WO2004005244A1 - Procede de fabrication de o-alkyl-n-cyanformimidates sans catalyseurs - Google Patents

Procede de fabrication de o-alkyl-n-cyanformimidates sans catalyseurs Download PDF

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Publication number
WO2004005244A1
WO2004005244A1 PCT/EP2003/007200 EP0307200W WO2004005244A1 WO 2004005244 A1 WO2004005244 A1 WO 2004005244A1 EP 0307200 W EP0307200 W EP 0307200W WO 2004005244 A1 WO2004005244 A1 WO 2004005244A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
alkyl
cyanamide
catalyst
cyanoformimidates
Prior art date
Application number
PCT/EP2003/007200
Other languages
German (de)
English (en)
Other versions
WO2004005244B1 (fr
Inventor
Thomas Gastmer
Mario GÒMEZ
Thomas GÜTHNER
Original Assignee
Degussa Ag
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 Degussa Ag filed Critical Degussa Ag
Priority to AU2003281221A priority Critical patent/AU2003281221A1/en
Publication of WO2004005244A1 publication Critical patent/WO2004005244A1/fr
Publication of WO2004005244B1 publication Critical patent/WO2004005244B1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
    • C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings

Definitions

  • the present invention relates to a process for the catalyst-free preparation of O-alkyl-N-cyanoformimidates.
  • O-alkyl-N-cyanformimidates are of great importance as starting compounds for the production of medicinal and crop protection agents and of various functional chemicals.
  • the object of the present invention was therefore to provide a process for the catalyst-free preparation of O-alkyl-N-cyanoformimidates which starts from cyanamide and alkyl orthoformate and with which the target compound is present better yields are made available than is possible with the methods according to the prior art.
  • the product should be obtained in high purity. For this reason too, the use of catalysts should be avoided, which later have to be separated from the product and can lead to contamination of the product. In particular, a competitive process should be developed through the highest possible space-time yield.
  • This object was achieved in accordance with the present invention by adding the orthoformate component and the cyanamide component in a molar ratio of 1: 0.8 to 10.0, at pressures between 0.1 and 10 bar and in the temperature range between 40 and 180 ° C Implementation.
  • Orthoformic acid esters whose alkyl radical has 1 to 6 C atoms are preferred by the present invention.
  • the reaction according to the present invention must be carried out at a pressure of 0.1 to 10 bar and within a temperature range of 40 to 180 ° C., pressures between 1 and 5 bar and in particular atmospheric pressure and temperatures between 90 and 100 ° C. to be regarded as preferred are. At these temperature and pressure ranges, the reaction time is between a few minutes and 2 hours depending on the dosing time, although longer reaction times do not have a negative effect on the product quality and the yield.
  • the removal of the alkanols formed during the reaction from the reaction mixture has also proven to be advantageous, which should above all be carried out continuously.
  • the removal of the alcohols can be carried out in any manner known to the person skilled in the art and suitable for removing alcohols from a reaction mixture, the distillation naturally offering particular advantages.
  • the method according to the invention shows particular advantages when it is carried out without solvent, which is the preferred variant of the invention as well as the isolation of the product by vacuum distillation.
  • the method according to the invention is characterized by a very simple technical feasibility and furthermore by a high environmental compatibility, so that the requirements for a production which can be carried out on an industrial scale are fulfilled in an outstanding manner.
  • Ortho ants acid esters are stable under the selected reaction conditions, which is why the excess that may be used can be recovered virtually quantitatively and reused.
  • the reaction mixture consists of a single liquid phase in which the product thus obtained is of sufficient purity so that it can generally be processed without further purification.
  • the crude product can be purified by distillation, preferably in vacuo, whereby O-alkyl-N-cyanformimidate is obtained in almost quantitative yield.
  • Trimethyl orthoformate (520.0 ml, 4.75 mol) and cyanamide (68.5 g, 1.63 mmol) were placed in a flask with a reflux condenser and thermometer under nitrogen and heated to boiling.
  • Formic acid (5 ml, 0.132 mol) was then added and the mixture was refluxed for a further 5 hours.
  • excess trimethyl orthoformate was distilled off in vacuo and the remaining oil was distilled in vacuo (3.2 mmHg, 73-75 ° C.).
  • Trimethyl orthoformate (1 56.0 ml, 1, 425 mol) and cyanamide (20.55 g, 489 mmol) were placed in a flask with reflux condenser and thermometer under nitrogen and carefully heated to 95 ° C. The methanol formed was distilled off over a packed column. After no more methanol passed over, stirring was continued at 95 ° C. for a further 30 minutes. The reaction took about 90 minutes in total. After cooling, the excess trimethyl orthoformate was distilled off in vacuo and the remaining oil was distilled in vacuo (4.2 mbar, 74 ° C.).
  • Triethyl orthoformate (21 2.0 ml, 1, 1 56 mol) and cyanamide (20.55 g, 489 mmol) were placed in a flask with a reflux condenser and thermometer under nitrogen and carefully heated to 95.degree. The ethanol formed was distilled off over a packed column. After no more ethanol passed over, stirring was continued at 95 ° C. for a further 30 minutes. After cooling, excess triethyl orthoformate was distilled off in vacuo and the remaining oil was distilled in vacuo (0.06 mbar, 50 ° C.).

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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 fabrication de O-alkyl-N-cyanformimidates au cours duquel la réaction de cyanamide avec des alkylesters d'acide orthoformique dans un rapport molaire de 1 : 0,8 à 10 est effectuée sans addition de catalyseurs, à des pressions de 0,1 à 10 bars et des températures de 40 à 180 °C. Il est avantageux d'extraire du mélange de réaction de l'alcanol produit lors de la réaction, et de conduire la réaction globalement sans solvant. Le procédé selon l'invention permet d'obtenir de façon techniquement simple et écologique le produit avec un rendement et une pureté élevés.
PCT/EP2003/007200 2002-07-05 2003-07-04 Procede de fabrication de o-alkyl-n-cyanformimidates sans catalyseurs WO2004005244A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003281221A AU2003281221A1 (en) 2002-07-05 2003-07-04 Method for carrying out the catalyst-free production of o-alkyl-n-cyanoformimidates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10230311.8 2002-07-05
DE2002130311 DE10230311A1 (de) 2002-07-05 2002-07-05 Verfahren zur Katalysator-freien Herstellung von O-Alkyl-N-cyanformimidaten

Publications (2)

Publication Number Publication Date
WO2004005244A1 true WO2004005244A1 (fr) 2004-01-15
WO2004005244B1 WO2004005244B1 (fr) 2004-04-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/007200 WO2004005244A1 (fr) 2002-07-05 2003-07-04 Procede de fabrication de o-alkyl-n-cyanformimidates sans catalyseurs

Country Status (3)

Country Link
AU (1) AU2003281221A1 (fr)
DE (1) DE10230311A1 (fr)
WO (1) WO2004005244A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020724A1 (fr) * 2001-08-28 2003-03-13 Schering Corporation Inhibiteurs polycycliques de la phosphodiesterase v de la guanine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020724A1 (fr) * 2001-08-28 2003-03-13 Schering Corporation Inhibiteurs polycycliques de la phosphodiesterase v de la guanine

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AGASIMUNDIN, YANKANAGOUDA S. ET AL., J. ORG. CHEM., vol. 50, 1985, pages 2468 - 2474, XP002261800 *
BRIDSON P K ET AL: "1-SUBSTITUTED XANTHINES", SYNTHESIS, GEORG THIEME VERLAG. STUTTGART, DE, vol. 7, July 1995 (1995-07-01), pages 855 - 858, XP001153976, ISSN: 0039-7881 *
HOSMANE, RAMACHANDRA S. ET AL., J. ORG. CHEM., vol. 46, 1981, pages 1457 - 1465, XP002261801 *
HUFFMAN, ROBERT K. ET AL., J. ORG. CHEM., vol. 28, 1963, pages 1816 - 1821, XP001091329 *

Also Published As

Publication number Publication date
WO2004005244B1 (fr) 2004-04-08
AU2003281221A1 (en) 2004-01-23
DE10230311A1 (de) 2004-01-22

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