US 3,943,132 A · Process for the preparation of hydrazones

Abstract

This invention relates to a method of preparing hydrazones of the formula ##EQU1## in which R.sub.1 and R.sub.2, which may be identical or different, represent a linear alkyl radical of from 1 to 12 carbon atoms, a branched alkyl or cycloalkyl radical of from 3 to 12 carbon atoms, an aromatic radical of from 6 to 12 carbon atoms having a benzene or naphthalene nucleus, or a radical of from 5 to 12 carbon atoms having a pyridine nucleus, or R.sub.1 and R.sub.2 together form a linear or branched alkylene radical of from 3 to 12 carbon atoms in which one of the carbon atoms of the chain may be replaced by an oxygen atom, all of the above radicals being unsubstituted or substituted by one or more atoms or groups such as chlorine, bromine, fluorine, or iodine atoms or hydroxy, ether, carboxylic acid, carboxylic amide or ester, nitrile, nitro, or sulphonic acid or amide groups, or one of the two radicals R.sub.1 and R.sub.2 may be a hydrogen atom, and in which R.sub.3 and R.sub.4, which may be identical or different, represent a hydrogen atom, a linear alkyl or cycloalkyl radical of from 3 to 12 carbon atoms, in which one of the carbon atoms of the cycloalkyl radical may be replaced by an oxygen atom, or an aromatic hydrocarbon radical of from 6 to 12 carbon atoms or R.sub.3 and R.sub.4 together represent a linear or branched alkylene radical of from 3 to 11 carbon atoms, the above radicals being unsubstituted or substituted by atoms or groups such as chlorine, bromine, fluorine, ethylenic groups, nitro, hydroxy, alkoxy, or carboxylic acid or ester radicals , which comprises reacting a primary or secondary amine of the formula Wherein R.sub.1 and R.sub.2 are as defined above, ammonia, and a carbonyl compound of the formula Wherein R.sub.3 and R.sub.4 are as defined above, with a peroxide compound.

A method for preparing hydrazones which comprises reacting

a. ammonia;
b. an amine selected from methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, di-n-butylamine, t-butylamine, an amylamine, cyclohexylamine, dicyclohexylamine, n-dodecylamine, mono- and di- ethanoloamines, 2-methoxyethylamine, morpholine, pyrrolidine, piperidine, .beta.-aminopropionitrile, .beta.-aminopropionamide, aniline, a toluidine, mono- and dichloro-anilines and -toluidines, a bromoaniline, a fluoro-aniline, nitro- and diniutro-anilines and -toluidines, and anisidine, a trifluoromethylaniline, anthranilic acid, sulphanilic acid, diphenylamine, a naphthylamine and an aminopyridine;
c. carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-pentanal, pivalaldehyde, oenanthal, 2-ethylhexanol, .DELTA.-3-tetrahydrobenzaldehyde, hexahydrobenzaldehyde, 5-norbornene, 2-carboxyaldehyde, tetrahydropyran-2-carboxyaldehyde, benzaldehyde, a monochlorobenzaldehyde, p-nitrobenzaldehyde, .beta.-chloropropionaldehyde, .beta.-methoxypropionaldehyde, 4-cyano-2,2-dimethylbutyraldehyde acetone, 2-butanone, 2-pentanone, 3-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, ethylamylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, a methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof;
and
d. a peroxide compound selected from (i) the percarboxylic acids of formic, acetic, propionic, butyric, isobutyric, valeric, isolvaleric, pivalic, hexanoic, heptanoic, octanoic, .alpha..alpha.'-dimethyloctanoic, lauric, palmitic, stearic, hexahydrobenzoic, trifluoroacetic, .beta.-chloropropionic, .beta.-methoxypropionic, .epsilon.-hydroxycaproic, benzoic and its chlorine, bromine, fluorine, methoxyl, nitro, and trifluoro-methyl derivatives, a toluic, succinic, glutaric, adipic, crotonic, maleic, fumaric and phthalic acids;
(ii) acetyl, monochloroacetyl, trifluoroacetyl, propionyl, .beta.-chloropropionyl, .beta.-methoxypropionyl, .beta.-carboxypropionyl, n-butyryl, perfluoro-n-butyryl, isobutyryl, perfluorosobutyryl, crotonyl, valeryl, isovaleryl, pivaloyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, noanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearyl, cyclohexanecarbonyl, norbornane-2 carbonyl, benzoyl, o-toluyl-m-chlorobenzoyl, p-chlorobenzoyl, p-methoxybenzoyl, p-nitro-benzyol, m-trifluoromethyl-benzoyl, p-phenylbenzoyl, o-carboxyl-benzoyl, a naphthoyl, 2-furoyl and nicotinoyl peroxides and mixed acetyl and benzoyl peroxides, acetyl and butyryl peroxides, isobutyryl, and benzoyl peroxides, acetyl and lauroyl peroxides and stearyl and benzoyl peroxides;
(iii) polymeric peroxides and mixed peroxides of oxalic, succinic, glutaric, adipic, pimelic, dodecanedioic, 1,2- or 3,4-cyclohexane dicarboxylic, o-phthalic, isophthalic, and terephthalic acids;
(iv) isopropoxycarbonyl and benzoyl peroxide, methoxycarbonyl and lauroyl peroxide, 3,3,5-trimethylcyclohexyloxycarbonyl and lauroyl peroxide, and isopropyl peroxydicarbonate;
mixed dianhydrides or diperoxy-carbonic and benzoyl, caproyl, lawcoyl, or 2-ethylhexanoyl;
and (v) hydrogen peroxide in the presence of a catalyst selected from the chlorides, bromides, fluorides, nitrates, sulphates, phosphtates, chlorates, perchlorates, borates, carbonates, formiates, acetates, propionates, butyrates, isobutyrates, octanoates, benzoates, methanesulphonates, benzenesulphonates, and p-toluenesulphonates of lithium, sodium, potassium, magnesium, calcium, strontium, barium, ammonia, mono-, di-, and trialkylated amines in which the alkyl radicals contain from 1 to 12 carbon atoms, piperidine, morpholine, and pyrrolidine, or in the presence of a co-reactant selected from acetonitrile, propionitrile, butyronitrile, a tolunitrile, p-methoxybenzonitrile, chlorobenzonitrile, p-nitrobenzonitrile, mono-, di-, and trichloroacetonitrile, glycolonitrile, .epsilon.-hydroxycapronitrile, cyanacetic acid and its alkyl esters, .beta.-cyanopropionic acid and its alkyl esters, .beta.-cyanopyridine, nicotinic nitrile, isonicotinic nitrile, acrylonitrile, methacrylonitrile, crotononitrile, .DELTA.-3-tetrahydrobenzonitrile, 3,4-epoxyhexahydrobenzonitrile, .beta..beta.'-dicyanoethylether, .beta..beta.'-dicyanoethyl sulphide, sulphoxide, or sulphone, cyanogen, malononitrile, succinontrile, glutaronitrile, adiponitrile, pimelonitride, suberonitrile, a phthalodinitrile, iminodiacetonitrile, nitrolotriacetonitrile, ethylenediamine, tetracetic acid nitrile, .beta.-hydroxypropionitrile, .beta.m-methoxyproionitrile, and the cyanoethyl derivatives of ethyleneglycol, glycerol, and sorbitol;
formiates, acetates, monochloracetates, trichloroacetates, trifluoroacetates, propionates, butyrates, isobutyrates, valerates, hexanoates, octanoates, nonanoates, dodecanoates, benzoates, chlorobenzoates, p-methoxybenzoates, nitrobenzoates, oxalates, malonates, succinates, glutarates, adipates, pimelates, butane-1,2,4-tricarboxylates, o-phthalates, isophthalates, terephthalates, trimellitates, pyromellitates, .beta.-hydroxypropionates, tartrates, and citrates of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, tertiary butanol, an amyl alcohol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, n-dodecanol, cyclohexanol, methylcyclohexanol, allyl alcohol, crotyl alcohol, .DELTA.-3-tetrahydrobenzyl alcohol, benzyl alcohol, 2-methoxyethanol, 3-methoxypropanol, 2-ethoxyethanol, ethyleneglycol, propyleneglycol, glycerol, 1,1,1-trimethylolethane, pentaerythritol, sorbitol, phenol and its chlorine, bromine, nitro, and methoxyl derivatives, cresols, pyroatechlol;
resorcinol and hydroquinone, .beta.-propiolactone, .DELTA.-butyrolactone, .delta.-valerolactone, .epsilon.-caprolactone, and their alkyl homoloques, formamides, monochloroacetamie, monobromoacetamide, dichloroacetamide, trichloroacetamide, trifluoroacetamide, .beta.-chloropropionamide, .alpha..alpha.-dichloropropionamide, .alpha.-bromopropionamide, perfluorobutyramide, glycolamide, lactamide, phenylacetamide and its derivatives halogenated in the core, diphenylacetamide, benzamide, o-toluamide, m-tolyamide, a chlorobenzamide, a bromobenzamide, a fluorobenzamide, perfluorobenzamide, a nitrobenzamide, salicylamide, p-hydroxybenzamide, the amic acids, diamides, and imides of oxalic, malonic, succinic, .alpha..alpha.-dichlorosuccinic, malic, tartric, maleic, citric, itaconic, citraconic, o-phthalic, isophthalic, terephthalic, trimellitic, pyromellitic, and tetrachloro-o-phthalic acids;
and the cyanides, cyanates, and thiocyanates of ammonium, alkali metals, and alkaline earth metals, magnesium and zinc, potassium ferrocyanide cyanogen chloride and bromide, cyanamide and its alkali metal and alkaline earth metal salts, the lower alkyl cyanates in which the alkyl group contains from 1 to about 6 carbon atoms, the phenyl cyanates, dicyandiamide, cyanuric halides, and melamine.

10 more elements

Process for the preparation of hydrazones

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Process for the preparation of hydrazones

Life of this patent

Abstract

Claims2