WO1990009988A2 - Preparations d'amides - Google Patents

Preparations d'amides Download PDF

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Publication number
WO1990009988A2
WO1990009988A2 PCT/GB1990/000315 GB9000315W WO9009988A2 WO 1990009988 A2 WO1990009988 A2 WO 1990009988A2 GB 9000315 W GB9000315 W GB 9000315W WO 9009988 A2 WO9009988 A2 WO 9009988A2
Authority
WO
WIPO (PCT)
Prior art keywords
process according
aromatic
reaction
nitrile
perborate
Prior art date
Application number
PCT/GB1990/000315
Other languages
English (en)
Other versions
WO1990009988A3 (fr
Inventor
Alexander Mckillop
Duncan Kemp
Original Assignee
Interox Chemicals Limited
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 Interox Chemicals Limited filed Critical Interox Chemicals Limited
Publication of WO1990009988A2 publication Critical patent/WO1990009988A2/fr
Publication of WO1990009988A3 publication Critical patent/WO1990009988A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen 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
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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

Definitions

  • the present invention relates to the preparation of amides and more specifically to a process for theLr preparation from the corresponding nitrile. It is often desired to employ oxidising systems in carrying out reactions. When these are contemplated on a commercial scale, it is generally recognised that in an ideal world, it would be advantageous for such oxidising systems to be widely available, storage stable, easy to handle and relatively cheap, but also beneficial if they could also perform the desired reaction under mild conditions. Unfortunately, the world is often far from ideal, because the demands for good storage stability and safe handling of oxidising systems can be incompatible with the counter-demands of good reactivity at mild conditions.
  • a process for preparing an aromatic amide from the corresponding aromatic nitrile in which the nitrile is contacted with an alkali metal perborate in an aqueous alcoholic reaction medium at a mild reaction temperature until at least some of the corresponding aromatic amide has been formed.
  • the range of aromatic nitriles which are suitable starting materials for the present invention process is extremely wide. Results that were regarded as at least satisfactory were obtained from a very large number of different nitrile substituted compounds.
  • the aromatic nucleus can comprise a carbocyclic nucleus or a nucleus substituted by a heteroatom.
  • Suitable nuclei include benzene, furan, thiophene, pyridine or a fused ring system such as quinoline.
  • Present trials have not demonstrated a positive result from a polycyclic carbocyclic nucleus, and such nuclei are deemed to be excluded herein from the term aromatic for the purpose of the present invention process unless or until they are shown to yield the desired product.
  • the reaction has been demonstrated most often when the nitrile substituent is a direct substituent of the aromatic nucleus but an acceptable result has also been obtained when the nitrile was separated from the nucleus by an interposed methylene group. It will be understood, however, that the present invention process does not extend to the use of aliphatic nitriles as starting materials.
  • the aromatic nucleus can be further substituted by a wide range of substituents, including both electron withdrawing and electron donating substituents, in any position around the nucleus, although it will be recognised that their presence will affect to a greater or lesser extent the efficiency of the reaction, depending also upon their position around the nucleus relative to the nitrile substituent. Whilst the invention process has been best characterised in the presence of a single additional substituent, a number of results demonstrate that a plurality of substituents can be present, provided that they are so positioned around the nucleus as to avoid shielding the nitrile from reaction, ie avoiding substitution simultaneously at the 2,6 positions by bulky groups, such as groups that are significantly larger than fluoro.
  • Suitable substituents can be selected from alkyl groups, and especially methyl, halo groups, specifically chloro or fluoro groups, alkoxy, preferably methoxy groups, thioalkyl, such as thiomethyl, nitro or nitrile groups. It is also possible to employ substrates containing amino or hydroxyl groups although the efficiency of the present invention reaction in their presence is somewhat diminished, to the extent demonstrated by the examples provided herein.
  • the present invention provides a convenient process for the preparation of a lagre number of substituted aromatic amides.
  • the reaction employs an oxidising system, which is reduced by interaction with the substrate, it is possibly referred to more accurately as an hydrolysis reaction rather than as an oxidation reaction.
  • the alkali perborate is particularly conveniently a sodium perborate on account of the bulk availability and excellent storage and handling properties of the two industrially available products sodium perborate monohydrate and sodium perborate tetrahydrate, which have respectively the empirical formulae aI.O3.H2O and a-.O3.4H2O, though these do not properly represent the structure of the compounds.
  • a particularly safe way comprises introducing it progressively, such as in small portions or continuously during an introductory period, either at or below the desired reaction temperature.
  • the invention reaction conditions permit the hydration reaction of the nitrile to be effected using only a modest excess of perborate.
  • a mole ratio for perboraternitrile selected in the range of from at least 1.5:1 to 6:1 and particularly from 2.5:1 to 4:1.
  • the efficiency of the reaction depending upon which substituents are present, but by appropriate selection of conditions, it is possible to obtain very high conversion to the amide at a mole ratio chosen within the aforementioned ranges.
  • the reaction medium for the present reaction comprises an aqueous alcohol solution.
  • the alcohol is particularly suitably a low molecular weight aliphatic alcohol, and especially one that is free from olefinic unsaturation.
  • An advantageously convenient example comprises methanol.
  • the ratio of alcohol : water in the reaction mixture is often chosen within the range of ratios of from 2:1 to 1:2 v/v.
  • the alcohol component of the reaction medium can be introduced progressively, into a preformed aqueous mixture of the perborate, water and substrate, ie in portions or continuously throughout an extended period of reagent introduction.
  • the reaction is carried out at a mild temperature, by which is meant that there is no need to maintain a high temperature during the reaction or even approach closely reflux temperature for the medium. In many instances, it is convenient to employ a temperature that is above ambient, and preferably above 40°C, up to about 70°C. Very effective oxidations have been achieved in the region of or around 45 to 55°C throughout the reaction period.
  • the total reaction period will usually be determined in practice by taking into account the reaction temperature and the substrate and will often include a period during which perborate is introduced and a subsequent period in which the reaction is allowed to progress.
  • the alcohol introduction period is often chosen within the range of 10 to 60 minutes.
  • the subsequent period is often chosen in the range of from 45 minutes to 10 hours and for many of the substrates in the range of from 45 minutes to 200 minutes.
  • Some reaction can occur whilst the alcohol is being introduced so that the total reaction period is often selected in the range of from 1 hour to 10 hours, and for many substrates from 1 hour to 4 hours.
  • reaction can be monitored, for example by thin layer chromatography. Recovery of the product can be commenced when the monitoring indicates that either a desired proportion of the substrate has been consumed or converted to the product, or the consumption or production rate has slowed to a rate at or near zero, thereby indicating that little further product could be obtained.
  • reaction periods can be gauged in small scale trials and refined in bulk-scale operation.
  • the invention process is particularly suitable for a batch style reaction procedure, but it will be recognised that by a suitable choice of reactor design such as a once through tubular reactor, it is a practical proposition to carry out the reaction continuously, especially for those substrates that employ a relatively short reaction period.
  • the product can be recovered from the reaction mixture by removal if desired of at least part of the alcohol from the reaction medium, such as by evaporation, preferably under reduced pressure, and subsequent addition of a stripping immiscible solvent to the residue, thereby transferring the product mainly into the solvent.
  • Suitable solvents include halogenated hydrocarbons such as chloroform.
  • the total amount of solvent employed is often chosen within the range of from 1 to 10 parts v/v per part of reaction mixture.
  • the conventional techniques of solvent stripping, viz continuous co- or counter-current contact or multiple batch contact are applicable.
  • the solvent can subsequently be removed, preferably by evaporation under reduced pressure to yield a solid product.

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

Abstract

On décrit une préparation d'amides aromatiques obtenues par la réaction d'un nitrile aromatique avec un perborate de métal alcalin en excès, de préférence un monohydrate ou un tétrahydrate de perborate de sodium, dans un milieu de réaction alcoolique, de préférence du méthanol, dans des conditions de réaction modérées comprises entre 40°C et 70°C. Le rapport moléculaire pour le perborate: nitrile est de préférence compris entre environ 2,5:1 et 4:1. Le nitrile aromatique peut être remplacé par une grande variété de substituants additionnels, tels que des groupes alkyle, halo, alkoxy thioalkyle ou nitro, et le noyau aromatique peut être carbocyclique ou hétérocyclique, y compris benzène, furane, thiophène, pyridine et quinoléine.
PCT/GB1990/000315 1989-03-02 1990-02-28 Preparations d'amides WO1990009988A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8904799.7 1989-03-02
GB898904799A GB8904799D0 (en) 1989-03-02 1989-03-02 Amide preparation

Publications (2)

Publication Number Publication Date
WO1990009988A2 true WO1990009988A2 (fr) 1990-09-07
WO1990009988A3 WO1990009988A3 (fr) 1990-10-18

Family

ID=10652608

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1990/000315 WO1990009988A2 (fr) 1989-03-02 1990-02-28 Preparations d'amides

Country Status (2)

Country Link
GB (1) GB8904799D0 (fr)
WO (1) WO1990009988A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017053A (zh) * 2015-07-16 2015-11-04 合肥祥晨化工有限公司 一种水杨酰胺的合成方法
CN112495391A (zh) * 2020-12-21 2021-03-16 中国科学院山西煤炭化学研究所 一种适用于乙腈水合反应制备乙酰胺的负载型复合金属催化剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE828247C (de) * 1948-10-02 1953-07-02 Degussa Verfahren zur Herstellung von Nicotinsaeureamid
CH471081A (de) * 1965-11-29 1969-04-15 Reynolds Tobacco Co R Verfahren zur Herstellung von Amiden
US4222960A (en) * 1978-06-08 1980-09-16 Chemie Linz Aktiengesellschaft Process for the manufacture of α-hydroxycarboxylic acid amides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE828247C (de) * 1948-10-02 1953-07-02 Degussa Verfahren zur Herstellung von Nicotinsaeureamid
CH471081A (de) * 1965-11-29 1969-04-15 Reynolds Tobacco Co R Verfahren zur Herstellung von Amiden
US4222960A (en) * 1978-06-08 1980-09-16 Chemie Linz Aktiengesellschaft Process for the manufacture of α-hydroxycarboxylic acid amides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis, International Journal of Methods in Synthetic Organic Chemistry, No. 3, March 1980, Georg Thieme Verlag (Stuttgart, New York) S. CACCHI et al.: "Amides from Nitriles using Basic Hydrogen Peroxide under Phase-Transfer Catalysed Conditions", pages 243-244 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017053A (zh) * 2015-07-16 2015-11-04 合肥祥晨化工有限公司 一种水杨酰胺的合成方法
CN112495391A (zh) * 2020-12-21 2021-03-16 中国科学院山西煤炭化学研究所 一种适用于乙腈水合反应制备乙酰胺的负载型复合金属催化剂及其制备方法和应用

Also Published As

Publication number Publication date
WO1990009988A3 (fr) 1990-10-18
GB8904799D0 (en) 1989-04-12

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