Process for preparing tertiary amines

Claim 2

A process for preparing tertiary amines which comprises in absence of added formic acid reacting a carbonyl compound with a formyl derivative of a secondary amine at a temperature of 200° to 300° C. in the presence of at least one compound selected from the group consisting of water and lower aliphatic alcohols containing 1 to 4 carbon atoms, the amount of said at least one compound selected from the group consisting of water and lower alcohols containing 1 to 4 carbon atoms being 1 to 10 mols per mol of the carbonyl compound, said carbonyl compound being selected from the group consisting of: 1. aliphatic aldehydes of the general formula ##STR12## wherein R 2 is an aliphatic radical containing 1 to 40 carbon atoms,

Claim 3

alicyclic aldehydes of the general formula ##STR13## wherein R 2 is an alicyclic radical containing 5 to 20 carbon atoms,

Claim 4

alicyclic aldehydes of the general formula ##STR13## wherein R 2 is an alicyclic radical containing 5 to 20 carbon atoms,

Claim 5

aromatic aldehydes of the general formula ##STR14## wherein R 2 is an aromatic radical,

Claim 6

aromatic aldehydes of the general formula ##STR14## wherein R 2 is an aromatic radical,

Claim 7

aliphatic ketones of the general formula ##STR15## wherein R 1 and R 2 represent an aliphatic radical containing 1 to 20 carbon atoms, 5.

Claim 8

aliphatic ketones of the general formula ##STR15## wherein R 1 and R 2 represent an aliphatic radical containing 1 to 20 carbon atoms, 5.

Claim 9

aliphatic-aromatic ketones of the general formula ##STR16## wherein R 1 is an aliphatic radical containing 1 to 20 carbon atoms and R 2 is an aromatic radical, 6.

Claim 10

aliphatic-aromatic ketones of the general formula ##STR16## wherein R 1 is an aliphatic radical containing 1 to 20 carbon atoms and R 2 is an aromatic radical, 6.

Claim 11

aliphatic-heterocyclic ketones of the general formula ##STR17## wherein R 1 is an aliphatic radical containing 1 to 20 carbon atoms and R 2 is a heterocyclic radical, 7.

Claim 12

aliphatic-heterocyclic ketones of the general formula ##STR17## wherein R 1 is an aliphatic radical containing 1 to 20 carbon atoms and R 2 is a heterocyclic radical, 7.

Claim 13

aromatic ketones of the general formula ##STR18## wherein R 1 and R 2 represent an aromatic radical, and

Claim 14

aromatic ketones of the general formula ##STR18## wherein R 1 and R 2 represent an aromatic radical, and

Claim 15

alicyclic ketones of the general formula ##STR19## wherein R 1 -R 2 is a biradical containing 4 to 40 carbon atoms, said formyl derivative of a secondary amine being selected from i. formyl derivatives of aliphatic secondary amines of the general formula ##STR20## wherein R 3 and R 4 represent an aliphatic radical containing 1 to 20 carbon atoms, and ii. formyl derivatives of cyclic secondary amines of the general formula ##STR21## wherein R 3 -R 4 represents a biradical containing 3 to 20 carbon atoms, all of said aliphatic and alicyclic radicals and alcohols being

Claim 16

alicyclic ketones of the general formula ##STR19## wherein R 1 -R 2 is a biradical containing 4 to 40 carbon atoms, said formyl derivative of a secondary amine being selected from i. formyl derivatives of aliphatic secondary amines of the general formula ##STR20## wherein R 3 and R 4 represent an aliphatic radical containing 1 to 20 carbon atoms, and ii. formyl derivatives of cyclic secondary amines of the general formula ##STR21## wherein R 3 -R 4 represents a biradical containing 3 to 20 carbon atoms, all of said aliphatic and alicyclic radicals and alcohols being

Claim 17

saturated. 2. A process of claim 1 wherein a secondary amine is present at the start of the reaction, said secondary amine being the same as that

Claim 18

present as the formyl derivative. 3. A process according to claim 1 wherein an aliphatic aldehyde is employed as the carbonyl compound and said aldehyde is selected from the group consisting of ethanal, propanal, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal, pentadecanal, hexadecanal, heptadecanal, octadecanal, nonadecanal, eicosanal, heneicosanal, docosanal, tricosanal, tetracosanal, pentacosanal, hexacosanal, heptacosanal, octacosanal, nonacosanal, triacontanal, hentriacontanal, ditriacontanal, tritriacontanal, tetratriacontanal, pentatriacontanal, hexatriacontanal, heptatriacontanal, octatriacontanal, nonatriacontanal, tetracontanal hentetracontanal, pentanedial, hexanedial, octanedial, decanedial, dodecanedial, straight chain oxoaldehydes obtained by the oxo-reaction of stright-chain monolefins containing 10 to 40 carbon atoms; 2-methylpropanal, 2-methylbutanal, 2-methylpentanal, 2-methylhexanal, 2-methylheptanal, 2-methyloctanal, 2-methylnonanal, 2-methyldecanal, 2-methylundecanal, 2-methyldodecanal, 2-methyltridecanal, 2-methyltetradecanal, 2-methylpentadecanal, 2-methylhexadecanal, 2-methylheptadecanal, 2-methyloctadecanal, 2-methylnonadecanal, 2-methyleicosanal, 2,2-dimethylpropanal, 2-ethylbutanal, 2-ethylhexanal, 2-propylheptanal, 2-butyloctanal, 2-pentylnonanal, 2-hexyldecanal, 2-octyldodecanal and 2-methyloxoaldehyde mixtures obtained by the oxo-reaction of straight-chain monolefins containing 10 to 40 carbon

Claim 19

atoms. 4. A process according to claim 1 wherein an alicyclic aldehyde is employed as the carbonyl compound and said aldehyde is selected from the group consisting of cyclopentane-aldehyde, cyclohexane-aldehyde, cycloheptane-aldehyde, cyclooctane-aldehyde, cyclodecane-aldehyde, cyclododecanealdehyde, cyclononadecane-aldehyde, cyclohexane-1,2-dialdehyde, cyclohexane-1,3-dialdehyde, cyclohexane-1,4-dialdehyde, 2-methylcyclohexane-aldehyde, 3-methylcyclohexane-aldehyde, 4-methylcyclohexane-aldehyde, and

Claim 20

4-methoxycyclohexane-aldehyde. 5. A process according to claim 1 wherein an aromatic aldehyde is employed as the carbonyl compound and said aldehyde is selected from the group consisting of benzaldehyde, o-phthalic aldehyde, m-phthalic aldehyde, p-phthalic aldehyde, α-naphthoic aldehyde, β-napththoic aldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, o-anisaldehyde, m-anisaldehyde, p-anisaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-bromobenzaldehyde, m-bromobenzaldehyde, p-bromobenzaldehyde, 2,4-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, p-dimethylaminobenzaldehyde, and

Claim 21

cumic aldehyde. 6. A process according to claim 1 wherein an aliphatic ketone is employed as the carbonyl compound and said ketone is selected from the group consisting of 2-propanone, 2-butanone, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodeconones, tridecanones, tetradecanones, pentadecanones, hexadecanones, heptadecanones, octadecanones, nonadecanones, eicosanones, heneisosanones, docosanones, tricosanones, tetracosanones, pentacosanones, hexacosanones, heptacosanones, octacosanones, nonacosanones, triacontanones, hentriacontanones, dotriacontanones, tritriacontanones, tetratriacontanones, pentatriacontanones, hexatriacontanones, heptatriacontanones, octatriacontanones nonatriacontanones, tetracontanones, hentetracontanones, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,6-dimethyl-4-heptanone, 1-phenyl-2-propanone, 1-(o-chloro)-phenyl-2-propanone, 1-(m-nitro)-phenyl-2-propanone, methyl cyclohexyl ketone, ketone mixtures obtained by the oxidation of straight chain hydrocarbons containing 10 to 40 carbon atoms, and ketone mixtures obtained by the dehydrogenation of secondary alcohols containing 10 to 40

Claim 22

carbon atoms. 7. A process according to claim 1 wherein an aliphatic aromatic ketone is employed as the carbonyl compound and said ketone is selected from the group consisting of acetophenone, propionphenone, isobutyrophenone, isovalerophenone, laurophenone, β-acetonaphthone, p-chloroacetophenone, p-bromoacetophenone, p-methoxyacetophenone, p-methylacetophenone, m-nitroacetophenones, p-phenoxyacetophenone, and

Claim 23

p-phenylacetophenone. 8. A process according to claim 1 wherein an aliphatic heterocylic ketone is employed and said ketone is selected from the group consisting of α-acetothienone and α-propiothenone.

Claim 24

A process according to claim 1 wherein an aromatic ketone is employed and said ketone is selected from the group consisting of benzophenone and fluorenone.

Claim 25

A process according to claim 1 wherein an alicyclic ketone is employed and said ketone is selected from the group consisting of cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone, cyclopentadecanone, fenchone, menthone, 2-camphanone, 3-cholestanone, thujone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, and 4-methylcyclohexanone.

Claim 26

A process according to claim 1 wherein a formyl derivative of a aliphatic secondary amine is employed and said derivative is selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-dihexylformamide, N,N-dioctylformamide, N,N-didecylformamide, N,N-didodecylformamide, N,N-dioctadecylformamide, N,N-dieicosylformamide, N-methyl-N-benzylformamide, and N-dodecyl-N-benzylformamide.

Claim 27

A process according to claim 1 wherein a formyl derivative of a cyclic secondary amine is employed and said derivative is selected from the group consisting of N-formylpyrrolidine, N-formylpiperidine, N-formylmorpholine, N-formylthiamorpholine, N,N'-diformylpiperazine, N-formyl-N'-methylpiperazine, N-formylanabasine, N-formylindazole, N-formylimidazoline, N-formylpyrazoline, N-formylpurine, N-formylcarbazole, N-formylphenoxazine, N-formylindoline, and N-formylisoindoline.

Claim 28

The process of claim 1 wherein said lower alcohol is methanol.

Claim 29

The process of claim 2 wherein said lower alcohol is methanol.

Claim 30

The process of claim 2 wherein said secondary amine is an aliphatic secondary amine.

Claim 31

The process of claim 2 wherein said secondary amine is a cyclic secondary amine.