Granted Patent B2

US 9,663,443 · App. 14/233,328 · Granted May 30, 2017

Abstract

Claims (65)

1. A process for making a compound of formula I:

wherein

each R 2 is independently H or C 1 -C 6 alkyl;

each R 5 is independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, or R 2 and R 5 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl; and

R 3 and R 4 are independently C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, or —C(OH)R 2 R 5 , or R 3 and R 4 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl,

the process comprising:

(a) reacting a compound of formula III

with a compound of formula IV

wherein R and R 1 are independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, in the presence of a catalytic amount of the compound of formula I to produce an intermediate product mixture comprising free compound of formula III and a nitroalcohol compound of formula II

 and

(b) hydrogenating the intermediate product mixture in the presence of hydrogen and a catalyst.

2. The process of claim 1 wherein the intermediate product mixture of step (a) comprises at least two moles of free carbonyl compound of formula III per mole of nitroalcohol compound of formula II.

3. The process according to claim 2 wherein additional carbonyl compound of formula III is added following step (b).

4. The process according to claim 2 wherein R 3 and R 4 are each independently C 1 -C 3 alkyl.

5. The process according to claim 2 wherein R 2 and R 5 are H.

6. The process according to claim 2 wherein R 3 and R 4 are each meth.

7. The process according to claim 2 wherein all R 2 groups are the same and all R 5 groups are the same.

8. The process of claim 1 wherein additional carbonyl compound of formula III is added following step (b).

9. The process of claim 1 wherein R 3 and R 4 are each independently C 1 -C 3 alkyl.

10. The process of claim 1 wherein R 3 and R 4 are each —C(OH)R 2 R 5 .

11. The process of claim 1 wherein R 3 is —C(OH)R 2 R 5 and R 4 is C 1 -C 6 alkyl.

12. The process of claim 1 wherein R 3 and R 4 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl.

13. The process of claim 1 wherein R 2 and R 5 are H.

14. The process of claim 1 , further comprising depolymerizing paraformaldehyde to generate at least a portion of the carbonyl compound of formula III.

15. The process of claim 14 wherein said depolymerization is catalyzed by a compound of formula I.

16. The process according to claim 1 wherein all R 2 groups are the same and all R 5 groups are the same.

17. A process for preparing a solution of a compound of formula III

wherein each R 2 is independently H or C 1 -C 6 alkyl;

each R 5 is independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, or R 2 and R 5 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl;

the process comprising

providing a solution of a polymer formed from aldehyde or ketone monomers in a solvent system comprising an alcohol; and

reacting the polymer with an amount of a compound of formula I sufficient to depolymerize the polymer

wherein R 2 and R 5 are as described above and R 3 and R 4 are independently C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, or —C(OH)R 2 R 5 , or R 3 and R 4 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl.

18. A composition comprising a mixture of

a compound of formula III

a compound of formula IV

and a catalytic amount of a compound of formula I

the catalytic amount of the compound of formula I being less than the amount of either the compound of formula III or the compound of formula IV, in an alcohol solvent, the composition being substantially free of a compound of formula II

wherein R and R 1 are independently C 1 -C 6 alkyl or C 3 -C 12 cycloalkyl;

each R 2 is independently H or C 1 -C 6 alkyl;

each R 5 is independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, or R 2 and R 5 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl; and

R 3 and R 4 are independently C 1 -C 6 alkyl or C 3 -C 12 cycloalkyl, or R 3 and R 4 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl.

19. A composition consisting of a mixture of

a solvent,

a compound of formula I

and either

(a) a compound of formula III

 or

(b) a compound of formula IV

the composition being substantially free of a compound of formula II

wherein

R and R 1 are independently C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl;

each R 2 is independently H or C 1 -C 6 alkyl;

each R 5 is independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, or R 2 and R 5 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl; and

R 3 and R 4 are independently C 1 -C 6 alky or C 3 -C 12 cycloalkyl, or R 3 and R 4 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl.

20. A process for making a compound of formula I:

wherein

each R 2 is independently H or C 1 -C 6 alkyl;

each R 5 is independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, or R 2 and R 5 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl; and

R 3 and R 4 are independently C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, or —C(OH)R 2 R 5 , or R 3 and R 4 together with the carbon to which they are attached form C 3 -C 12 cycloalkyl,

the process comprising:

(a) treating, in an alcohol solvent, a polymer formed from monomers of formula III

with (1) a catalytic amount of the compound of formula I and (2) a compound of formula IV

wherein R and R 1 are independently H, C 1 -C 6 alkyl, or C 3 -C 12 cycloalkyl, to produce an intermediate product mixture; and

(b) hydrogenating the intermediate product mixture in the presence of hydrogen and a catalyst.

Assignments (8)