Process for the Epoxidation of a Tetrasubstituted Alkene

Abstract

This invention relates to a process for the epoxidation of a tetrasubstituted alkene such as terpinolene to the corresponding epoxide such as terpinolene epoxide by reacting the tetrasubstituted alkene with peracetic acid prepared in situ from acetic anhydride and hydrogen peroxide in the presence of at least one buffering agent. Further, the invention relates to the use of an oxidizing agent comprising hydrogen peroxide and acetic anhydride for the in-situ epoxidation of a tetrasubstituted alkene.

Claims

1-20. (canceled)

21. A process for the epoxidation of a tetrasubstituted alkene to the corresponding epoxide comprising reacting the tetrasubstituted alkene with peracetic acid prepared in situ from acetic anhydride and hydrogen peroxide in the presence of at least one buffering agent wherein the hydrogen peroxide is used as an aqueous solution and the reaction is carried out in the presence of at least one inert organic solvent selected from non-halogenated aromatic hydrocarbons.

22. The process of claim 21, wherein the buffering agent is selected from the group consisting of salts of inorganic acids, salts of organic acids and any combination thereof.

23. The process of claim 21, wherein the buffering agent is a salt selected from the group consisting of phosphates, formates, acetates, carbonates, citrates, sulfates and any combination thereof.

24. The process claim 21, wherein the buffering agent is selected from the group consisting of alkali metal and alkaline earth metal phosphates, alkali metal and alkaline earth metal acetates, alkali metal and alkaline earth metal carbonates and any combination thereof.

25. The process of claim 21, wherein the molar ratio of hydrogen peroxide to acetic anhydride is from 2.0:1.9 to 1.1:1.05.

26. The process of claim 21, wherein the temperature is from 0 to 50 C.

27. The process of claim 21, wherein the tetrasubstituted alkene contains at east one additional carbon-carbon double bond.

28. The process of claim 21, wherein the tetrasubstituted alkene is terpinolene of the formula (Ia) ##STR00007## and the corresponding epoxide is terpinolene epoxide of formula (IIa) ##STR00008##

29. The process of claim 28, wherein the terpinolene epoxide of formula (IIa) is further converted via limonene-4-ol to terpinene-4-ol.

30. The process of claim 28, wherein the terpinolene epoxide of formula (IIa), limonene-4-ol or terpinene-4-ol is further converted into ()-2-exo-(2-Methylbenzyloxy)-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane, any of its individual enantiomers or any non-racemic mixture thereof.

Description

EXAMPLE 1

Epoxidation of Terpinolene in Toluene with 1.8 eq Acetic Anhydride Using Sodium Acetate as Buffering Agent at 30 C.

[0154] 148.5 g (1.0 mol) terpinolene (91.7%), 200 g (2.17 mol) toluene, 183.7 g (1.8 mol) acetic anhydride and 14.4 g (0.18 mol) sodium acetate were placed in a 1 L glass reactor and heated up to 30 C. After that 85.0 g (1.25 mol) H.sub.2O.sub.2 (50%) was dosed continuously under vigorous stirring over 3 h at 30 C. to the reaction mixture. The reaction mixture was stirred for further 1 h at 30 C. After addition of 50 g water and 100 g (1.08 mol) toluene the reaction mixture was cooled to 20 C. After phase split the water phase was extracted with 50 g (0.54 mol) toluene. The collected organic phases were washed with 35.5 g sodium sulfite solution (20% in water) at 20 C. to remove the peroxide. The organic phase was washed with twice with 100 g water and with 10% NaOH solution. The solvent of the organic phase was distilled off under reduced pressure (40 C.; 20 mbar).

[0155] Distillation residue: 183.4 g (raw epoxide)

[0156] Quantitative GC (gas chromatography): 61.4% w/w terpinolene oxide (content of residual terpinolene: 1.3 w/w %)

[0157] Yield: 74.0%

EXAMPLE 2

Epoxidation of Terpinolene in Toluene with 1.8 eq Acetic Anhydride Using Sodium Acetate as Buffering Agent at 15 C.

[0158] 148.5 g (1.0 mol) terpinolene (91.7%), 200 g (2.17 mol) toluene, 183.7 g (1.8 mol) acetic anhydride and 14.4 g (0.18 mol) sodium acetate were placed in a 1 L glass reactor and cooled up to 15 C. After that 85.0 g (1.25 mol) H.sub.2O.sub.2 (50%) was dosed continuously under vigorous stirring over 3 h at 15 C. to the reaction mixture. The reaction mixture was stirred for further 1 h at 15 C. After addition of 50 g water and 100 g (1.08 mol) toluene the reaction mixture was cooled to 15 C. After phase split the water phase was extracted with 50 g (0.54 mol) toluene. The collected organic phases were washed with 35.5 g sodium sulfite solution (20% in water) at 15 C. to remove the peroxide. The organic phase was washed with twice with 100 g water and with 10% NaOH solution. The solvent of the organic phase was distilled off under reduced pressure (40 C.; 20 mbar).

[0159] Distillation residue: 183.4 g (raw epoxide)

[0160] Quantitative GC: 60.1% w/w terpinolene oxide (content of residual terpinolene: 8.4 w/w %)

[0161] Yield: 72.4%

EXAMPLE 3

Epoxidation of Terpinolene in Toluene with 1.4 eq Acetic Anhydride Using Sodium Acetate as Buffering Agent at 20 C.

[0162] 146.5 g (1.0 mol) terpinolene (93%), 200 g (2.17 mol) toluene, 142.9 g (1.4 mol) acetic anhydride and 28.9 g (0.35 mol) sodium acetate were placed in a 1 L glass reactor and heated up to 30 C. After that 85.0 g (1.25 mol) H.sub.2O.sub.2 (50%) was dosed continuously under vigorous stirring over 3 h at 30 C. to the reaction mixture. The reaction mixture was stirred for further 1 h at 30 C. After addition of 50 g water and 100 g (1.08 mol) toluene the reaction mixture was cooled to 20 C. After phase split the water phase was extracted with 50 g (0.54 mol) toluene. The collected organic phases were washed with 35.5 g sodium sulfite solution (20% in water) at 20 C. to remove the peroxide. The organic phase was washed with twice with 100 g water and with 10% NaOH solution. The solvent of the organic phase was distilled off under reduced pressure (40 C.; 20 mbar).

[0163] Distillation residue: 196.1 g (raw epoxide)

[0164] Quantitative GC: 55.7% w/w terpinolene oxide (content of residual terpinolene: 4.0 w/w %)

[0165] Yield: 71.7%

EXAMPLE 4

Epoxidation of Terpinolene in Toluene with 1.2eq Acetic Anhydride Using Sodium Acetate as Buffering Agent at 20 C.

[0166] 146.5 g (1.0 mol) terpinolene (93%), 200 g (2.17 mol) toluene, 122.5 g (1.2 mol) acetic anhydride and 28.9 g (0.35 mol) sodium acetate were placed in a 1 L glass reactor and heated up to 30 C. After that 85.0 g (1.25 mol) H.sub.2O.sub.2 (50%) was dosed continuously under vigorous stirring over 3 h at 30 C. to the reaction mixture. The reaction mixture was stirred for further 1 h at 30 C. After addition of 50 g water and 100 g (1.08 mol) toluene the reaction mixture was cooled to 20 C. After phase split the water phase was extracted with 50 g (0.54 mol) toluene. The collected organic phases were washed with 35.5 g sodium sulfite solution (20% in water) at 20 C. to remove the peroxide. The organic phase was washed with twice with 100 g water and with 10% NaOH solution. The solvent of the organic phase was distilled off under reduced pressure (40 C.; 20 mbar).

[0167] Distillation residue: 173.4 g (raw epoxide)

[0168] Quantitative GC: 62.6% w/w terpinolene oxide (content of residual terpinolene: 6.2 w/w %)

[0169] Yield: 71.3%

EXAMPLE 5

Epoxidation of Terpinolene in Toluene with 1.4 eq Acetic Anhydride Using Potassium Acetate as Buffering Agent at 20 C.

[0170] 146.5 g (1.0 mol) terpinolene (93%), 200 g (2.17 mol) toluene, 142.9 g (1.4 mol) acetic anhydride and 34.6 g (0.35 mol) potassium acetate were placed in a 1 L glass reactor and heated up to 30 C. After that 85.0 g (1.25 mol) H.sub.2O.sub.2 (50%) was dosed continuously under vigorous stirring over 3 h at 30 C. to the reaction mixture. The reaction mixture was stirred for further 1 h at 30 C. After addition of 50 g water and 100 g (1.08 mol) toluene the reaction mixture was cooled to 20 C. After phase split the water phase was extracted with 50 g (0.54 mol) toluene. The collected organic phases were washed with 35.5 g sodium sulfite solution (20% in water) at 20 C. to remove the peroxide. The organic phase was washed with twice with 100 g water and with 10% NaOH solution. The solvent of the organic phase was distilled off under reduced pressure (40 C.; 20 mbar).

[0171] Distillation residue: 172.1 g (raw epoxide)

[0172] Quantitative GC: 63.6% w/w terpinolene oxide (content of residual terpinolene: 4.4 w/w %) Yield: 71.9%

EXAMPLE 6

Epoxidation of Terpinolene in Toluene with 1.2 eq Acetic Anhydride Using Sodium Acetate as Buffering Agent at 20 C.

[0173] 150.3 g (1.0 mol) terpinolene (90.5%), 415 g (4.50 mol) toluene, 122.5 g (1.2 mol) acetic anhydride and 29.0 g (0.35 mol) sodium acetate were placed in a 1.6 L glass reactor and heated up to 20 C. After that 85.0 g (1.25 mol) H.sub.2O.sub.2 (50%) was dosed continuously under vigorous stirring over 3 h at 20 C. to the reaction mixture. The reaction mixture was stirred for further 4 h at 20 C. After addition of 50 g water and 100 g (1.08 mol) toluene the reaction mixture was cooled to 20 C. After phase split the water phase was extracted with 50 g (0.54 mol) toluene. The collected organic phases were washed with 30.0 g sodium sulfite solution (10% in water) at 20 C. to remove the peroxide. The organic phase was washed with twice with 100 g water and with 10% NaOH solution. The solvent of the organic phase was distilled off under reduced pressure (40 C.; 20 mbar).

[0174] Distillation residue: 253.1 g (raw epoxide)

[0175] Quantitative GC: 46.3% w/w terpinolene oxide (content of residual terpinolene: 2.3 w/w %)

[0176] Yield: 77.0%