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

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

reacting at least one triacetonediamine compound (I) with at least one carbonyl compound (II) under reductive conditions,

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):

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

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;

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;

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 composed of 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), and (ii);

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;

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

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

Y 1 may also be a direct bond if at least one of p 1 and p 2 has the value of 1;

Y 2 may also be a direct bond if at least one of p 3 and p 4 has the value of 1;

Y 3 may also be a direct bond if at least one of p 5 and p 6 has the value of 1;

Y 4 may also be a direct bond if at least one of p 8 and p 9 has the value of 1;

Y 5 may also be a direct bond if at least one of p 10 and p 11 has the value of 1;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 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 ) 2 , —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 ) 2 , —N(CH 3 ) 2 , —NH(CH 2 CH 3 ), —N(CH 2 CH 3 ), 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);

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

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 —;

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;

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

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

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;

in the chemical structures (iii), (iv), (v), (vi), (vii), (viii), (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 );

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

hydrogen,

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

a group having the chemical structure (x);

R 18 , R 19 , R 20 , R 21 , R 22 , and R 23 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 );

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

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

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 —;

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;

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

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

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;

in the chemical structures (xi), (xii), (xiii), (xiv), (xv), (xvi), (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 );

with the proviso that R 12 and R 17 , when p 13 =p 14 =p 15 =p 16 =0, may each independently also be a group of the chemical structure (xviii);

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;

the carbonyl compound (II) is selected from the group consisting of the 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 composed of 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);

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;

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

R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 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 , and —N(CH 3 )(CH 2 CH 3 ), and

a radical having a chemical structure selected from the group consisting of (xxi), (xxii), (xxiii), (xxiv), (xxv), and (xxvi);

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

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 —;

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;

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

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

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 );

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;

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 an unsupported catalyst; and

the unsupported catalyst comprises at least one metal M selected from the group consisting of Ag, V, Cr, Mo, Mn, Ni, Pd, Pt, Fe, Ru, Os, Co, Rh, Ir, and Cu.

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

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:

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

divalent saturated hydrocarbyl group having 3 to 30 carbon atoms and having at least one saturated ring composed of 3 to 30 carbon atoms.

4. The process according to claim 1 , wherein;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 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 ),

a radical having a chemical structure (ix):

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;

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

hydrogen,

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

a group having the chemical structure (x):

R 18 , R 19 , R 20 , R 21 , R 22 , and R 23 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):

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;

with the proviso that R 12 and R 17 , when p 13 =p 14 =p 15 =p 16 =0, may each independently also be a group of the chemical structure (xviii):

and

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 (I) is selected from the group consisting of the chemical structures (I-A), and (I-B); and

R 1 , and R 2 are each independently selected from the group consisting of

hydrogen, and

unbranched or branched alkyl group which has 1 to 12 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 ).

7. The process according to claim 1 , wherein:

the triacetonediamine compound (I) is selected from the group consisting of the chemical structures (I-A), and (I-B); and

R 1 , and R 2 are each independently selected from the group consisting of

hydrogen, and

unbranched or 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,

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

divalent saturated hydrocarbyl group having 3 to 30 carbon atoms and having at least one saturated ring composed of 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 (I) is selected from the group consisting of the chemical structures (I-A), and (I-B);

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

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, and

unbranched or 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

unbranched or branched alkyl group having 1 to 12 carbon atoms, and

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 1 , wherein

the triacetonediamine compound (I) has the chemical structure (I-A); and

the carbonyl compound (11) has the chemical structure (II-A);

X 1 =hydrogen;

R 1 is selected from the group consisting of:

hydrogen, and

unbranched or branched alkyl group having 1 to 8 carbon atoms;

R 24 , R 25 are selected from the group consisting of:

hydrogen, and

unbranched or branched alkyl group having 1 to 8 carbon atoms;

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

12. The process according to claim 1 , wherein

the triacetonediamine compound (I) has the chemical structure (I-A);

the carbonyl compound (II) has the chemical structure (II-A);

X 1 =H;

R 1 =H;

R 24 is selected from the group consisting of hydrogen, and methyl; and

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 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.

15. The process according to claim 1 , wherein the metal M is selected from the group consisting of Ni, Co, Cu, Fe, and Ag.