Method for preparing azines and hydrazones

Claim 1

A method for preparing an azine or a mixture of azines which comprises reacting (i) at least one carbonyl compound having the formula ##EQU1##wherein R 1 and R 2 , which can be identical or different, are each an atom of hydrogen or a (C 1 -C 12 ) straight chain alkyl radical, a (C 3 -C 12 ) branched alkyl or cycloalkyl radical, a phenyl radical, a naphthyl radical, or a pyridine radical, or R 1 and R 2 together represent a C 3 -C 11 alkylene radical, straight-chained or branched, wherein one of the carbons may be replaced by an oxygen atom, the aforementioned radicals being unsubstituted or substituted with one or more halogen atoms or nitrile, nitro, hydroxy, alkoxy, carboxy, carbamyl or carbalkoxy groups, with (ii) a mixture of ammonia and hydrogen peroxide in the presence of (iii) both (a) an amide of a carboxylic acid having a pK equal to or greater than 4.3 or of a polycarboxylic acid having a first ionization constant equal to or greater than 4.3 and (b) a co-catalyst selected from the acids and the alkali-metal and ammonium salts of a phosphate, a phosphite, a mono- or di- (C 1 -C 6 ) alkyl phosphate ester, a polyphosphate, a pyrophosphate, an arsenate, a benzene or toluene sulfonate or phosphonate, a (C 1 -C 6 ) alkyl sulfate ester, a bicarbonate, an antimonate or a stannate.

Claim 2

A method for preparing an azine or a mixture of azines which comprises reacting (i) at least one carbonyl compound having the formula ##EQU1##wherein R 1 and R 2 , which can be identical or different, are each an atom of hydrogen or a (C 1 -C 12 ) straight chain alkyl radical, a (C 3 -C 12 ) branched alkyl or cycloalkyl radical, a phenyl radical, a naphthyl radical, or a pyridine radical, or R 1 and R 2 together represent a C 3 -C 11 alkylene radical, straight-chained or branched, wherein one of the carbons may be replaced by an oxygen atom, the aforementioned radicals being unsubstituted or substituted with one or more halogen atoms or nitrile, nitro, hydroxy, alkoxy, carboxy, carbamyl or carbalkoxy groups, with (ii) a mixture of ammonia and hydrogen peroxide in the presence of (iii) both (a) an amide of a carboxylic acid having a pK equal to or greater than 4.3 or of a polycarboxylic acid having a first ionization constant equal to or greater than 4.3 and (b) a co-catalyst selected from the acids and the alkali-metal and ammonium salts of a phosphate, a phosphite, a mono- or di- (C 1 -C 6 ) alkyl phosphate ester, a polyphosphate, a pyrophosphate, an arsenate, a benzene or toluene sulfonate or phosphonate, a (C 1 -C 6 ) alkyl sulfate ester, a bicarbonate, an antimonate or a stannate.

Claim 11

A method for preparing an azine or a mixture of azines which comprises reacting: a. hydrogen peroxide; b. ammonia; c. a carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-pentanal, caproic aldehyde, caprylic aldehyde, 2-ethylhexanal, trimethylacetaldehyde, oenanthal, 3-Δ-tetrahydrobenzaldehyde, hexahydrobenzaldehyde, 5-norbornene-2-carboxaldehyde, tetrahydropyran-2-carboxaldehyde, benzaldehyde, the monochlorbenzaldehydes, p-nitrobenzaldehyde, anisaldehyde, β-chloropropionaldehyde, β-methoxypropionaldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, ethylamylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof; d. an amide of acetic, propionic, n-butyric, isobutyric, n-valeric, trimethylacetic, caproic, n-heptylic, hexahydrobenzoic, caprylic, pelargonic, capric, undecanoic, lauric, n-tridecyclic, myristic, n-pentadecyclic, palmitic, margaric, stearic, nonadecanoic, arachidic, heneicosanoic, adipic, pimelic, suberic, azelaic, sebacic, p-hydroxybenzoic, anisic acid, gallic acid, anthranilic acid, m-aminobenzoic or p-aminobenzoic acid; and e. a co-catalyst selected from sodium orthophosphate, trisodium phosphate (TSP), disodium hydrogen orthophosphate, sodium dihydrogen orthophosphate, sodium pyrophosphate or dipolyphosphate (TSPP), disodium dihydrogen pyrophosphate Na 2 H 2 P 2 O 7 , anhydrous or as hexahydrate, trisodium pyrophosphate, anhydrous or as heptahydrate, sodium trihydrogen pyrophosphate, pentasodium tripolyphosphate Na 5 P 3 H 10 , (STPP), metaphosphoric acid HPO 3 , sodium mono-metaphosphate NaPO 3 , sodium trimetaphosphate Na 3 (PO 3 ) 3 , sodium tetrametaphosphate Na 4 (PO 3 ) 4 or sodium hexametaphosphate (NaPO 3 ) 6 , sodium phosphite (Na 2 HPO 3 , 5H 2 O), a sodium salt of ethylphosphonic or butylphosphonic acid, lithium benzene phosphonate, disodium arsenate (Na 2 HAsO 4 ), sodium selenate (Na 2 SeO 4 , 10H 2 O), sodium bicarbonate, ammonium p-toluene sulfonate, potassium acid pyroantimonate (K 2 H 2 Sb 2 O 7 .H 2 O), sodium tellurate (Na 2 TeO 3 ) and sodium stannate (Na 2 SnO 3 . 3H 2 O), and from n-propyl dihydrogen phosphate, di(isopropyl) hydrogen phosphate, n-butyl dihydrogen phosphate, di(n-butyl) hydrogen phosphate, sec-butyl dihydrogen phosphate, n-amyl dihydrogen phosphate, n-hexyl dihydrogen phosphate and cylcohexyl dihydrogen phosphate and the alkali-metal and ammonium salts thereof.

Claim 12

A method for preparing an azine or a mixture of azines which comprises reacting: a. hydrogen peroxide; b. ammonia; c. a carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-pentanal, caproic aldehyde, caprylic aldehyde, 2-ethylhexanal, trimethylacetaldehyde, oenanthal, 3-Δ-tetrahydrobenzaldehyde, hexahydrobenzaldehyde, 5-norbornene-2-carboxaldehyde, tetrahydropyran-2-carboxaldehyde, benzaldehyde, the monochlorbenzaldehydes, p-nitrobenzaldehyde, anisaldehyde, β-chloropropionaldehyde, β-methoxypropionaldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, ethylamylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof; d. an amide of acetic, propionic, n-butyric, isobutyric, n-valeric, trimethylacetic, caproic, n-heptylic, hexahydrobenzoic, caprylic, pelargonic, capric, undecanoic, lauric, n-tridecyclic, myristic, n-pentadecyclic, palmitic, margaric, stearic, nonadecanoic, arachidic, heneicosanoic, adipic, pimelic, suberic, azelaic, sebacic, p-hydroxybenzoic, anisic acid, gallic acid, anthranilic acid, m-aminobenzoic or p-aminobenzoic acid; and e. a co-catalyst selected from sodium orthophosphate, trisodium phosphate (TSP), disodium hydrogen orthophosphate, sodium dihydrogen orthophosphate, sodium pyrophosphate or dipolyphosphate (TSPP), disodium dihydrogen pyrophosphate Na 2 H 2 P 2 O 7 , anhydrous or as hexahydrate, trisodium pyrophosphate, anhydrous or as heptahydrate, sodium trihydrogen pyrophosphate, pentasodium tripolyphosphate Na 5 P 3 H 10 , (STPP), metaphosphoric acid HPO 3 , sodium mono-metaphosphate NaPO 3 , sodium trimetaphosphate Na 3 (PO 3 ) 3 , sodium tetrametaphosphate Na 4 (PO 3 ) 4 or sodium hexametaphosphate (NaPO 3 ) 6 , sodium phosphite (Na 2 HPO 3 , 5H 2 O), a sodium salt of ethylphosphonic or butylphosphonic acid, lithium benzene phosphonate, disodium arsenate (Na 2 HAsO 4 ), sodium selenate (Na 2 SeO 4 , 10H 2 O), sodium bicarbonate, ammonium p-toluene sulfonate, potassium acid pyroantimonate (K 2 H 2 Sb 2 O 7 .H 2 O), sodium tellurate (Na 2 TeO 3 ) and sodium stannate (Na 2 SnO 3 . 3H 2 O), and from n-propyl dihydrogen phosphate, di(isopropyl) hydrogen phosphate, n-butyl dihydrogen phosphate, di(n-butyl) hydrogen phosphate, sec-butyl dihydrogen phosphate, n-amyl dihydrogen phosphate, n-hexyl dihydrogen phosphate and cylcohexyl dihydrogen phosphate and the alkali-metal and ammonium salts thereof.

Claim 13

A method for preparing a mixture of at least one azine and at least one hydrazone which comprises reacting (i) at least one carbonyl compound having the formula ##STR8##wherein R 1 and R 2 , which can be identical or different are each an atom of hydrogen or a (C 1 -C 12 ) straight chain alkyl radical, a (C 3 -C 12 ) branched alkyl or cycloalkyl radical, a phenyl radical, a naphthyl radical, or a pyridine radical, or R 1 and R 2 together represent a C 3 -C 11 alkylene radical, straight-chained or branched, wherein one of the carbons may be replaced by an oxygen atom, the aforementioned radicals being unsubstituted or substituted with one or more halogen atoms or nitrile, nitro, hydroxy, alkoxy, carboxy, carbamyl or carbalkoxy groups, with (ii) a mixture of ammonia, hydrogen peroxide and at least one amine of formula ##STR9##wherein R 3 and R 4 , which can be identical or different, are each a (C 1 -C 12 ) straight-chained alkyl radical, a (C 3 -C 12 ) branched alkyl or cycloalkyl radical, a phenyl radical, a naphthyl radical, or a pyridine radical, or R 3 and R 4 together can be a straight-chained or branched (C 3 -C 11 ) alkylene radical wherein one of the carbon atoms may be replaced by an oxygen atom, the aforementioned radicals being unsubstituted or substituted by one or more halogen atoms or hydroxy, alkoxy, carboxyl, carbamyl, nitrile, nitro, sulfonic or sulfonamide groups, or R 4 can be hydrogen, in the presence of (iii) both (a) an amide of a carboxylic acid having a pK equal to or greater than 4.3 or of a polycarboxylic acid having a first ionization constant equal to or greater than 4.3 and (b) a co-catalyst selected from the acids and the alkali-metal and ammonium salts of a phosphate, a phosphite, a mono- or di- (C 1 -C 6 ) alkyl phosphate ester, a polyphosphate, a pyrophosphate, an arsenate, a benzene or toluene sulfonate or phosphonate, a (C 1 -C 6 ) alkyl phosphonate, a sulfate, a (C 1 -C 6 ) alkyl sulfate ester, a bicarbonate, an antimonate or a stannate.

Claim 14

A method for preparing a mixture of at least one azine and at least one hydrazone which comprises reacting (i) at least one carbonyl compound having the formula ##STR8##wherein R 1 and R 2 , which can be identical or different are each an atom of hydrogen or a (C 1 -C 12 ) straight chain alkyl radical, a (C 3 -C 12 ) branched alkyl or cycloalkyl radical, a phenyl radical, a naphthyl radical, or a pyridine radical, or R 1 and R 2 together represent a C 3 -C 11 alkylene radical, straight-chained or branched, wherein one of the carbons may be replaced by an oxygen atom, the aforementioned radicals being unsubstituted or substituted with one or more halogen atoms or nitrile, nitro, hydroxy, alkoxy, carboxy, carbamyl or carbalkoxy groups, with (ii) a mixture of ammonia, hydrogen peroxide and at least one amine of formula ##STR9##wherein R 3 and R 4 , which can be identical or different, are each a (C 1 -C 12 ) straight-chained alkyl radical, a (C 3 -C 12 ) branched alkyl or cycloalkyl radical, a phenyl radical, a naphthyl radical, or a pyridine radical, or R 3 and R 4 together can be a straight-chained or branched (C 3 -C 11 ) alkylene radical wherein one of the carbon atoms may be replaced by an oxygen atom, the aforementioned radicals being unsubstituted or substituted by one or more halogen atoms or hydroxy, alkoxy, carboxyl, carbamyl, nitrile, nitro, sulfonic or sulfonamide groups, or R 4 can be hydrogen, in the presence of (iii) both (a) an amide of a carboxylic acid having a pK equal to or greater than 4.3 or of a polycarboxylic acid having a first ionization constant equal to or greater than 4.3 and (b) a co-catalyst selected from the acids and the alkali-metal and ammonium salts of a phosphate, a phosphite, a mono- or di- (C 1 -C 6 ) alkyl phosphate ester, a polyphosphate, a pyrophosphate, an arsenate, a benzene or toluene sulfonate or phosphonate, a (C 1 -C 6 ) alkyl phosphonate, a sulfate, a (C 1 -C 6 ) alkyl sulfate ester, a bicarbonate, an antimonate or a stannate.

Claim 24

A method for preparing a mixture of at least one azine and at least one hydrazone which comprises reacting: a. hydrogen peroxide; b. ammonia; c. a carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-pentanal, caproic aldehyde, caprylic aldehyde, 2-ethylhexanal, trimethylacetaldehyde or pivalaldehyde, oenanthal, 3-Δ-tetrahydrobenzaldehyde, hexahydrobenzaldehyde, 5-norbornene-2-carboxaldehyde, tetrahydropyran-2-carboxaldehyde, benzaldehyde, the monochlorbenzaldehydes, p-nitrobenzaldehyde, anisaldehyde, β-chloropropionaldehyde, β-methoxypropionaldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, ethylamylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof; d. one or more amines selected from methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, di-(n-butyl)amine, isobutylamine, sec-butylamine, tert-butylamine, the amylamines, cyclohexylamine, di(cyclohexyl)amine, n-dodecyclamine, 2-methoxyethylamine, morpholine, pyrrolidine, piperidine, beta-aminopropionitrile, beta-aminopropionamide, aniline, the toluidines, mono- and di-chloroanilines or chlorotoluidines, the bromoanilines, the fluoroanilines, the nitroanilines, the dinitroanilines, the nitro and dinitro toluidines, ortho-anisidine, meta-anisidine, para-anisidine, the trifluoromethylanilines, anthranilic acid, sulfanilic acid, diphenylamine, alpha-naphthylamine, beta-naphthylamine and the amino pyridines, and mixtures thereof; e. an amide of acetic, propionic, n-butyric, isobutyric, n-valeric, trimethylacetic, caproic, n-heptylic, cyclohexanecarboxylic or hexahydrobenzoic, caprylic, pelargonic, capric, undecanoic, lauric, n-tridecylic, myristic, n-pentadecylic, palmitic, margaric, stearic, nonadecanoic, arachidic, heneicosanoic, adipic, pimelic, suberic, azelaic, sebacic, p-hydroxybenzoic, anisic, gallic, anthranilic, m-aminobenzoic or p-aminobenzoic acid; and f. a phosphate selected from sodium orthophosphate or trisodium phosphate (TSP), disodium hydrogen orthophosphate, sodium dihydrogen orthophosphate, sodium pyrophosphate or dipolyphosphate (TSPP), disodium dihydrogen pyrophosphate Na 2 H 2 P 2 O 7 , anhydrous or as hexahydrate, trisodium pyrophosphate, anhydrous or as heptahydrate, sodium trihydrogen pyrophosphate, pentasodium tripolyphosphate Na 5 P 3 H 10 , (STPP), metaphosphoric acid HPO 3 , sodium mono-metaphosphate NaPO 3 , sodium trimetaphosphate Na 3 (PO 3 ) 3 , sodium tetrametaphosphate Na 4 (PO 3 ) 4 or sodium hexametaphosphate (NaPO 3 ) 6 , a sodium phosphite (Na 2 HPO 3 , 5H 2 O), a sodium salt of ethylphosphonic or butylphosphonic acid, lithium benzene phosphonate, disodium arsenate (Na 2 HAsO 4 ), sodium selenate (Na 2 SeO 4 , 10H 2 O), sodium bicarconate, ammonium p-toluene sulfonate, potassium acid pyroantimonate (K 2 H 2 Sb 2 O 7 . H 2 O), sodium tellurate (Na 2 TeO 3 ) and sodium stannate (Na 2 SnO 3 . 3H 2 O), n-propyl dihydrogen phosphate, di(isopropyl) hydrogen phosphate, n-butyl dihydrogen phosphate, di(n-butyl hydrogen phosphate, sec-butyl dihydrogen phosphate, n-amyl dihydrogen phosphate, n-hexl dihydrogen phosphate and cyclohexyl dihydrogen phosphate and the alkali-metal and ammonium salts thereof.

Claim 25

A method for preparing a mixture of at least one azine and at least one hydrazone which comprises reacting: a. hydrogen peroxide; b. ammonia; c. a carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-pentanal, caproic aldehyde, caprylic aldehyde, 2-ethylhexanal, trimethylacetaldehyde or pivalaldehyde, oenanthal, 3-Δ-tetrahydrobenzaldehyde, hexahydrobenzaldehyde, 5-norbornene-2-carboxaldehyde, tetrahydropyran-2-carboxaldehyde, benzaldehyde, the monochlorbenzaldehydes, p-nitrobenzaldehyde, anisaldehyde, β-chloropropionaldehyde, β-methoxypropionaldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, ethylamylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof; d. one or more amines selected from methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, di-(n-butyl)amine, isobutylamine, sec-butylamine, tert-butylamine, the amylamines, cyclohexylamine, di(cyclohexyl)amine, n-dodecyclamine, 2-methoxyethylamine, morpholine, pyrrolidine, piperidine, beta-aminopropionitrile, beta-aminopropionamide, aniline, the toluidines, mono- and di-chloroanilines or chlorotoluidines, the bromoanilines, the fluoroanilines, the nitroanilines, the dinitroanilines, the nitro and dinitro toluidines, ortho-anisidine, meta-anisidine, para-anisidine, the trifluoromethylanilines, anthranilic acid, sulfanilic acid, diphenylamine, alpha-naphthylamine, beta-naphthylamine and the amino pyridines, and mixtures thereof; e. an amide of acetic, propionic, n-butyric, isobutyric, n-valeric, trimethylacetic, caproic, n-heptylic, cyclohexanecarboxylic or hexahydrobenzoic, caprylic, pelargonic, capric, undecanoic, lauric, n-tridecylic, myristic, n-pentadecylic, palmitic, margaric, stearic, nonadecanoic, arachidic, heneicosanoic, adipic, pimelic, suberic, azelaic, sebacic, p-hydroxybenzoic, anisic, gallic, anthranilic, m-aminobenzoic or p-aminobenzoic acid; and f. a phosphate selected from sodium orthophosphate or trisodium phosphate (TSP), disodium hydrogen orthophosphate, sodium dihydrogen orthophosphate, sodium pyrophosphate or dipolyphosphate (TSPP), disodium dihydrogen pyrophosphate Na 2 H 2 P 2 O 7 , anhydrous or as hexahydrate, trisodium pyrophosphate, anhydrous or as heptahydrate, sodium trihydrogen pyrophosphate, pentasodium tripolyphosphate Na 5 P 3 H 10 , (STPP), metaphosphoric acid HPO 3 , sodium mono-metaphosphate NaPO 3 , sodium trimetaphosphate Na 3 (PO 3 ) 3 , sodium tetrametaphosphate Na 4 (PO 3 ) 4 or sodium hexametaphosphate (NaPO 3 ) 6 , a sodium phosphite (Na 2 HPO 3 , 5H 2 O), a sodium salt of ethylphosphonic or butylphosphonic acid, lithium benzene phosphonate, disodium arsenate (Na 2 HAsO 4 ), sodium selenate (Na 2 SeO 4 , 10H 2 O), sodium bicarconate, ammonium p-toluene sulfonate, potassium acid pyroantimonate (K 2 H 2 Sb 2 O 7 . H 2 O), sodium tellurate (Na 2 TeO 3 ) and sodium stannate (Na 2 SnO 3 . 3H 2 O), n-propyl dihydrogen phosphate, di(isopropyl) hydrogen phosphate, n-butyl dihydrogen phosphate, di(n-butyl hydrogen phosphate, sec-butyl dihydrogen phosphate, n-amyl dihydrogen phosphate, n-hexl dihydrogen phosphate and cyclohexyl dihydrogen phosphate and the alkali-metal and ammonium salts thereof.