TREA

PROCESS FOR ALKENYLATING CARBOXAMIDES

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  • Patent Application
  • 20090131657
  • Publication Number
    20090131657
  • Date Filed
    June 04, 2007
    17 years ago
  • Date Published
    May 21, 2009
    15 years ago
Information
Abstract
The present invention relates to a process for preparing N-(1-alkenyl)carboxamides of the formula I, which comprises reacting a carboxamide of the formula II with an alkyne of the formula III in the presence of a catalyst selected from among carbonyl complexes, halides and oxides of rhenium, manganese, tungsten, molybdenum, chromium and iron.
Description

The present invention relates to a process for preparing N-(1-alkenyl)carboxamides by reacting a carboxamide with a terminal alkyne.


The addition of carboxamides onto alkynes to produce the corresponding N-alkenyl carboxamides has been known for a long time. Suitable catalysts are strongly basic compounds, in particular potassium salts such as the potassium salt of the carboxamide participating in the reaction (W. Reppe, Liebigs Ann. Chem. 601, 81 (1956)). It is also possible to use alkali metals such as potassium (W. Reppe, Liebigs Ann. Chem. 601, 81 (1956)) or sterically hindered alkali metal alkoxides (WO 89/09210). Furthermore, T. Kondo et al. in J. Chem. Soc. Chem. Commun. 1995, 413, describe the reaction of 1-hexyne with, for example, acetanilide at 180° C. under super-atmospheric pressure over a ruthenium carbonyl catalyst.


In all the processes of the prior art, the yield of corresponding N-alkenyl carboxamides leaves something to be desired and/or the processes are technically very complicated.


It is therefore an object of the present invention to provide a simple process for preparing N-(1-alkenyl)carboxamides which proceeds in high yield.


In addition, the process should be able to be carried out at temperatures at which thermally labile carboxamides and N-(1-alkenyl)carboxamides do not decompose.


The process should allow the reaction of base-labile starting materials or the synthesis of base-labile products.


Finally, the process should be able to be carried out using small amounts of catalyst in order to limit the costs for the catalyst.


It has now surprisingly been found that this object is achieved when a carbonyl complex of rhenium, manganese, tungsten, molybdenum, chromium or iron is used as catalyst.


The present invention accordingly provides a process for preparing N-(1-alkenyl)carboxamides of the formula I







where


R1 is hydrogen or —C(═X)NR2—CH═CH—R; or

    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COO—CH═CH—R, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NR2—CH═CH—R; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COO—CH═CH—R, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NR2—CH═CH—R;


      R2 is hydrogen; or
    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen and C1-C4-alkoxy; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, C1-C4-alkyl, halogen and C1-C4-alkoxy; or
    • C(═X)R6;


      R3 is C1-C4-alkyl;


      R4, R5 are each hydrogen or C1-C4-alkyl;


      R6 is hydrogen; or
    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COO—CH═CH—R, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NR2—CH═CH—R; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COO—CH═CH—R, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NR2—CH═CH—R;


      or


      R1 and R2 together form a —(CH2)n—, —(CH2)m—Y—(CH2)o— or —(CH2)p—(CH═CH)q— chain,
    • where
    • n is 2, 3, 4, 5 or 6;
    • m is 1, 2 or 3;
    • o is 1, 2 or 3;
    • p is 1, 2 or 3;
    • q is 1 or 2;
    • Y is O, S or N(C1-C4-alkyl);
    • or
    • together form a radical (a12), (b12) or (c12)









    • which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;

    • or


      R1 and R6 together form a —(CH2)n—, —(CH2)m—Y—(CH2)o— or —(CH2)p—(CH═CH)q— chain,

    • where

    • n is 2, 3, 4, 5 or 6;

    • m is 1, 2 or 3;

    • o is 1, 2 or 3;

    • p is 0, 1, 2 or 3;

    • q is 1 or 2;

    • Y is O, S or N(C1-C4-alkyl);

    • or

    • together form arene-1,2-diyl, naphthalene-1,8-diyl or hetarene-1,2-diyl which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;

    • or

    • together form a radical (a16), (b16) or (C16)












    • which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;



  • X is O, S or NR7 where R7 is hydrogen or C1-C8-alkyl;

  • R is H, C1-C8-alkyl, C3-C7-cycloalkyl, phenyl-C1-C4-alkyl or phenyl, where the phenyl radical of the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4 alkoxy;


    by reacting a carboxamide of the formula II








where R1, R2 and X are as defined above and if the radical —(═X)NR2—CH═CH—R is comprised a plurality of times in the N-(1-alkenyl)carboxamide of the formula I, then additionally —C(═X)NHR2 in the corresponding position and if the radical —COO—CH═CH—R is comprised one or more times in the N-(1-alkenyl)carboxamide of the formula I, then additionally —COOH in the corresponding position;


with an alkyne of the formula III





H—C≡C—H  (III)


where R is as defined above;


in the presence of a catalyst selected from among carbonyl complexes, halides and oxides of ruthenium, manganese, tungsten, molybdenum, chromium or iron.


The alkyl groups can be straight-chain or branched alkyl groups having the indicated number of carbon atoms. Examples of such alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-dodecyl, etc., preferably methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl.


Examples of C2-C20-alkenyl groups are ethenyl, 1-propenyl, 2-propenyl, buten-1-yl, buten-2-yl, isobutenyl etc., preferably ethenyl, 2-propenyl or buten-2-yl.


Examples of C3-C7-cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, preferably cyclopentyl and cyclohexyl.


Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.


Aryl is, in particular, phenyl or naphthyl, preferably phenyl.


Hetaryl is, in particular, furyl, thienyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,3,4-triazinyl, 1,2,4-triazinyl or tetrazinyl, preferably pyridyl.


Arene-1,2-diyl is, in particular, benzene-1,2-diyl or naphthalene-2,3-diyl, preferably benzene-1,2-diyl.


Hetarene-1,2-diyl is, in particular, pyridine-2,3-diyl.


The alkyl radicals in the radicals C1-C4-alkoxy, C1-C4-alkylamino and di(C1-C4-alkyl)amino are in each case methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or t-butyl.


As catalyst, use is made of the carbonyl complexes, halides or oxides of rhenium, manganese, tungsten, molybdenum, chromium or iron. For the purposes of the present invention, carbonyl complexes are compounds which have at least one carbonyl group as ligand; the other coordination sites of the respective metal can be occupied by other ligands. Examples of such ligands are mentioned below. For the purposes of the present invention, halides and oxides also include compounds in which one or more coordination sites and/or valences of the respective metal are occupied by a C1-C8-alkyl group, and also oxyhalides. An example is CH3ReO3.


The catalysts can be present in all oxidation states; in the case of the carbonyl complexes, they are preferably present in the oxidation state 0 or 1.


Preferred catalysts are the carbonyl complexes, oxides or halides of rhenium, manganese or molybdenum, in particular rhenium. The carbonyl complexes of rhenium and of manganese, in particular of rhenium, have been found to be particularly useful. The carbonyl complexes of the abovementioned metals are particularly effective. One or more of the carbonyl groups can be replaced by suitable ligands such as halogens, in particular chlorine or bromine, phosphine ligands such as triphenylphosphine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, etc., amine ligands such as NH3, ethylenediamine, etc., alcohol ligands such as phenol, methanol, ethanol, etc., ether ligands, such as tetrahydrofuran (THF) etc., hydrocarbon ligands such as cyclopentadienyl(Cp), pentamethylcyclopentadienyl(pentamethyl-Cp), cycloocta-1,5-diene or acetonitrile etc., or H2O. Examples of suitable catalysts are Mn2(CO)10, W(CO)6, Mo(CO)6, Cr(CO)6, Fe(CO)5 and Fe2(CO)9.


Rhenium catalysts have been found to be particularly useful. Examples are rhenium carbonyl complexes such as Re2(CO)10, Re(CO)5Cl, Re(CO)5Br, ReBr(CO)3(CH3CN)2, ReCp(CO)3, Re(pentamethyl-Cp)(CO)3, ReCl(CO)3(CH3CN)2, ReBr(CO)3(THF)2 and ReCl(CO)3(THF)2, rhenium oxides such as Re2(pentamethyl-Cp)2O4, Re(pentamethyl-Cp)2OCl2, Re2O7 and ReCH3O3, rhenium halides such as ReCl3 or ReBr3, or ReCp2 and Re.


A particularly preferred catalyst is Re2(CO)10.


The reaction can be carried out in a homogenous or heterogeneous liquid phase. If a homogeneous liquid phase is desired, a catalyst which is soluble in the reaction medium or goes into solution during the reaction is used. Such catalysts are, in particular, the carbonyl complexes of the metals which come into question here and also ReCp2. Heterogeneous catalysts are generally the halides or “pure” oxides of these metals, e.g. Re2O7, and also rhenium metal. The heterogeneous catalysts can be used directly, for example in powder form, or applied to a support. Suitable supports are, for example, carbon, zeolites, aluminum oxides, silicon oxides.


In general, the catalyst is used in an amount of from 0.000005 to 1 mol %, preferably from 0.000005 to 0.5 mol %, more preferably from 0.00001 to 0.1 mol % and in particular from 0.00005 to 0.05 mol %, from 0.0001 to 0.05 mol %, from 0.0005 to 0.01 mol % or from 0.001 to 0.01 mol %, in each case based on the number of equivalents of the compound of the formula II. For the present purposes, the expression “equivalents” is based on —C(═X)NHR2 groups and —COOH groups of the formula II which can react with the compound of the formula III.


Suitable starting compounds are carboxamides of the formula II in which the radicals R1, R2 and X, both alone and in combination with one another, have the following meanings:


R1 is hydrogen or —C(═X)NHR2; or

    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2;
    • preferably
    • hydrogen or —C(═X)NHR2, or
    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen, C1-C4-alkoxy and —C(═X)NHR2; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy and —C(═X)NHR2;
    • in particular
    • hydrogen; or
    • C1-C20-alkyl or C2-C20-alkenyl, where the latter two radicals may optionally be substituted by a radical selected independently from among phenyl and —C(═X)NHR2; or
    • phenyl which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, C1-C4-alkoxy and —C(═X)NHR2;


      R2 is hydrogen; or
    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen and C1-C4-alkoxy; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, C1-C4-alkyl, halogen and C1-C4-alkoxy;
    • preferably
    • hydrogen; or
    • C1-C8-alkyl which may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen and C1-C4-alkoxy; or
    • aryl which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, C1-C4-alkyl, halogen and C1-C4-alkoxy;
    • in particular
    • hydrogen; or
    • C1-C8-alkyl; or
    • phenyl which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;


      R3 is C1-C4-alkyl;


      R4, R5 are each hydrogen or C1-C4-alkyl;


X is O.

Particularly useful starting compounds are aliphatic carboxamides such as aliphatic monocarboxamides per se (R2=hydrogen), aliphatic N—(C1-C8-alkyl)mono-carboxamides (R2═C1-C8-alkyl) or aliphatic monocarboxanilides (R2=phenyl) or cycloaliphatic monocarboxamides such as cycloaliphatic monocarboxamides per se (R2=hydrogen).


Examples of aliphatic monocarboxamides per se (R2=hydrogen) are formamide, acetamide, propionamide, butyramide, valeramide, hexanoamide, heptanoamide, octanoamide, nonanoamide, decanoamide, 2-methylpropionamide, 2-methyl-butyramide, 3-methylbutyramide, 2-methylpentanoamide, 2-ethylhexanoamide, 2-propylheptanoamide, pivalamide, neononanoamide, neodecanoamide, neotridecanoamide, stearamide, oleamide, lauramide, palmitamide, acrylamide, methacrylamide, crotonamide, cinnamamide or phenylacetamide.


Examples of aliphatic N—(C1-C8-alkyl)monocarboxamides (R2═C1-C8-alkyl) are N-methylformamide, N-methylacetamide, N-methylpropionamide, N-methylbutyramide, N-methylvaleramide, N-methylhexanoamide, N-methylheptanoamide, N-methyl-octanoamide, N-methylnonanoamide, N-methyldecanoamide, N-methyl-2-methyl-propionamide, N-methyl-2-methylbutyramide, N-methyl-3-methylbutyramide, N-methyl-2-methylpentanoamide, N-methyl-2-ethylhexanoamide, N-methyl-2-propyl-heptanoamide, N-methylpivalamide, N-methylneononanoamide, N-methylneodecano-amide, N-methylneotridecanoamide, N-methylstearamide, N-methyloleamide, N-methyllauramide, N-methylpalmitamide, N-methylacrylamide, N-methyl-methacrylamide, N-methylcrotonamide, N-methylcinnamamide, N-methylphenyl-acetamide, N-ethylformamide, N-ethylacetamide, N-ethylpropionamide, N-ethylbutyramide, N-ethylvaleramide, N-ethylhexanoamide, N-ethylheptanoamide, N-ethyloctanoamide, N-ethylnonanoamide, N-ethyldecanoamide, N-ethyl-2-methyl-propionamide, N-ethyl-2-methylbutyramide, N-ethyl-3-methylbutyramide, N-ethyl-2-methylpentanoamide, N-ethyl-2-ethylhexanoamide, N-ethyl-2-propylheptanoamide, N-ethylpivalamide, N-ethylneononanoamide, N-ethylneodecanoamide, N-ethylneo-tridecanoamide, N-ethylstearamide, N-ethyloleamide, N-ethyllauramide, N-ethyl-palmitamide, N-ethylacrylamide, N-ethylmethyacrylamide, N-ethylcrotonamide, N-ethyl-cinnamamide or N-ethylphenylacetamide.


Examples of aliphatic monocarboxanilides (R2=phenyl) are N-phenylformamide, N-phenylacetamide, N-phenylpropionamide, N-phenylbutyramide, N-phenylvaleramide, N-phenylhexanoamide, N-phenylheptanoamide, N-phenyloctanoamide, N-phenyl-nonanoamide, N-phenyldecanoamide, N-phenyl-2-methylpropionamide, N-phenyl-2-methylbutyramide, N-phenyl-3-methylbutyramide, N-phenyl-2-methylpentanoamide, N-phenyl-2-ethylhexanoamide, N-phenyl-2-propylheptanoamide, N-phenylpivalamide, N-phenylneononanoamide, N-phenylneodecanoamide, N-phenylneotridecanoamide, N-phenylstearamide, N-phenyloleamide, N-phenyllauramide, N-phenylpalmitamide, N-phenylacrylamide, N-phenylmethacrylamide, N-phenylcrotonamide, N-phenyl-cinnamamide, N-phenylphenylacetamide.


Examples of cycloaliphatic monocarboxamides per se (R2=hydrogen) are cyclo-hexanecarboxamide and cycloheptanecarboxamide, preferably cyclohexane-carboxamide.


Further particularly useful starting compounds are aliphatic polycarboxamides, in particular aliphatic dicarboxamides such as aliphatic dicarboxamides per se (R2=hydrogen), aliphatic N—(C1-C8-alkyl)dicarboxamides (R2═C1-C8-alkyl) or aliphatic dicarboxanilides (R2=phenyl).


Examples of aliphatic dicarboxamides per se (R2=hydrogen) are oxamide (R1=—CONH2), malonamide, succinamide, glutaramide, adipamide, sebacamide, maleamide and fumaramide.


Examples of aliphatic N—(C1-C8-alkyl)dicarboxamides (R2═C1-C8-alkyl) are bis(N-methyl)oxamide(R1=—CONHCH3), bis(N-methyl)malonamide, bis(N-methyl)-succinamide, bis(N-methyl)glutaramide, bis(N-methyl)adipamide, bis(N-methyl)sebacamide, bis(N-methyl)maleamide, bis(N-methyl)fumaramide, bis(N-ethyl)-oxamide (R1=—CONHCH3), bis(N-ethyl)malonamide, bis(N-ethyl)succinamide, bis(N-ethyl)glutaramide, bis(N-ethyl)adipamide, bis(N-ethyl)sebacamide, bis(N-ethyl)-maleamide and bis(N-ethyl)fumaramide.


Examples of aliphatic dicarboxanilides (R2=phenyl) are bis(N-phenyl)oxamide (R1=—CONHCH3), bis(N-phenyl)malonamide, bis(N-phenyl)succinamide, bis(N-phenyl)glutaramide, bis(N-phenyl)adipamide, bis(N-phenyl)sebacamide, bis(N-phenyl)maleamide and bis(N-phenyl)fumaramide.


Further particularly useful starting compounds are aromatic monocarboxamides such as aromatic monocarboxamides per se (R2=hydrogen), aromatic N—(C1-C8-alkyl) monocarboxamides (R2═C1-C8-alkyl) or aromatic monocarboxanilides (R2=phenyl).


Examples of aromatic monocarboxamides per se (R2=hydrogen) are benzoamide, 2-chlorobenzoamide, 3-chlorobenzoamide, 4-chlorobenzoamide, 2,3-dichlorobenzo-amide, 2,4-dichlorobenzoamide, 2,6-dichlorobenzoamide, 3,4-dichlorobenzoamide, 2,4,6-trichlorobenzoamide, 2-methylbenzoamide, 3-methylbenzoamide, 4-methyl-benzoamide, 2,3-dimethylbenzoamide, 2,4-dimethylbenzoamide, 2,6-dimethyl-benzoamide, 3,4-dimethylbenzoamide, 2,4,6-trimethylbenzoamide, 2-methoxy-benzoamide, 3-methoxybenzoamide, 4-methoxybenzoamide, 2,3-dimethoxy-benzoamide, 2,4-dimethoxybenzoamide, 2,6-dimethoxybenzoamide, 3,4-dimethoxy-benzoamide, 2,4,6-trimethoxybenzoamide and 3,4,5-trimethoxybenzoamide.


Examples of aromatic N—(C1-C8-alkyl) monocarboxamides (R2═C1-C8-alkyl) are N-methylbenzoamide, N-methyl-2-chlorobenzoamide, N-methyl-3-chlorobenzoamide, N-methyl-4-chlorobenzoamide, N-methyl-2,3-dichlorobenzoamide, N-methyl-2,4-dichlorobenzoamide, N-methyl-2,6-dichlorobenzoamide, N-methyl-3,4-dichloro-benzoamide, N-methyl-2,4,6-trichlorobenzoamide, N-methyl-2-methylbenzoamide, N-methyl-3-methylbenzoamide, N-methyl-4-methylbenzoamide, N-methyl-2,3-dimethyl-benzoamide, N-methyl-2,4-dimethylbenzoamide, N-methyl-2,6-dimethylbenzoamide, N-methyl-3,4-dimethylbenzoamide, N-methyl-2,4,6-trimethylbenzoamide, N-methyl-2-methoxybenzoamide, N-methyl-3-methoxybenzoamide, N-methyl-4-methoxybenzo-amide, N-methyl-2,3-dimethoxybenzoamide, N-methyl-2,4-dimethoxybenzoamide, N-methyl-2,6-dimethoxybenzoamide, N-methyl-3,4-dimethoxybenzoamide, N-methyl-2,4,6-trimethoxybenzoamide, N-methyl-3,4,5-trimethoxybenzoamide, N-ethylbenzo-amide, N-ethyl-2-chlorobenzoamide, N-ethyl-3-chlorobenzoamide, N-ethyl-4-chloro-benzoamide, N-ethyl-2,3-dichlorobenzoamide, N-ethyl-2,4-dichlorobenzoamide, N-ethyl-2,6-dichlorobenzoamide, N-ethyl-3,4-dichlorobenzoamide, N-ethyl-2,4,6-trichlorobenzoamide, N-ethyl-2-methylbenzoamide, N-ethyl-3-methylbenzoamide, N-ethyl-4-methylbenzoamide, N-ethyl-2,3-dimethylbenzoamide, N-ethyl-2,4-dimethyl-benzoamide, N-ethyl-2,6-dimethylbenzoamide, N-ethyl-3,4-dimethylbenzoamide, N-ethyl-2,4,6-trimethylbenzoamide, N-ethyl-2-methoxybenzoamide, N-ethyl-3-methoxy-benzoamide, N-ethyl-4-methoxybenzoamide, N-methyl-2,3-dimethoxybenzoamide, N-methyl-2,4-dimethoxybenzoamide, N-ethyl-2,6-dimethoxybenzoamide, N-ethyl-3,4-dimethoxybenzoamide, N-ethyl-2,4,6-trimethoxybenzoamide and N-ethyl-3,4,5-tri-methoxybenzoamide.


Examples of aromatic monocarboxanilides (R2=phenyl) are N-phenylbenzoamide, N-phenyl-2-chlorobenzoamide, N-phenyl-3-chlorobenzoamide, N-phenyl-4-chloro-benzoamide, N-phenyl-2,3-dichlorobenzoamide, N-phenyl-2,4-dichlorobenzoamide, N-phenyl-2,6-dichlorobenzoamide, N-phenyl-3,4-dichlorobenzoamide, N-phenyl-2,4,6-trichlorobenzoamide, N-phenyl-2-methylbenzoamide, N-phenyl-3-methyl-benzoamide, N-phenyl-4-methylbenzoamide, N-phenyl-2,3-dimethylbenzoamide, N-phenyl-2,4-dimethylbenzoamide, N-phenyl-2,6-dimethylbenzoamide, N-phenyl-3,4-dimethylbenzoamide, N-phenyl-2,4,6-trimethylbenzoamide, N-phenyl-2-methoxy-benzoamide, N-methyl-3-methoxybenzoamide, N-phenyl-4-methoxybenzoamide, N-methyl-2,3-dimethoxybenzoamide, N-phenyl-2,4-dimethoxybenzoamide, N-methyl-2,6-dimethoxybenzoamide, N-phenyl-3,4-dimethoxybenzoamide, N-methyl-2,4,6-tri-methoxybenzoamide.


Further particularly useful starting compounds are aromatic polycarboxamides such as aromatic dicarboxamides, tricarboxamides, tetracarboxamides, pentacarboxamides or hexacarboxamides per se (R2=hydrogen), preferably aromatic dicarboxamides per se (R2=hydrogen), aromatic N—(C1-C8-alkyl)dicarboxamides (R2═C1-C8-alkyl), aromatic dicarboxanilides (R2=phenyl).


Examples of aromatic dicarboxamides per se (R2=hydrogen) are phthalamide, isophthalamide and terephthalamide.


Examples of aromatic N—(C1-C8-alkyl)dicarboxamides (R2═C1-C8-alkyl) are bis(N-methyl)phthalamide, bis(N-methyl)isophthalamide, bis(N-methyl)terephthalamide, bis(N-ethyl)phthalamide, bis(N-ethyl)isophthalamide and bis(N-ethyl)terephthalamide.


Examples of aromatic dicarboxanilides (R2=phenyl) are bis(N-phenyl)phthalamide, bis(N-phenyl)isophthalamide, bis(N-phenyl)terephthalamide.


Further suitable starting compounds are carboxamides of the formula II in which the radicals R1, R2 and X, both alone and in combination, have the following meanings:


R1 is hydrogen or —C(═X)NHR2; or

    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2;
    • preferably
    • hydrogen, or
    • C1-C20-alkyl or C2-C20-alkenyl, where the latter two radicals may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen and C1-C4-alkoxy; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;
    • in particular
    • hydrogen; or
    • C1-C20-alkyl or C2-C20-alkenyl, where the latter two radicals may optionally be substituted by phenyl; or
    • phenyl which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;


R2 is C(═X)R6;

R3 is C1-C4-alkyl;


R4, R5 is hydrogen or C1-C4-alkyl;


R6 is hydrogen; or

    • C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2;
    • preferably
    • hydrogen; or
    • C1-C20-alkyl or C2-C20-alkenyl, where the latter two radicals may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen and C1-C4-alkoxy; or
    • aryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;
    • in particular
    • C1-C20-alkyl or C2-C20-alkenyl, where the latter two radicals may optionally be substituted by phenyl; or
    • phenyl which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;


X is O.

Particularly useful compounds are aliphatic carboximides such as N,N-bisformylamine, N,N-bisacetylamine or N,N-bispropionylamine.


Particularly useful compounds are aromatic carboximides such as N,N-bisbenzoyl-amine.


Particularly useful compounds are mixed aliphatic-aromatic carboximides such as N-benzoyl-N-formylamine, N-acetyl-N-benzoylamine or N-benzoyl-N-propionylamine.


Further suitable starting compounds are carboxamides of the formula II in which the radicals R1, R2 and X, either alone or in combination with one another, have the following meanings:


R1 and R2 together form a —(CH2)n—, —(CH2)m—Y—(CH2)o— or —(CH2)p—(CH═CH)q— chain,

    • where
    • n is 2, 3, 4, 5 or 6;
    • m is 1, 2 or 3;
    • o is 1, 2 or 3;
    • p is 1, 2 or 3;
    • q is 1 or 2;
    • Y is O, S or N(C1-C4-alkyl);
    • preferably a —(CH2)n— chain where n=2, 3, 4 or 5 or a —(CH2)p—(CH═CH)q— chain where p=0 and q=2;
    • or
    • together form a radical (a12), (b12) or (c12)









    • which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;

    • the compounds of the formula II are preferably compounds of the formula IIa12-1, IIa12-2, IIb12-1, IIb12-2 or IIc12-1










X is O.

Particularly useful compounds are cyclic carboxamides such as 2-pyrrolidone, pentane-5-lactam, 2-(1H)-pyridone, caprolactam (=azepan-2-one), in particular 2-pyrrolidone and caprolactam, preferably 2-pyrrolidone.


Further suitable starting compounds are carboxamides of the formula II in which the radicals R1, R6 and X, either alone or in combination with one another, have the following meanings:


R1 and R6 together form a —(CH2)n—, —(CH2)m—Y—(CH2)o— or —(CH2)p—(CH═CH)q— chain,

    • where
    • n is 2, 3, 4, 5 or 6;
    • m is 1, 2 or 3;
    • 0 is 1, 2 or 3;
    • p is 0, 1, 2 or 3;
    • q is 1 or 2;
    • Y is O, S or N(C1-C4-alkyl);
    • preferably a —(CH2)n— chain where n=2, 3, 4 or 5 or a —(CH2)p—(CH═CH)q— chain where p=0 and q=1;
    • or
    • together form arene-1,2-diyl, naphthalene-1,8-diyl or hetarene-1,2-diyl, which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;
    • preferably benzene-1,2-diyl or naphthalene-1,8-diyl;
    • or
    • together form a radical (a16), (b16) or (c16)









    • which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;

    • preferably the compound IIa16-1;










X is O.

Particularly useful compounds are cyclic biscarboxamides such as fumarimide, succinimide, maleimide, phthalimide, in particular phthalimide.


Suitable starting compounds of the formula III are, for example, acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene, with particular preference being given to using acetylene.


The ratio of compound of the formula II to compound of the formula III can be chosen within a wide range. In general, however, an excess of compound of the formula III is used, in particular an excess of from 0.1 to 20 mol %, based on the compound of the formula II. If the compound of the formula I comprises two or more groups —C(═X)NR2—CH═CH—R and/or one or more groups —COOCH═CHR, the excess is calculated per C(═X)NR2—CH═CH—R or —COOCH═CHR group, i.e. per equivalent of the compound of the formula II.


The reaction is generally carried out in a suitable inert solvent. If the compound of the formula II is liquid at the temperature employed, a solvent can also be dispensed with. Suitable inert solvents are aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, toluene, xylene, etc., ethers such as tetrahydrofuran or dioxane, chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane or chlorobenzene, acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methyl-pyrrolidone or polyethylene glycols or mixtures thereof.


The reaction temperature can be chosen freely within a wide range. It is generally selected so that rapid reaction occurs without starting compounds or the product decomposing. In general, the reactions are carried out at a temperature of less than 250° C. The temperature is usually in the range from 70 to 230° C., in particular from 110 to 210° C., preferably from 130 to 190° C., from 150 to 180° C., particularly preferably from 160 to 170° C.


Depending on the alkyne of the formula III which is used and on any solvent used, the reaction can be carried out under superatmospheric pressure or under atmospheric pressure. If superatmospheric pressure is employed, the reaction is usually carried out at a pressure of from 1 to 50 bar (absolute), with preference being given to setting a pressure of from 1 to 30 bar (absolute), preferably from 2 to 20 bar and in particular from 5 to 25 bar or from 10 to 20 bar. The reaction with acetylene is preferably carried out under superatmospheric pressure. The pressure can, for example, be set by means of the compound of the formula III employed and/or an inert gas such as nitrogen. If the reaction is carried out in the presence of an inert gas, the pressure can also be increased, in particular up to 100 bar, preferably up to 50 bar. The reaction time is usually in the range from 0.01 to 72 hours, in particular from 0.1 to 48 hours.


It is also possible to add, if appropriate, reaction-promoting additives such as zinc acetate, lithium salts, for example LiCl, Lewis acids such as BF3, etc., Lewis bases such as triethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene etc., substances which react with the catalyst at the CO and can thereby create free coordination sites, e.g. trimethylamine N-oxide.


The reaction can be carried out batchwise, continuously or by the semibatch method. The work-up is carried out in a customary manner, advantageously by distilling off the desired carboxamide of the formula I. The catalyst remains in the bottoms and can, if appropriate, be reused. The reaction and/or the work-up, in particular the purifying distillation, can advantageously be carried out in the presence of a polymerization inhibitor. As polymerization inhibitors, it is possible to use, for example, hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, nitroso compounds such as isoacryl nitrate, nitrosodiphenylamino of N-nitroso-cyclohexylhydroxylamine, methylene blue, phenothiazine, tannic acid or diphenylamine. The polymerization inhibitors are used in amounts of from 1 to 10 000 ppm, in particular from 100 to 1000 ppm, in each case based on the total batch.


A particular embodiment comprises the reaction of compounds of the formula II in which R1 and R2 form a —(CH2)3— chain and X is oxygen with acetylene. This reaction is preferably carried out at a temperature in the range from 70 to 220° C., in particular from 120 to 190° C. or from 150 to 170° C. The catalyst is used, in particular, in an amount of from 0.00001 to 0.1 mol %, in particular 0.0001 to 0.01 mol %, based on the carboxamide of the formula II.


A further particular embodiment comprises the reaction of phthalimide (compounds of the formula II in which R1 and R6 together form benzene-1,2-diyl and X is oxygen) with acetylene. This reaction is preferably carried out at a temperature in the range from 70 to 220° C., in particular from 120 to 190° C. or from 150 to 170° C. The catalyst is used, in particular, in an amount of from 0.00001 to 0.1 mol %, in particular from 0.0001 to 0.01 mol %, based on the phthalimide.


The following examples illustrate the invention without restricting its scope. The GC analyses (GC: gas chromatography) were carried out on a capillary column provided with a Carbowax (polyethylene glycol) film, e.g. DB Wax from J & W Scientific.







EXAMPLES
Example 1

A mixture of 2.65 g (59 mmol) of formamide, 0.5 g (0.77 mmol) of Re2(CO)10 and 20.7 g of dioxane were subjected to vinylation at 170° C. under a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 0.2 h. Vinylformamide could be detected by means of GC analysis.


Example 2
Without Polymerization Inhibitor

A mixture of 10.0 g (118 mmol) of 2-pyrrolidone, 0.5 g (0.77 mmol) of Re2(CO)10 and 17.4 g of toluene were subjected to vinylation at 170° C. under a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 0.2 h. The yield of N-vinyl-2-pyrrolidone determined by GC analysis was 95%.


Example 3
With Polymerization Inhibitor

A mixture of 10.0 g (118 mmol) of 2-pyrrolidone, 0.5 g (0.77 mmol) of Re2(CO)10, 53 mg (0.24 mmol) of di-tert-butyl-p-cresol and 17.4 g of toluene were subjected to vinylation at 170° C. under a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 0.2 h. The yield of N-vinyl-2-pyrrolidone determined by GC analysis was 98%.


Example 4

A mixture of 6.6 g (58 mmol) of caprolactam, 0.5 g (0.77 mmol) of Re2(CO)10 and 17.4 g of toluene were subjected to vinylation at 170° C. under a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 0.2 h. N-Vinylcaprolactam could be detected by means of GC analysis.


Example 5

A mixture of 29.4 g (200 mmol) of phthalimide, 652 mg (1.00 mmol) of Re2(CO)10 and 59.0 g of dioxane were subjected to vinylation at 160° C. under a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 0.2 h. The yield of N-vinylphthalimide determined by GC analysis was 94%.

Claims
  • 1. A process for preparing N-(1-alkenyl)carboxamides of the formula I
  • 2. The process according to claim 1, wherein the catalyst is selected from among carbonyl complexes of ruthenium and manganese.
  • 3. The process according to claim 2, wherein Re2(CO)10 is used as catalyst.
  • 4. The process according to claim 1, wherein the catalyst is used in an amount of from 0.000005 to 1 mol %, based on equivalents of the compound of the formula II.
  • 5. The process according to claim 1, wherein the compound of the formula III is selected from among acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne, and phenylacetylene.
  • 6. The process according to claim 5, wherein acetylene is used as compound of the formula III.
  • 7. The process according to claim 1, wherein a compound of the formula II in which R1 is hydrogen or —C(═X)NHR2; or C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2; oraryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2;R2 is hydrogen; or C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1 or 2 radicals selected independently from among phenyl, halogen and C1-C4-alkoxy; oraryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, C1-C4-alkyl, halogen and C1-C4-alkoxy;R3 is C1-C4-alkyl;R4, R5 are each hydrogen or C1-C4-alkyl;X is O;is reacted.
  • 8. The process according to claim 1, wherein a compound of the formula II in which R1 is hydrogen or —C(═X)NHR2; or C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2; oraryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2;R2 is C(═X)R6;R3 is C1-C4-alkyl;R4, R5 is hydrogen or C1-C4-alkyl;R6 is hydrogen; or C1-C20-alkyl, C2-C20-alkenyl or C3-C7-cycloalkyl, where the latter three radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among phenyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2; oraryl or heteroaryl, where the latter two radicals may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy, amino, C1-C4-alkylamino, di(C1-C4-alkyl)amino, —COR3, —COOR3, —COOH, —CONR4R5, —OCOR3, —OCOOR3, —OCONR4R5, —NR4COR5, —NR4COOR5, —NR4CONR4R5 and —C(═X)NHR2;X is O;is reacted.
  • 9. The process according to claim 1, wherein a compound of the formula II in which R1 and R2 together form a —(CH2)n—, —(CH2)m—Y—(CH2)o— or —(CH2)p—(CH═CH)q— chain, wheren is 2, 3, 4, 5 or 6;m is 1, 2 or 3;o is 1, 2 or 3;p is 1, 2 or 3;q is 1 or 2;Y is O, S or N(C1-C4-alkyl);ortogether form a radical (a12), (b12) or (c12)
  • 10. The process according to claim 9, wherein 2-pyrrolidone is reacted as compound of the formula II.
  • 11. The process according to claim 1, wherein a compound of the formula II in which R1 and R6 together form a —(CH2)n—, —(CH2)m—Y—(CH2)o— or —(CH2)p—(CH═CH)q— chain, wheren is 2, 3, 4, 5 or 6;m is 1, 2 or 3;o is 1, 2 or 3;p is 0, 1, 2 or 3;q is 1 or 2;Y is O, S or N(C1-C4-alkyl);ortogether form arene-1,2-diyl, naphthalene-1,8-diyl or hetarene-1,2-diyl, which may optionally be substituted by 1, 2 or 3 radicals selected independently from among C1-C4-alkyl, halogen and C1-C4-alkoxy;ortogether form a radical (a16), (b16) or (c16)
  • 12. The process according to claim 11, wherein phthalimide is reacted as compound of the formula II.
  • 13. The process according to claim 1, wherein the reaction is carried out at a temperature of up to 250° C.
  • 14. The process according to claim 13, wherein the reaction is carried out at a temperature in the range from 140 to 230° C.
  • 15. The process according to claim 1, wherein the catalyst is used in an amount of from 0.000001 to 0.0025 mol %, based on equivalents of the compound of the formula II.
  • 16. The process according to claim 1, wherein the reaction and/or the work-up of the reaction mixture obtained by means of the reaction is/are carried out in the presence of at least one polymerization inhibitor.
  • 17. The process according to claim 1, wherein the compound of the formula III is used in an excess of from 0.1 to 20 mol %, based on equivalents of the compound of the formula II.
Priority Claims (1)
Number Date Country Kind
10 2006 028 000.8 Jun 2006 DE national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2007/055444 6/4/2007 WO 00 12/12/2008