-04 1985-04-09 Philip Morris Incorporated Smoking compositions
EP0583651A1 (fr) * 1992-08-06 1994-02-23 Haarmann & Reimer Gmbh Compositions donnant une impression de fraicheur physiologique et composés actifs utilisables dans ces compositions
WO1999028288A1 (fr) * 1997-11-27 1999-06-10 Firmenich S.A. Nouveaux composes derives du menthol et leur utilisation en tant qu'agent rafraichissant
GB2401865A (en) * 2003-05-22 2004-11-24 Givaudan Sa Antibacterial and antifungal glycerol monocarbonates

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE BEILSTEIN [Online] BEILSTEIN INSTITUT ZUR FOERDERUNG DER CHEMISCHEN WISSENSCHAFTEN; XP002320470 Database accession no. 8584834 & GARDNER HW & HOU CT: J. AM. OIL CHEM. SOC., Bd. 76, Nr. 10, 1999, Seiten 1151-1156, *
DATABASE BEILSTEIN [Online] BEILSTEIN INSTITUT ZUR FOERDERUNG DER CHEMISCHEN WISSENSCHAFTEN; XP002320471 Database accession no. 773995 & EINHORN & ROTHLAUF: JUSTUS LIEBIGS ANN. CHEM., Bd. 382, 1911, Seite 263, *
DATABASE BEILSTEIN [Online] BEILSTEIN INSTITUT ZUR FOERDERUNG DER CHEMISCHEN WISSENSCHAFTEN; XP002320472 Database accession no. 5324476 & BANDIN M ET AL.: EUR. J. ORG. CHEM., Bd. 3, 2000, Seiten 491-498, *
DATABASE BEILSTEIN [Online] BEILSTEIN INSTITUT ZUR FOERDERUNG DER CHEMISCHEN WISSENSCHAFTEN; XP002320473 Database accession no. 5142350 & CHU F ET AL: TETRAHEDRON LETT., Bd. 40, Nr. 10, 1999, Seiten 1847-1850, *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008145525A3 (fr) * 2007-05-25 2009-08-13 Hoffmann La Roche Procédé de préparation d'un dérivé de dibenzo [b,d]azépin-6-one
US7579464B2 (en) 2007-05-25 2009-08-25 Hoffmann-La Roche Inc. Process for preparation of enantiomerically pure compounds
CN101679278B (zh) * 2007-05-25 2013-08-14 霍夫曼-拉罗奇有限公司 用于制备二苯并[b,d]氮杂*-6-酮衍生物的方法
WO2009123355A3 (fr) * 2008-04-01 2009-12-10 Takasago International Corporation Composition d'agent de sensation de fraîcheur et composition d'agent de stimulation sensorielle
WO2009123355A2 (fr) * 2008-04-01 2009-10-08 Takasago International Corporation Composition d'agent de sensation de fraîcheur et composition d'agent de stimulation sensorielle
US8632792B2 (en) 2008-04-01 2014-01-21 Takasago International Corporation Cooling sensation agent composition and sensory stimulation agent composition
CN102625866A (zh) * 2009-04-01 2012-08-01 高露洁-棕榄公司 薄荷醇衍生化合物及其作为口腔和全身活性剂的用途
JP2012522771A (ja) * 2009-04-01 2012-09-27 コルゲート・パーモリブ・カンパニー 口腔ケア組成物における使用のための抗バイオフィルムカーボネート化合物
US10426752B2 (en) 2009-04-01 2019-10-01 Colgate-Palmolive Company Menthol-derivative compounds and use thereof as oral and systemic active agents
US9802885B2 (en) 2011-09-01 2017-10-31 Takasago International Corporation (Usa) Substituted cyclohexane compounds
EP3262955A2 (fr) 2011-09-01 2018-01-03 Takasago International Corporation (USA) Nouveaux composés de cyclohéxane substitués
WO2020030582A1 (fr) 2018-08-06 2020-02-13 Basf Se Procédé de production d'esters d'acide carbonique
CN112513015A (zh) * 2018-08-06 2021-03-16 巴斯夫欧洲公司 生产碳酸酯的方法
CN112513015B (zh) * 2018-08-06 2024-04-02 巴斯夫欧洲公司 生产碳酸酯的方法

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Publication number Publication date
WO2005023749A3 (fr) 2005-05-26
DE10341699A1 (de) 2005-04-28

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