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1. (WO1992009590) PROCESS FOR THE PREPARATION OF $g(a)-ALKYL LACTONES
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CLAIMS
1. A process for preparing an «-alkyl-γ-butyrolactone of the formula V



(V)

wherein
R1, R2, R3, R*, and R' are independently hydrogen or a hydrocarbon radical having from 1 to 20
carbon atoms comprising the steps of:
(A) reacting (a) an acyl lactone of formula I

wherein R1, R2, R3, and R4, are independently hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms, R* is a C B alkyl group, (b) an aldehyde of the formula R-CHO wherein R is hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms, and (c) an alkali metal hydroxide at a temperature of from about 50*C to about 150*C in an inert diluent while removing water of reaction to form an «-alkylidene-γ-butyrolactone; and
(B) hydrogenating said «-alkylidene-γ-butyrolactone under conditions which selectively reduce the alkylidene group of said «-alkylidene-γ-butyrolactone.
2. The process of claim 1 wherein in step (A) components (a) , (b) and (c) are present in substantially equimolar quantities.
3. The process of Claim 1 wherein the hydrocarbon radicals R1# R2, R3, and R4 are selected from the group consisting of C^g alkyl, C3.6 cycloalkyl, phenyl, C^_B alkyl- substituted phenyl, benzyl and C^.B alkyl-substituted benzyl.
4. The process of claim 1 wherein R* is C^ alkyl, R1# R^ R3 and R4 are hydrogen or C^.B alkyl and R' is hydrogen, C^,B alkyl or alkenyl, ^.g cycloalkyl or cycloalkenyl, phenyl or substituted phenyl, or benzyl or substituted benzyl. 5. The process of claim 1 wherein the hydrogenation is carried out at a pressure in the range of from about 1 to about 30 atmospheres and at a temperature of from about O'C to about 120*C utilizing from about 0.025 to about 10 weight percent of a heterogeneous supported catalyst of platinum, palladium, nickel or ruthenium, said metal being present on the support in an amount of from about 1- to about 15 weight percent.
6. The process of claim 1 wherein the inert diluent of step (A) forms and azeotrope with water boiling in the range of from about 50*C to about 95'C and is present at a volume ratio of diluent: total reactant charge of about 1:1 to about 20:1.
7. The process of claim 5 wherein the hydrogenation is carried out in an inert diluent at a temperature of from about 25*C to about 85*C.
8. The process of claim 1 wherein in step (A) the «-acyl lactone and alkali metal hydroxide are combined and reacted prior to addition of the aldehyde.
9. The process of claim 8 wherein the aldehyde is added after about 60% to 75% of the theoretical amount of water is removed.
10. The process of claim 8 wherein a molar excess of component (b) in step (A) is employed.
11. The process of claim 5 wherein the hydrogenation catalyst is a supported platinum or palladium catalyst wherein the metal is present on the support in an amount of from about 2 to about 10 weight percent.
12. The process of claim 1 wherein the same diluent is employed for steps (A) and (B) and is selected from the group consisting of benzene, toluene, xylene, and cyclohexane.
13. A process for the preparation of «-alkyl-5-valerolactones of formula VI


wherein R1f R2, R3, R4, Rj, R6 and R' are selected from the group consisting of hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms comprising the steps of (A) reacting at a temperature in the range of from about 50'C to about 150*C and in an inert diluent while removing water of reaction (a) an «-acyl lactone of formula II

wherein R,, R2, R3, R4, Rg and 6 are hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms and R* is a C^g alkyl group, (b) an aldehyde of the formula R' CHO where R' is hydrogen or a hydrocarbon radical having from 1-20 carbon atoms, and (c) an alkali metal hydroxide; and
(B) hydrogenating the product obtained from step (A) under conditions which do not reduce the carbonyl group or effect ring opening.
14 The process of claim 13 wherein the hydrocarbon radicals R1f R2, R3, R4, Rg and R6 are selected from the group consisting of C , alkyl, C3.6 cycloalkyl, phenyl, C^.B alkyl-substituted phenyl, benzyl and C^g alkyl- substituted benzyl.
15, The process of claim 13 wherein the hydrogenation in step (B) is carried out at a pressure of from about 1 to about 30 atmospheres and at a temperature of from about O'C to about 120*C utilizing from about 0.025 to about 10 weight percent of a heterogeneous supported catalyst of platinum, palladium, nickel or ruthenium, said metal being present on the support in an amount of from about 1 "to about 15 weight percent.
16. The process of claim 13 wherein the inert diluent of step (A) forms an azeotrope with water boiling in the range of from about 50*C to about 95*C and is present at a volume ratio of diluent: total reactant charge of from about 1:1 to about 20:1.
17. The process of claim 15 wherein the hydrogenation is carried out in an inert diluent at a temperature of from about 25'C to about 85*C.
18. The process of claim 13 wherein R* is C,.4 alkyl, R,, R2, Rj, R4, Rj and R6 are hydrogen or C^g alkyl and R' is hydrogen, C^_ alkyl or alkenyl, C^.g cycloalkyl or cycloalkenyl, phenyl or substituted phenyl, or benzyl or substituted benzyl.
19. The process of claim 13 wherein in step (A) the «-acyl lactone and alkali metal hydroxide are combined and reacted prior to addition of the aldehyde.
20. The process of claim 19 wherein the aldehyde is added after about 60% to about 75% of the theoretical amount of water is removed.
21. The process of claim 13 wherein in step (A) components (a) , (b) and (c) are present in approximately equimolar quantities.
22. The process of claim 19 wherein a molar excess of component (b) in step (A) is employed.
23. The process of claim 15 wherein the hydrogenation catalyst is a supported platinum or palladium catalyst

Wherein the metal is present on the support in an amount of from about 2 to about 10 weight percent.
24. The process of claim 13 wherein the same diluent is employed for steps (A) and (B) and is selected from the group consisting of benzene, toluene, xylene, and cyclohexane.
25. A process for preparing a cis «-alkyl-γ-butyrolactone of formula VIII



( V I M )

wherein R, is a hydrocarbon radical having from 1 to 20 carbon atoms, and R3, R4 and R' are independently hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms comprising the steps of: (A) reacting together (a) an acyl lactone of formula IX



( I X )

wherein Rv R3, and R4 have the meanings given above, and

R* is a C^g alkyl group, (b) an aldehyde of the formula

R-CHO wherein R is hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms, and (c) an alkali metal hydroxide at a temperature of from about 50*C to about

150*C in an inert diluent while removing water of reaction to form an «-alkylidene-γ-butyrolactone; and
(B) hydrogenating said «-alkylidene-γ-butyrolactone under conditions which selectively reduce the alkylidene group of said «-alkylidene-γ-butyrolactone to form a cis «- alkyl-γ-butyrolactone.
26. The process of claim 25 wherein the radicals R,, R3, and R4 are selected from the group consisting of C^g alkyl, Cj.6 cycloalkyl, phenyl, C,.8 alkyl-substituted phenyl, benzyl and C},B alkyl-substituted benzyl.
27. The process of claim 25 wherein R* is C1-4 alkyl, Rt is C alkyl, R3 and R4 are hydrogen or C,^ alkyl, and R' is hydrogen, C^g alkyl or alkenyl, C3.8 cycloalkyl or cycloalkenyl, phenyl or substituted phenyl, or benzyl or substituted benzyl.
28. The process of claim 25 wherein in step (A) components (a) , (b) , and (c) are present in substantially equimolar quantities.
29. The process of claim 25 wherein the hydrogenation is carried out at a pressure in the range of from about 1 to about 30 atmospheres and at a temperature of from about O'C to about 120'C utilizing from about 0.025 to about 10 weight percent of a heterogeneous supported catalyst of platinum, palladium, nickel or ruthenium, said metal being present on the support in an amount of from about 1 to about 15 weight percent.
30. The process of claim 25 wherein the inert diluent of step (A) forms an azeotrope with water boiling in the range of from about 50*C to about 95'C and is present at a volume ratio of diluent: total reactant charge of about 1:1 to about 20:1.
31. The process of claim 29 wherein the hydrogenation is carried out in an inert diluent at a temperature of from about 25 *C to about 85'C.
32. The process of claim 25 wherein in step (A) the «-acyl lactone and alkali metal hydroxide are combined and reacted prior to addition of the aldehyde.

33. The process of claim 32 wherein the aldehyde is added after about 60% to 75% of the theoretical amount of water is removed.
34. The process of claim 32 wherein a molar excess of component (b) in step (A) is employed.
35. The process of claim 29 wherein the hydrogenation catalyst is a supported platinum or palladium catalyst wherein the metal is present on the support in an amount of from about 2 to about 10 weight percent.
36. The process of claim 25 wherein the same diluent is employed for steps (A) and (B) and is selected from the group consisting of benzene, toluene, xylene, and cyclohexane.
37. The process of claim 25 wherein R, and -CH2R' are independently each an alkyl radical having from 1 to 7 carbon atoms and R3 and R4 are hydrogen.
38. The process of claim 37 wherein R, is methyl and -CH2R' is butyl.
39. The process of claim 37 wherein R, is propyl and -CH2R' is butyl.
40. The process of claim 37 wherein R, is butyl and -CH2R' is propyl.
41. The process of claim 37 wherein R, is methyl and -CH2 R' is heptyl.
42. A process for the preparation of cis «-alkyl-5- valerolactone of formula X

wherein R, is a hydrocarbon radical having from 1 to 20 carbon atoms, and Rj, R4, Rj, R6 and R' are selected from the group consisting of hydrogen or a hydrocarbon radical having from 1 to 20 carbon atoms comprising the steps of: (A) reacting at a temperature in the range of from about 50'C to about 150'C and in an inert diluent while removing water of reaction (a) an «-acyl lactone of formula XI

wherein R,, R3, R4, Rj and R6 have the meaning given above and R* is a C^g alkyl group, (b) an aldehyde of the formula R' CHO where R' is hydrogen or a hydrocarbon radical having from 1-20 carbon atoms, and (e) an alkali metal hydroxide; and
(B) hydrogenating the product obtained from step (A) under conditions which do not reduce the carbonyl group or effect ring opening to form a cis «-alkyl-5- valerolactone.
43. The process of claim 42 wherein in step (A) components

(a) , (b) , and (c) are present in substantially equi olar quantities.
44. The process of claim 42 wherein R* is C,.4 alkyl, R, is a C^g alkyl, R^ R4, Rj and R6 are hydrogen or Q. .B alkyl and R' is hydrogen, C^g alkyl or alkenyl, C3.g cycloalkyl or cycloalkenyl, phenyl or substituted phenyl, or benzyl or substituted benzyl.
45. The process of claim 42 wherein the hydrogenation is carried out at a pressure in the range of from about 1 to about 30 atmospheres and at a temperature of from about O'C to about 120'C utilizing from about 0.025 to about 10 weight percent of a heterogeneous supported catalyst of platinum, palladium, nickel or ruthenium, said metal being present on the support in an amount of from about 1 to about 15 weight percent.
46. The process of claim 42 wherein the inert diluent of step (A) forms an azeotrope with water boiling in the range of from about 50 ' C to about 95*C and is present at a volume ratio of diluent: total reactant charge of about 1:1 to about 20:1.
47. The. process of claim 42 wherein the hydrogenation is carried out in an inert diluent at a temperature of from about 25*C to about 85'C.
48. The process of claim 42 in step (A) the «-acyl lactone and alkali metal hydroxide are combined and reacted prior to addition of the aldehyde.
49. The process of claim 48 wherein the aldehyde is added after about 60% to 75% of the theoretical amount of water is removed.
50. The process of claim 48 wherein a molar excess of component (b) in step (A) is employed.
51. The process of claim 45 wherein the hydrogenation catalyst is a supported platinum or palladium catalyst wherein the metal is present on the support in an amount of from about 2 to about 10 weight percent.
52. The process of claim 42 wherein the same diluent is employed for steps (A) and (B) and is selected from the group consisting of benzene, toluene, xylene, and cyclohexane.