Synthesis of triacetonediamine compounds by reductive amination proceeding from triacetonediamine and derivatives thereof

1. A process for preparing an N-substituted triacetonediamine compound, comprising:

reacting at least one triacetonediamine compound (I) with at least one carbonyl compound (II) under reductive conditions to obtain the N-substituted triacetonediamine compound,

wherein the triacetonediamine compound (I) is selected from the group consisting of the chemical structures (I-A), (I-B), (I-C), (I-D), and (I-E):

wherein the carbonyl compound (II) is selected from the group consisting of the chemical structures (II-A), (II-B), and (II-C):

and

wherein reductive conditions are established by reacting the at least one triacetonediamine compound (I) with the at least one carbonyl compound (II) in the presence of hydrogen and in the presence of a supported catalyst, wherein the supported catalyst comprises at least one metal M, wherein the metal M is selected from the group consisting of V, Cr, Mo, Mn, Ni, Pd, Pt, Fe, Ru, Os, Co, Rh, Ir, and Cu,

wherein in chemical structures (I-A), (I-B), (I-C), (I-D), and (I-E)

n is an integer from the range of 1 to 20:

wherein p 1 , p 2 , p 3 , p 4 , p 5 , p 6 , p 7 , p 8 , p 9 , p 10 , p 11 , p 12 , p 13 , p 14 , p 15 , p 16 are each independently 0 or 1;

wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 are each independently selected from the group consisting of hydrogen, OH, —O., unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms;

wherein Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 are each independently selected from the group consisting of

unbranched or branched alkylene group having 1 to 30 carbon atoms,

divalent saturated hydrocarbyl group having 3 to 30 carbon atoms and having at least one saturated ring comprising 3 to 30 carbon atoms,

divalent hydrocarbyl group having 6 to 30 carbon atoms, of which at least 6 carbon atoms are present in an aromatic system and the other carbon atoms, if present, are saturated, and

a bridging radical having a chemical structure selected from the group consisting of (i), (ii) with

wherein

Q 1 , Q 2 are each independently selected from the group consisting of —O—, —S—, —NH— and —NR′— with R′=unbranched or branched alkyl group having 1 to 6 carbon atoms,

wherein a is an integer selected from the range of 1 to 50,

wherein b is an integer selected from the range of 0 to 50,

and wherein Y 1 , if at least one of p 1 and p 2 has the value of 1, is selected from the list above including a direct bond,

and wherein Y 2 , if at least one of p 3 and p 4 has the value of 1, is selected from the list above including a direct bond,

and wherein Y 3 , if at least one of p 5 and p 6 has the value of 1, is selected from the list above including a direct bond,

and wherein Y 4 , if at least one of p 7 and p 8 has the value of 1, is selected from the list above including a direct bond,

and wherein Y 5 , if at least one of p 9 and p 10 has the value of 1, is selected from the list above including a direct bond,

wherein the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 1 , R 8 , R 9 , R 10 , R 11 radicals are each independently selected from the group consisting of

hydrogen,

unbranched or branched alkyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 ,

—NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 ),

unbranched or branched acyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 ,

—NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 ), and

a radical having a chemical structure selected from the group consisting of (iii), (iv), (v), (vi), (vii), (viii), and (ix) with

wherein J 1 , J 2 are each independently selected from the group consisting of CH, and N,

wherein K 1 , K 2 are each independently selected from the group consisting of —O—, —NH—, —N(CH 3 )—, —N(CH 2 CH 3 )—, —S—, and —CH 2 —,

wherein V 1 , V 2 , V 3 are each independently selected from the group consisting of —O—, —S—, —NH—, and —NR″— with R″=unbranched or branched alkyl group having 1 to 6 carbon atoms,

wherein W 1 , W 2 , W 3 are each independently selected from the group consisting of H, methyl, and ethyl,

wherein c, d, e, f, g, h are each independently an integer from the range of 0 to 50,

wherein X 13 is selected from the group consisting of hydrogen, —OH, —O., unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms,

wherein, in the chemical structures (iii), (iv), (v), (vi), (vii), (viii), and (ix), at least one hydrogen radical bonded to a carbon atom may be replaced by a radical selected from the group consisting of

—OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 , —NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 );

wherein the R 12 , R 13 , R 14 , R 15 , R 16 , R 17 radicals are each independently selected from the group consisting of

hydrogen,

unbranched or branched alkyl group having 1 to 30 carbon atoms, and

a group having the chemical structure (x) with

wherein the R 18 , R 19 , R 20 , R 21 , R 22 , R 23 radicals are each independently selected from the group consisting of

hydrogen,

unbranched or branched alkyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 ,

—NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 ),

unbranched or branched acyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 ,

—NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 ), and

a radical having a chemical structure selected from the group consisting of (xi), (xii), (xiii), (xiv), (xv), (xvi), and (xvii) with

wherein J 3 , J 4 are each independently selected from the group consisting of CH, and N,

wherein K 3 , K 4 are each independently selected from the group consisting of —O—, —NH—, —N(CH 3 )—, —N(CH 2 CH 3 )—, —S—, and —CH 2 —,

wherein V 4 , V 5 , V 6 are each independently selected from the group consisting of —O—, —S—, —NH—, and —NR′″— with R′″=unbranched or branched alkyl group having 1 to 6 carbon atoms,

wherein W 4 , W 5 , W 6 are each independently selected from the group consisting of H, methyl, and ethyl,

wherein j, k, m, q, r, s are each independently an integer from the range of 0 to 50,

wherein X 14 is selected from the group consisting of hydrogen, —OH, —O—, unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms,

where, in the chemical structures (xi), (xii), (xiii), (xiv), (xv), (xvi), and (xvii), at least one hydrogen radical bonded to a carbon atom may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 ,

OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 , —NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and

—N(CH 3 )(CH 2 CH 3 ),

and with the proviso that R 12 and R 17 , if p 13 =p 14 =p 15 =p 16 =0, are each independently selected from the list above including a group of the chemical structure (xviii) with

wherein X 15 is selected from the group consisting of hydrogen, OH, —O., unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms;

and wherein in chemical structures (II-A), (II-B), and II-C)

Z 1 , Z 2 , Z 3 are each independently selected from the group consisting of

direct bond, unbranched or branched alkylene group having 1 to 30 carbon atoms,

divalent saturated hydrocarbyl group having 3 to 30 carbon atoms and having at least one saturated ring comprising 3 to 30 carbon atoms,

divalent hydrocarbyl group having 6 to 30 carbon atoms, of which at least 6 carbon atoms are present in an aromatic system and the other carbon atoms, if present, are saturated, and

a bridging radical having a chemical structure selected from the group consisting of (xix), and (xx) with

wherein

T 1 , T 2 are each independently selected from the group consisting of —O—, —S— and —NR″″— with R″″=unbranched or branched alkyl group having 1 to 6 carbon atoms,

wherein a′ and b′ are each independently an integer selected from the range of 1 to 50;

and wherein the R 24 , R 25 , R 26 , R 27 , R 28 , R 29 radicals are selected from the group consisting of hydrogen, unbranched or branched alkyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —OCH 3 , —OCH 2 CH 3 , —N(CH 3 ) 2 , —N(CH 2 CH 3 ) 2 , —N(CH 3 )(CH 2 CH 3 ), a radical having a chemical structure selected from the group consisting of (xxi), (xxii), (xxiii), (xxiv), (xxv), and (xxvi):

wherein J 5 , J 6 are each independently selected from the group consisting of CH, and N,

wherein K 5 , K 6 are each independently selected from the group consisting of —O—, —N(CH 3 )—, —N(CH 2 CH 3 )—, —S—, and —CH 2 —,

wherein V 7 , V 8 , V 9 are each independently selected from the group consisting of —O—, —S—, and —NR′″″ with R′″″=unbranched or branched alkyl group having 1 to 6 carbon atoms,

wherein W 7 , W 8 , W 9 are each independently selected from the group consisting of H, methyl, and ethyl,

wherein j′, k′, m′, q′, r′, s′ are each independently an integer selected from the range of 0 to 50,

wherein, in the chemical structure (xxi), (xxii), (xxiii), (xxiv), (xxv), (xxvi), at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —OCH 3 , —OCH 2 CH 3 , —N(CH 3 ) 2 , —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 );

and wherein R 24 , R 25 , R 26 , R 27 , R 28 , R 29 are each selected independently, with the exclusion of: R 24 =R 25 =hydrogen.

2. The process according to claim 1 , wherein p 1 =p 2 =p 3 =p 4 =p 5 =p 6 =p 8 =p 9 =p 10 =p 11 =0 and wherein p 7 , p 12 , p 13 , p 14 , p 15 , p 16 are each independently 0 or 1.

3. The process according to claim 1 , wherein Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 are each independently selected from the group consisting of an unbranched alkylene group having 1 to 30 carbon atoms, a branched alkylene group having 1 to 30 carbon atoms, and a divalent saturated hydrocarbyl group having 3 to 30 carbon atoms and having at least one saturated ring comprising 3 to 30 carbon atoms.

4. The process according to claim 1 , wherein the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 radicals are each independently selected from the group consisting of hydrogen, unbranched or branched alkyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 , —NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH 3 )(CH 2 CH 3 ), and a radical having a chemical structure (ix)

wherein X 13 is selected from the group consisting of hydrogen, —OH, —O., unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms;

and wherein the R 12 , R 13 , R 14 , R 15 , R 16 , R 17 radicals are each independently selected from the group consisting of hydrogen, an unbranched or branched alkyl group having 1 to 30 carbon atoms, and a group having the chemical structure (x)

wherein the R 18 , R 19 , R 20 , R 21 , R 22 , R 23 radicals are each independently selected from the group consisting of hydrogen, unbranched or branched alkyl group which has 1 to 30 carbon atoms and in which at least one hydrogen radical may be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 , —NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH)(CH 2 CH 3 ), and a radical having a chemical structure (xvii)

wherein X 14 is selected from the group consisting of hydrogen, —OH, —O., unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms,

and with the proviso that R 12 and R 17 , if p 13 =p 14 =p 15 =p 16 =0, are each independently selected from the list above including a group of the chemical structure (xviii)

wherein X 15 is selected from the group consisting of hydrogen, OH, —O., unbranched or branched alkyl group having 1 to 10 carbon atoms, and unbranched or branched alkoxy group having 1 to 10 carbon atoms.

5. The process according to claim 1 , wherein X 1 =X 2 =X 3 =X 4 =X 5 =X 6 =X 7 =X 8 =X 9 =X 10 =X 11 =X 12 =X 13 =X 14 =X 15 =hydrogen.

6. The process according to claim 1 , wherein the triacetonediamine compound (1) is selected from the group consisting of the chemical structures (I-A), and (I-B) and wherein the R 1 , R 2 radicals are each independently selected from the group consisting of hydrogen, an unbranched alkyl group which has 1 to 12 carbons, and a branched alkyl group which has 1 to 12 carbon atoms, wherein at least one hydrogen radical of the branched and unbranched alkyl group may optionally be replaced by a radical selected from the group consisting of —OH, —NH 2 , —OCH 3 , —OCH 2 CH 3 , —NH(CH 3 ), —N(CH 3 ) 2 , —NH(CH 2 CH 3 ), —N(CH 2 CH 3 ) 2 , and —N(CH)(CH 2 CH 3 ).

7. The process according to claim 6 , wherein the triacetonediamine compound (I) is selected from the group consisting of the chemical structures (I-A), and (I-B) and wherein the R 1 , R 2 radicals are each independently selected from the group consisting of hydrogen, an unbranched alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 1 to 12 carbon atoms.

8. The process according to claim 1 , wherein Z 1 , Z 2 , Z 3 are each independently selected from the group consisting of direct bond, an unbranched alkylene group having 1 to 30 carbon atoms, a branched alkylene group having 1 to 30 carbon atoms, and a divalent saturated hydrocarbyl group having 3 to 30 carbon atoms and having at least one saturated ring comprising 3 to 30 carbon atoms.

9. The process according to claim 1 , wherein the carbonyl compound (II) is selected from the group consisting of the chemical structures (II-A), and (II-B).

10. The process according to claim 1 , wherein the triacetonediamine compound (1) is selected from the group consisting of the chemical structures (I-A), and (I-B) and wherein the carbonyl compound (II) is selected from the group consisting of the chemical structures (II-A), and (II-B), wherein

p 1 =p 2 =0;

X 1 =X 2 =X 3 =hydrogen;

Y 1 and Z 1 are each independently an unbranched or branched alkylene group having 1 to 12 carbon atoms;

R 1 , R 2 are each independently selected from the group consisting of hydrogen, an unbranched alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 1 to 12 carbon atoms;

R 24 , R 25 , R 26 , R 27 are selected from the group consisting of hydrogen, and an unbranched alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 1 to 12 carbon atoms;

wherein R 24 , R 25 , R 26 , R 27 are each selected independently, with the exclusion of: R 24 =R 25 =hydrogen.

11. The process according to claim 10 , wherein the triacetonediamine compound (I) has the chemical structure (I-A) and wherein the carbonyl compound (II) has the chemical structure (II-A), where

X 1 =hydrogen;

R 1 is selected from the group consisting of hydrogen, an unbranched alkyl group having 1 to 8 carbon atoms and a branched alkyl group having 1 to 8 carbon atoms;

R 24 , R 25 are selected from the group consisting of hydrogen, an unbranched alkyl group having 1 to 8 carbon atoms and a branched alkyl group having 1 to 8 carbon atoms;

wherein R 24 , R 25 are each selected independently, with the exclusion of: R 24 =R 25 =hydrogen.

12. The process according to claim 11 , wherein the triacetonediamine compound (I) has the chemical structure (I-A) and wherein the carbonyl compound (II) has the chemical structure (II-A), wherein X 1 =H; R 1 =H; R 24 is selected from the group consisting of hydrogen, and methyl; R 25 is an unbranched or branched alkyl group having 1 to 8 carbon atoms.

13. The process according to claim 1 , which is conducted in at least one solvent, wherein the solvent is selected from the group consisting of aliphatic solvents, aromatic solvents, ethers, halogenated solvents, amides, thio compounds, carboxylic acids, alcohols, and water.

14. The process according to claim 1 , which is conducted at a temperature in the range from 20° C. to 350° C. and a pressure in the range from 2 bar to 500 bar.