[go: up one dir, main page]

WO2004031128A1 - Improved method for the production of n-substituted amides from nitriles - Google Patents

Improved method for the production of n-substituted amides from nitriles Download PDF

Info

Publication number
WO2004031128A1
WO2004031128A1 PCT/EP2003/010277 EP0310277W WO2004031128A1 WO 2004031128 A1 WO2004031128 A1 WO 2004031128A1 EP 0310277 W EP0310277 W EP 0310277W WO 2004031128 A1 WO2004031128 A1 WO 2004031128A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
alkyl
substituted
radical
alcohol
Prior art date
Application number
PCT/EP2003/010277
Other languages
German (de)
French (fr)
Inventor
Wolfram Hendel
Wolfgang Skranc
Peter Pöchlauer
Martin Weisgram
Original Assignee
Dsm Fine Chemicals Austria Nfg 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 Dsm Fine Chemicals Austria Nfg Gmbh & Co Kg filed Critical Dsm Fine Chemicals Austria Nfg Gmbh & Co Kg
Priority to AU2003267367A priority Critical patent/AU2003267367A1/en
Publication of WO2004031128A1 publication Critical patent/WO2004031128A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • 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

Landscapes

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

Abstract

An improved method for the production of N-substituted amides of formula RCONHR1 (I) wherein R represents an optionally monosubstituted or polysubstituted C1-C20-alkyl-, C5 -C20-aryl- or C5-C20--heterocyclic radical and R1 represents an optionally monosubstituted or polysubstituted C1-C20-alkyl- or C5-C20-aryl radical from corresponding nitriles of formula RCN (II) wherein R1 is defined as above, wherein a nitril of formula (II) is reacted in polyphosphoric acid with an alcohol of formula R10H (III) wherein R1 is as defined above, in the presence of a compound from the group consisting of phosphorpentoxide, phosphoroxychloride, sulfurylchloride, dialkylcarbonate and dialkylsulfate at a temperature of 80 -190 °C to form the corresponding N-substituted amide.

Claims

Patentansprüche: claims:
1. Verbessertes Verfahren zur Herstellung von N-substituierten Amiden der Formel1. Improved process for the preparation of N-substituted amides of the formula
RCONHR1 (I) in der R einen gegebenenfalls ein- oder mehrfach substituierten CrC2o-Alkyl-, C5- C20-Aryl- oder C5-C2o-Heterocyclusrest und R1 einen gegebenenfalls ein- oder mehrfach substituierten CrC20-Alkyl-oder C5-C2o-Arylrest bedeuten aus den korrespondierenden Nitrilen der FormelRCONHR1 (I) in which R represents an optionally mono- or polysubstituted -C 2 o alkyl, C 5 - C 20 aryl or C 5 -C 2 o-heterocyclic radical and R1 is an optionally mono- or poly-substituted CrC 20 - Alkyl or C 5 -C 2 o-aryl radical mean from the corresponding nitriles of the formula
RCN (II) in der R wie oben definiert ist, dadurch gekennzeichnet, dass ein Nitril der Formel (II) in Polyphosphorsäure mit einem Alkohol der FormelRCN (II) in which R is as defined above, characterized in that a nitrile of the formula (II) in polyphosphoric acid with an alcohol of the formula
R10H (III) in der R1 wie oben definiert ist, in Gegenwart einer Verbindung aus der Gruppe Phosphorpentoxid, Phosphoroxychlorid, Sulfurylchlorid, Dialkylcarbonat und Dialkylsulfat bei einer Temperatur zwischen 80 und 190°C zu dem entsprechenden N- substituierten Amid umgesetzt wird.R10H (III) in which R1 is as defined above, is reacted in the presence of a compound from the group phosphorus pentoxide, phosphorus oxychloride, sulfuryl chloride, dialkyl carbonate and dialkyl sulfate at a temperature between 80 and 190 ° C. to give the corresponding N-substituted amide.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass Nitrile der Formel (II) in der R einen gesättigten oder ein- oder mehrfach ungesättigten, linearen, verzweigten oder cyclischen, polycyclischen oder überbrückten cyclischen C1-C20- Alkylrest, einen Cs-C2o-Aryl- oder C5-C2o-Heterocyclusrest bedeutet, wobei die Reste gegebenenfalls ein- oder mehrfach durch gegebenenfalls substituierte Aryl- oder Heteroarylgruppen, Cι-C6-Alkyl-, Halogen-, CrCβ-Alkoxy-, Aryloxy-, bevorzugt C6-C2o-Aryloxy-, C C6-Alkylthio-, Alkylamino-, bevorzugt CrCβ-Alkylamino-, Arylamino-, bevorzugt C6-C20-Arylamino-, Ether-* Thioether, Carbonsäure-, Carbonsäureester-, Carbonsäureamid-, Sulfoxid-, Sulfon-, Sulfonsäure, Sulfonsäu- reester-, Sulfinsäure-, Cyano- oder Nitrogruppen substituiert sein können, mit einem Alkohol der Formel (III) in der R1 einen gesättigten, linearen oder verzweigten Cι-C6-Alkylrest oder einen Phenylrest bedeutet, wobei die Reste gegebenen- falls ein- oder mehrfach durch Halogen oder Phenyl susbtituiert sein können, umgesetzt werden.2. The method according to claim 1, characterized in that nitriles of the formula (II) in which R is a saturated or mono- or polyunsaturated, linear, branched or cyclic, polycyclic or bridged cyclic C1-C20-alkyl radical, a Cs-C 2 means o-aryl or C 5 -C 2 o-heterocycle radical, where the radicals are optionally substituted one or more times by optionally substituted aryl or heteroaryl groups, C 1 -C 6 -alkyl, halogen, CrCβ-alkoxy, aryloxy, preferably C 6 -C 2 o-aryloxy, CC 6 alkylthio, alkylamino, preferably CrCβ alkylamino, arylamino, preferably C 6 -C 20 arylamino, ether * thioether, carboxylic acid, carboxylic acid ester, Carboxamide, sulfoxide, sulfonic, sulfonic acid, sulfonic acid ester, sulfinic acid, cyano or nitro groups can be substituted, with an alcohol of formula (III) in R1 a saturated, linear or branched C 1 -C 6 alkyl radical or denotes a phenyl radical, the radicals given if one or more can be substituted by halogen or phenyl, are reacted.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass Nitrile der Formel (II) eingesetzt werden, in der R einen gesättigten oder einfach ungesättigten, linearen verzeigten oder cyclischen CrC12-Alkylrest, einen Cs-C-io-Arylrest oder C5-C10- Heterocyclusrest bedeutet, der gegebenenfalls ein- oder mehrfach durch CrC4- Alkyl, C-ι-C -Alkoxy, Phenyl, Carbonsäure, Halogen, Cyano oder Nitro substituiert sein kann.3. The method according to claim 1, characterized in that nitriles of the formula (II) are used in which R is a saturated or monounsaturated, linear branched or cyclic CrC 12 alkyl radical, a Cs-C-io-aryl radical or C 5 - C1 0 - heterocycle radical, which can optionally be substituted one or more times by CrC 4 alkyl, C 1 -C 4 alkoxy, phenyl, carboxylic acid, halogen, cyano or nitro.
4Nerfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Molverhältnis von Nitril der Formel (II) zu Alkohol der Formel (IM) 1 :1 bis 1 :5 beträgt.4Nerfahren according to claim 1, characterized in that the molar ratio of nitrile of the formula (II) to alcohol of the formula (IM) is 1: 1 to 1: 5.
5. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Molverhältnis von Polyphosphorsäure zu Alkohol der Formel (IM) 1 :0,1 bis 1 :2 beträgt.5. The method according to claim 1, characterized in that the molar ratio of polyphosphoric acid to alcohol of the formula (IM) is 1: 0.1 to 1: 2.
6. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Molverhältnis von Alkohol zu Phosphorpentoxid, Phosphoroxychlorid, Sulfurylchlorid, Dialkylcarbonat oder Dialkylsulfat 1 :0,1 bis 1 :2 beträgt.6. The method according to claim 1, characterized in that the molar ratio of alcohol to phosphorus pentoxide, phosphorus oxychloride, sulfuryl chloride, dialkyl carbonate or dialkyl sulfate is 1: 0.1 to 1: 2.
7.Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Dialkylcarbonat und das Dialkylsulfat 1 bis 6 C-Atome in der Alkylkette aufweisen.7. The method according to claim 1, characterized in that the dialkyl carbonate and the dialkyl sulfate have 1 to 6 carbon atoms in the alkyl chain.
δ.Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass kommerziell erhältliche, etwa 85%ige Polyphosphorsäure eingesetzt wird.δ.Verfahren according to claim 1, characterized in that commercially available, about 85% polyphosphoric acid is used.
9. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Reaktionstemperatur bei 100 bis 170 C liegt. 9. The method according to claim 1, characterized in that the reaction temperature is 100 to 170 C.
0. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass bei Verwendung von Dialkylcarbonaten, die Reaktion gegebenenfalls in Abwesenheit des Alkohols der Formel (III) durchgeführt wird. 0. The method according to claim 1, characterized in that when using dialkyl carbonates, the reaction is optionally carried out in the absence of the alcohol of the formula (III).
PCT/EP2003/010277 2002-10-01 2003-09-16 Improved method for the production of n-substituted amides from nitriles WO2004031128A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003267367A AU2003267367A1 (en) 2002-10-01 2003-09-16 Improved method for the production of n-substituted amides from nitriles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA1483/2002 2002-10-01
AT0148302A AT413101B (en) 2002-10-01 2002-10-01 IMPROVED METHOD FOR THE PRODUCTION OF N-SUBSTITUTED AMIDES FROM NITRILES

Publications (1)

Publication Number Publication Date
WO2004031128A1 true WO2004031128A1 (en) 2004-04-15

Family

ID=32046366

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/010277 WO2004031128A1 (en) 2002-10-01 2003-09-16 Improved method for the production of n-substituted amides from nitriles

Country Status (3)

Country Link
AT (1) AT413101B (en)
AU (1) AU2003267367A1 (en)
WO (1) WO2004031128A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012202885A1 (en) 2012-02-24 2012-05-10 Symrise Ag Producing menthane carbaldehyde, menthane carboxylic acid or its secondary product, comprises reacting an ester of menthane glycidic carbaldehyde with menthane
CN112004796A (en) * 2018-04-27 2020-11-27 昭和电工株式会社 Process for producing N, N-disubstituted amide and catalyst for producing N, N-disubstituted amide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246199A (en) * 1977-06-08 1981-01-20 Bayer Aktiengesellschaft Process for the preparation of N-alkyl-substituted carboxylic acid amides
EP1182191A1 (en) * 2000-08-10 2002-02-27 INTERNATIONAL FLAVORS & FRAGRANCES INC. Method for making amides
WO2003011816A1 (en) * 2001-07-31 2003-02-13 Millennium Specialty Chemicals, Inc. Process for obtaining n-monosubstituted amides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246199A (en) * 1977-06-08 1981-01-20 Bayer Aktiengesellschaft Process for the preparation of N-alkyl-substituted carboxylic acid amides
EP1182191A1 (en) * 2000-08-10 2002-02-27 INTERNATIONAL FLAVORS & FRAGRANCES INC. Method for making amides
WO2003011816A1 (en) * 2001-07-31 2003-02-13 Millennium Specialty Chemicals, Inc. Process for obtaining n-monosubstituted amides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LEBEDEV M Y ET AL: "Lower primary alkanols and their esters in a Ritter-type reaction with nitriles. An efficient method for obtaining N-primary-alkyl amides", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 43, no. 8, 18 February 2002 (2002-02-18), pages 1397 - 1399, XP004334949, ISSN: 0040-4039 *
MARTINEZ A G ET AL: "AN IMPROVED MODIFICATION OF RITTER REACTION", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 30, 1989, pages 581 - 582, XP001119550, ISSN: 0040-4039 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012202885A1 (en) 2012-02-24 2012-05-10 Symrise Ag Producing menthane carbaldehyde, menthane carboxylic acid or its secondary product, comprises reacting an ester of menthane glycidic carbaldehyde with menthane
CN112004796A (en) * 2018-04-27 2020-11-27 昭和电工株式会社 Process for producing N, N-disubstituted amide and catalyst for producing N, N-disubstituted amide
CN112004796B (en) * 2018-04-27 2023-06-06 株式会社力森诺科 Method for producing N,N-disubstituted amide and catalyst for producing N,N-disubstituted amide

Also Published As

Publication number Publication date
AU2003267367A1 (en) 2004-04-23
ATA14832002A (en) 2005-04-15
AT413101B (en) 2005-11-15

Similar Documents

Publication Publication Date Title
US9284262B2 (en) Process for preparing esteramide compounds
IS5883A (en) Method for the production of pure citalopram
DE602006021411D1 (en) PROCESS FOR PREPARING OPTIONAL 2-SUBSTITUTED 1,6-DIHYDRO-6-OXO-4-PYRIMIDINCARBOXYLIC ACIDS
ATE422200T1 (en) METHOD FOR PRODUCING SUBSTITUTED NICOTINIC ACID ESTERS
ATE207884T1 (en) METHOD FOR PRODUCING AMINOBENZENE DERIVATIVES
DE1146486B (en) Process for the preparation of O, O-dialkyl-dithiophosphoryl fatty acid amides
DE69915713D1 (en) METHOD FOR PRODUCING CITALOPRAM
ATE343385T1 (en) METHOD FOR PRODUCING DONEPEZIL
WO2004031128A1 (en) Improved method for the production of n-substituted amides from nitriles
JP2008222606A5 (en)
CS239903B2 (en) Processing of aminomethyl phosphoric acid derivatives
EP0297369B1 (en) Process for the preparation of N-phosphonomethylglycine
DE69802388D1 (en) METHOD FOR PRODUCING NICOTINIC ACIDS
ATE491686T1 (en) AMLODIPINE GENTISAT AND METHOD FOR THE PRODUCTION THEREOF
EP0026736B1 (en) Process for preparing 2,3,5-trichloropyridine and ammonium salts of the methyl ester of methane phosphonic acid, and their preparation
US4670193A (en) Process for preparing phosphonic acids
ES2513565T3 (en) Steramide compound preparation process
RU2011143755A (en) METHOD FOR PRODUCING 1,5-BENZODIAZEPINE DERIVATIVE
SU958425A1 (en) Cyclic amidophosphites as antioxidant additive for carboxylic acid esters
DE3780616D1 (en) METHOD FOR PRODUCING A 2-ALKYL- OR 2-PHENYL-1,4,5,6-TETRAHYDROPYRIMIDINE AND METHOD FOR PRODUCING 2-ALKYL- OR 2-PHENYL-PYRIMIDINS.
DE2613172A1 (en) PROCESS FOR THE PRODUCTION OF PENICILLINES AND CEPHALOSPORINES
EP0591773A1 (en) 3-imino-3-alkoxy-propionicacidlactates and the tautomer acroylicacidlactates
SU1302665A1 (en) Method of producing 2-oxo-1,4,2-dioxaphospholanes
US4051133A (en) Process for converting penicillin sulfoxides to the corresponding 3-desacetoxycephalosporins
RU2292339C1 (en) Method for preparing 5-amino-1,2,4-triazol-3-ylcarboxylic acid amides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AT AU BG BR BY CA CH CN CZ DE DK EE ES FI GB HR HU IL IN JP KP KR LT LU LV MX NO NZ PH PL PT RO RU SE SK TR UA US ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP