WO2000032564A1 - Procede de preparation d'esters d'acide hydroxame - Google Patents

Procede de preparation d'esters d'acide hydroxame Download PDF

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Publication number
WO2000032564A1
WO2000032564A1 PCT/EP1999/009121 EP9909121W WO0032564A1 WO 2000032564 A1 WO2000032564 A1 WO 2000032564A1 EP 9909121 W EP9909121 W EP 9909121W WO 0032564 A1 WO0032564 A1 WO 0032564A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
hydroxamic acid
sulfate
general formula
methyl
Prior art date
Application number
PCT/EP1999/009121
Other languages
German (de)
English (en)
Inventor
Paul Hanselmann
Stefan Hildbrand
Original Assignee
Lonza 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 Lonza Ag filed Critical Lonza Ag
Priority to AU13863/00A priority Critical patent/AU1386300A/en
Publication of WO2000032564A1 publication Critical patent/WO2000032564A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms

Definitions

  • the invention relates to a process for the preparation of hydroxamic acid esters of the general formula
  • RC, _ £ - alkyl and R 1 to R 3 are independently hydrogen or C, ⁇ - alkyl.
  • C, _ "- alkyl here and below are to be understood to mean all linear or branched primary, secondary or tertiary alkyl groups having 1 to n carbon atoms, that is to say C, _ 6 - alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl , sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neopentyl, hexyl or isohexyl.
  • the object of the present invention was therefore to provide a process for the preparation of the hydroxamic acid alkyl esters (I) defined above and in particular of the methyl methacrylate hydroxamic acid. According to the invention, this object is achieved by the method according to claim 1.
  • hydroxamic acid esters have the general formula
  • RC, _ 6 -alkyl and R 1 to R 3 independently of one another denote hydrogen or C, ⁇ , - alkyl from esters of the general formula
  • R ' is C M - alkyl, and R 1 to R 3 have the meanings mentioned above, to isolate by reaction with a Hydroxylammomumsalz with the addition of an aqueous strong base and anschhessende Alkyherung of Hydroxamklaresalzes thus obtained, without this, with a dialkyl sulfate of the general formula (RO) 2 SO 2 (III) or an alkyl chloride of the general formula R-Cl (IV), in which R in each case has the meaning given above, can be prepared in the presence of a base.
  • a dialkyl sulfate of the general formula (RO) 2 SO 2 (III) or an alkyl chloride of the general formula R-Cl (IV) in which R in each case has the meaning given above, can be prepared in the presence of a base.
  • Dimethyl sulfate or diethyl sulfate is preferably used as the dialkyl sulfate (III).
  • esters (II) used are preferably those in which R 'is methyl.
  • Hydroxamic acid esters (I) are preferably prepared in which R 1 , R 2 and R 3 independently of one another are hydrogen or methyl. These include, in particular, acrylic hydroxamic acid esters, methacrylic hydroxamic acid esters, ice and trans-croton hydroxamic acid esters and 3,3-dimethylacrylhydroxamic acid esters.
  • hydroxamic acid esters (I) in which R 1 and R 2 are hydrogen and R 3 is methyl, namely methacrylhydroxamic acid esters.
  • An alkali metal hydroxide is preferably used as the strong base in the reaction of the ester (II) with the hydroxylammonium salt (for example hydroxylamine hydrochloride or hydroxylammonium sulfate).
  • Sodium hydroxide is particularly preferred.
  • the strong base is advantageously used in an approximately stoichiometric amount, ie approximately the sum of the molar amounts of ester (II) and hydroxylammonium salt.
  • An alkali carbonate is preferably used as the base in the alkylation of the hydroxamic acid salt with the dialkyl sulfate (III).
  • Sodium carbonate is particularly preferred.
  • dialkyl sulfate is advantageously used in a slight excess, for example in an amount of 1.0 to 1.5 mol per 1 mol of the hydroxamic acid salt.
  • Both reaction steps of the process according to the invention are advantageously carried out at relatively low temperatures, for example at 0-10 ° C.
  • the solvent was distilled off from the combined organic phases in vacuo at low temperature ( ⁇ 30 ° C.). The residue was filtered and the separated solid was washed with ethyl acetate. The filtrate was concentrated on a rotary evaporator and freed from solvent residues in a fine vacuum.
  • Methyl methacrylate hydroxamic acid N-ethoxy-2-methylpropenamide
  • the reaction mixture was warmed to 10 ° C, stirred at 10 ° C for 24 hours and then filtered.
  • the filtrate was extracted with dichloromethane (3x150ml). After drying over sodium sulfate and distilling off the solvent on a rotary evaporator and stripping off solvent residues in a fine vacuum (4 h), 18.12 g of slightly yellowish product which was still contaminated with diethyl sulfate were obtained.
  • the dialkylated product could not be detected in ⁇ NMR ( ⁇ 3%).

Abstract

L'invention concerne des esters d'acide hydroxame de la formule générale (I) dans laquelle R désigne alkyle C1-C6 et R1 à R3 désignent indépendamment les uns des autres, hydrogène ou alkyle C¿1?-C4. Ces esters d'acide hydroxame sont obtenus dans le cadre d'un procédé en récipient unique, à partir des esters correspondants, par réaction avec un sel d'hydroxylammonium, puis avec un dialkylsulfate ou du chlorure d'alkyle. Les composés obtenus selon l'invention s'utilisent comme agents de blocage pour des isocyanates.
PCT/EP1999/009121 1998-12-03 1999-11-25 Procede de preparation d'esters d'acide hydroxame WO2000032564A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU13863/00A AU1386300A (en) 1998-12-03 1999-11-25 Method of producing hydroxamic acid esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98122927 1998-12-03
EP98122927.1 1998-12-03

Publications (1)

Publication Number Publication Date
WO2000032564A1 true WO2000032564A1 (fr) 2000-06-08

Family

ID=8233081

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/009121 WO2000032564A1 (fr) 1998-12-03 1999-11-25 Procede de preparation d'esters d'acide hydroxame

Country Status (2)

Country Link
AU (1) AU1386300A (fr)
WO (1) WO2000032564A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001055096A1 (fr) * 2000-01-25 2001-08-02 Lonza Ag Procede de preparation de n-alcoxy-n-alkylamides
US6891049B2 (en) 2000-03-15 2005-05-10 Lonza Ag Method for producing N-alkoxy-N-alkylamides
CN110804146A (zh) * 2019-12-06 2020-02-18 万华化学集团股份有限公司 一种存储稳定的封闭型异氰酸酯组合物及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB852176A (en) * 1957-08-19 1960-10-26 Ici Ltd Improved process for the manufacture of hydroxamic acids
GB852100A (en) * 1957-08-19 1960-10-26 Ici Ltd New hydroxamic acids and derivatives thereof
US5008455A (en) * 1984-10-24 1991-04-16 Nippon Soda Co., Ltd. Method for the production of hydroxylamine derivatives
WO1998046560A1 (fr) * 1997-04-14 1998-10-22 Eastman Chemical Company Procede permettant de preparer des derives d'hydroxylamine o-substitues de haute purete

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB852176A (en) * 1957-08-19 1960-10-26 Ici Ltd Improved process for the manufacture of hydroxamic acids
GB852100A (en) * 1957-08-19 1960-10-26 Ici Ltd New hydroxamic acids and derivatives thereof
US5008455A (en) * 1984-10-24 1991-04-16 Nippon Soda Co., Ltd. Method for the production of hydroxylamine derivatives
WO1998046560A1 (fr) * 1997-04-14 1998-10-22 Eastman Chemical Company Procede permettant de preparer des derives d'hydroxylamine o-substitues de haute purete

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001055096A1 (fr) * 2000-01-25 2001-08-02 Lonza Ag Procede de preparation de n-alcoxy-n-alkylamides
US6891049B2 (en) 2000-03-15 2005-05-10 Lonza Ag Method for producing N-alkoxy-N-alkylamides
CN110804146A (zh) * 2019-12-06 2020-02-18 万华化学集团股份有限公司 一种存储稳定的封闭型异氰酸酯组合物及其制备方法和应用

Also Published As

Publication number Publication date
AU1386300A (en) 2000-06-19

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