Ethers of bis(hydroxymethyl)cyclohexanes

Abstract

The present invention relates to ethers of 1,2-, 1,3- and 1,4-bis(hydroxymethyl)cyclohexanes, to the preparation of such ethers and also to the use of such ethers as fragrances and as formulation auxiliaries in fragrance-comprising preparations.

Claims

1. A cyclohexane derivative with a structure according to formula 1c ##STR00033## wherein the substituents on the cyclohexyl ring may be in cis or trans position to one another, and R1 to R6 independently of one another are selected from the group consisting of C.sub.2-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, C.sub.2-C.sub.6-alkenyl and hydrogen, and R1 and R2 are not hydrogen, with the proviso that the summed total number of the carbon atoms in all radicals R1 to R6 is only a whole numerical value up to 20.

2. The cyclohexane derivative according to claim 1, wherein the cyclohexane derivative has a cis/trans ratio of at least 70:30.

3. The cyclohexane derivative according to claim 1, wherein the cyclohexane derivative has a trans/cis ratio of at least 70:30.

4. The cyclohexane derivative according to claim 1, wherein the cyclohexane derivative is 1,2-bis(ethoxymethyl)cyclohexane or 1,2-bis(vinyloxymethyl)cyclohexane.

5. A fragrance, flavor, or formulation auxiliary comprising a cyclohexane derivative with a structure according to formula 1c ##STR00034## wherein the substituents on the cyclohexyl ring may be in cis or trans position to one another, and R1 to R6 independently of one another are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, C.sub.2-C.sub.6-alkenyl and hydrogen, and at least one radical from R1 and R2 is not hydrogen, with the proviso that the summed total number of the carbon atoms in all radicals R1 to R6 is only a whole numerical value up to 20.

6. A composition comprising the fragrance, flavor, or formulation auxiliary according to claim 5, wherein the composition is a detergent, cosmetic preparation, fragranced hygiene article, food, food supplement, perfume, pharmaceutical preparation, or crop protection composition.

7. A formulating agent in a preparation comprising the fragrance, flavor, or formulation auxiliary according to claim 5.

8. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein R1 and R2 are C.sub.1-C.sub.4-alkyl.

9. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein R3, R4, R5, and R6, are hydrogen or methyl.

10. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein R1 and R2 have the same definition.

11. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein R1 and R2 are ethyl and R3 to R6 are hydrogen.

12. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein the cyclohexane derivative is 1,2-bis(ethoxymethyl)cyclohexane or 1,2-bis(vinyloxymethyl)cyclohexane.

13. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein the cis/trans ratio has a value of at least 70:30.

14. The fragrance, flavor, or formulation auxiliary according to claim 5, wherein the trans/cis ratio has a value of at least 70:30.

15. A process for preparing a cyclohexane derivative with a structure according to formula 1c ##STR00035## R1 and R2 independently of one another are selected from the group consisting of Rb and hydrogen, R3 to R6 independently of one another are selected from the group consisting of Ra and hydrogen, Ra is C.sub.1- to C.sub.6-alkyl, C.sub.3- to C.sub.6-cycloalkyl, C.sub.3- to C.sub.6-cycloalkenyl, or C.sub.2- to C.sub.6-alkenyl, and Rb is C.sub.1- to C.sub.6-alkyl, C.sub.3- to C.sub.6-cycloalkyl or C.sub.2- to C.sub.6-alkenyl, with the proviso that at least one radical from R1 and R2 is C.sub.2-C.sub.6-alkenyl; said process comprising reacting a cyclohexane derivative of the corresponding formula 2c ##STR00036## with at least one C.sub.2-C.sub.6-alkyne to obtain the cyclohexane derivative of the formula 1c, wherein, in the cyclohexane derivative of the formula 2c, R3 to R6 independently of one another are selected from the group consisting of Ra and hydrogen, R11 and R12 are hydrogen or a group Rd, wherein at least one of the radicals, R11 and/or R12, is hydrogen, Ra is C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl or C.sub.2-C.sub.6-alkenyl, and Rd is C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.2-C.sub.6-alkenyl, wherein the radicals R11, R12, R3 to R6 and the C.sub.2-C.sub.6-alkyne are selected such that the summed total number of carbon atoms in all radicals R1 to R6 in the resultant compounds of the formula 1c, respectively, is a whole numerical value from 2 to 20, and wherein the cyclohexane derivative of the formula 1c is obtained, in which R1 is selected from C.sub.2-C.sub.6-alkenyl if R11 is hydrogen, and in which R2 is selected from C.sub.2-C.sub.6-alkenyl if R12 is hydrogen.

16. The process according to claim 15, wherein in the cyclohexane derivative of the formula 1c, the radicals R1 and R2 are C.sub.2-C.sub.6-alkenyl.

17. The process according to claim 15, wherein R1 is the same as R2.

18. The process according to claim 15, wherein the C.sub.2-C.sub.6-alkyne is ethyne.

19. A process for preparing a cyclohexane derivative with a structure according to formula 1c ##STR00037## R1 is selected from the group consisting of Rc and hydrogen, R2 is Rc, R3 to R6, independently of one another, are selected from the group consisting of Rc and hydrogen, and Rc is C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-cycloalkyl, with the proviso that at least one of the radicals, R1 and/or R2, is C.sub.2-C.sub.6-alkyl or C.sub.3-C.sub.6-cycloalkyl; said process comprising hydrogenating a cyclohexane derivative of the formula 3c ##STR00038## with hydrogen to obtain the cyclohexane derivative of the formula 1c, wherein, in the further cyclohexane derivative of the formula 3c, R21 is selected from the group consisting of Ra and hydrogen, R22 is Ra, R23 to R26 independently of one another are selected from the group consisting of Ra and hydrogen, Ra is C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl or C.sub.2-C.sub.6-alkenyl, and at least one of the radicals R21 to R26 is C.sub.3-C.sub.6-cycloalkenyl or C.sub.2-C.sub.6-alkenyl, wherein the radicals R21 to R26 are selected such that the summed total number of carbon atoms in all radicals R21 to R26 may only represent a whole numerical value from 2 to 20.

20. The process according to claim 19, wherein at least one radical from R21 and R22 is C.sub.2-C.sub.6-alkenyl.

21. The process according to claim 19, wherein, in the cyclohexane derivative of the formula 3c, R21 is hydrogen.

22. The process according to claim 20, wherein, in the cyclohexane derivative of the formula 3c, R21 and R22 independently of one another are C.sub.2-C.sub.6-alkenyl.

23. The process according to claim 19, wherein, in the cyclohexane derivative of the formula 3c, R21 is the same as R22.

24. The process according to claim 19, wherein the C.sub.2-C.sub.6-alkenyl group is vinyl.

25. A process for preparing a cyclohexane derivative with a structure according to formula 1c, ##STR00039## R1 is selected from the group consisting of hydrogen and Rc, R2 is selected from the group consisting of hydrogen and Rc, R3 to R6 independently of one another are selected from the group consisting of Rc and hydrogen Rc is C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-cycloalkyl, with the proviso that at least one of R1 and R2 is C.sub.2-C.sub.6-alkyl, said process comprising: reacting a cyclohexane derivative of the corresponding formula 2c ##STR00040## with at least one C.sub.2-C.sub.6-alkyne, wherein, in the second cyclohexane derivatives of the formula 2c, R3 to R6 independently of one another are selected from the group consisting of Rf and hydrogen, R11 and R12 are hydrogen or a group Re, wherein at least one of the radicals R11 and/or R12 is hydrogen, Re and Rf are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-cycloalkenyl, R11, R12, R3 to R6 and the C.sub.2-C.sub.6-alkyne are selected such that the summed total number of carbon atoms in all radicals R1 to R6 in the resultant compounds of the formula 1c represents a whole numerical value from 2 to 20, wherein a cyclohexane derivative of the formula 1cc is obtained, ##STR00041## wherein R1 and R2 are hydrogen or a group Re, R1 is C.sub.2-C.sub.6-alkenyl if R11 is hydrogen, R2 is C.sub.2-C.sub.6-alkenyl if R12 is hydrogen, R3 to R6 independently of one another are selected from the group consisting of Rf and hydrogen, the summed total number of carbon atoms in all radicals R1, R2, R3, R4, R5 and R6 represents a whole numerical value from 2 to 20, and hydrogenating the cyclohexane derivative of the formula 1cc with hydrogen.

26. The process according to claim 25 wherein R1 and R2 are ethyl, wherein a compound of the general formula 2c in which R11 and R12 are hydrogen is reacted with ethyne to give a compound of the general formula 1cc in which R1 and R2 are vinyl, and wherein said compound is hydrogenated with hydrogen.

27. A process for preparing a cyclohexane derivative of the formula 1cc, ##STR00042## wherein the substituents on the cyclohexyl ring may be in cis or trans position to one another, and R1 and R2 are hydrogen or a group Re, wherein at least one of R1 and R2 is C.sub.2-C.sub.6-alkenyl, R3 to R6 independently of one another are selected from the group consisting of Rf and hydrogen, Re and Rf are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-cycloalkenyl, and the summed total number of carbon atoms in all radicals R1, R2, R3, R4, R5 and R6 of the formula 1cc, respectively, represents a whole numerical value from 2 to 20, said process comprising: reacting a cyclohexane derivative of the corresponding formula 2c ##STR00043## with at least one C.sub.2-C.sub.6-alkenyl donor compound in the presence of a transition metal catalyst or a base, wherein, in the cyclohexane derivative of the formula 2c, R3 to R6 independently of one another are selected from the group consisting of Rf and hydrogen, R11 and R12 are hydrogen or a group Re, wherein at least one of R11 and R12 is hydrogen, Re and Rf are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-cycloalkenyl, R11, R12, R3 to R6 and the alkyne are selected such that the summed total number of carbon atoms in all radicals R1 to R6 in the resultant compounds of the formula 1c represents a whole numerical value from 2 to 20, to give a cyclohexane derivative of the formula 1cc, wherein R1 is C.sub.2-C.sub.6-alkenyl if R11 is hydrogen, and R2 is C.sub.2-C.sub.6-alkenyl if R12 is hydrogen.

28. The process according to claim 27, wherein the alkenyl donor compound is a compound of the general formula III ##STR00044## wherein Ra and Rb independently of one another are hydrogen or C.sub.1-C.sub.4-alkyl, the total carbon number in Ra and Rb being 0, 1, 2, 3 or 4; X is O or N-Rz; Ry is C.sub.2-C.sub.6-alkyl, formyl, C.sub.1-C.sub.6-alkylcarbonyl, a C.sub.1-C.sub.6-alkylcarbonyl substituted by a group C(O)ORq, or a radical of the formula (CH.sub.2CH.sub.2O).sub.k-Rq, in which k is 2 to 10; Rz is hydrogen or C.sub.1-C.sub.4-alkyl, or Rz, together with Ry and the nitrogen atom, forms an N-lactamyl radical, and Rq is a radical C(Rb)=CHRa.

29. A process for preparing a cyclohexane derivative with a structure according to formula 1c, ##STR00045## R1 is selected from the group consisting of hydrogen and Rc, R2 is selected from the group consisting of hydrogen and Rc, R3 to R6 independently of one another are selected from the group consisting of Rc and hydrogen, Rc is C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-cycloalkyl, with the proviso that at least one radical from R1 and R2 is C.sub.2-C.sub.6-alkyl; said process comprising reacting a cyclohexane derivative of the corresponding formula 2c ##STR00046## with at least one C.sub.2-C.sub.6-alkenyl donor compound in the presence of a transition metal catalyst or a base, wherein, in the cyclohexane derivative of the formula 2c, R3 to R6 independently of one another are selected from the group consisting of Rf and hydrogen, R11 and R12 are hydrogen or a group Re, wherein at least one of R11 and R12 is hydrogen, Re and Rf are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-cycloalkenyl, R11, R12, R3 to R6 and the alkyne are selected such that the summed total number of carbon atoms in all radicals R1 to R6 in the resultant compounds of the formula 1c represents a whole numerical value from 2 to 20, to give a cyclohexane derivative of the formula 1cc ##STR00047## wherein R1 is C.sub.2-C.sub.6-alkenyl if R11 is hydrogen, and R2 is C.sub.2-C.sub.6-alkenyl if R12 is hydrogen, and hydrogenating the cyclohexane derivative of the formula 1cc with hydrogen.

30. The process according to claim 29, wherein R1 and R2 are ethyl, said process comprising reacting a compound of the general formula 2c ##STR00048## in which R11 and R12 are hydrogen with at least one C.sub.2-C.sub.6-alkenyl donor compound in the presence of a transition metal catalyst or a base, wherein, in the compound of the general formula 2c, R3 to R6 independently of one another are selected from the group consisting of Rf and hydrogen, R11 and R12 are hydrogen or a group Re, wherein at least one of R11 and R12 is hydrogen, wherein Re and Rf are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-cycloalkenyl, wherein the radicals R11, R12, R3 to R6 and the alkyne are selected such that the summed total number of carbon atoms in all radicals R1 to R6 in the resultant cyclohexane derivative of the formula 1a represents a whole numerical value from 2 to 20, to give a compound of the general formula 1cc ##STR00049## in which R1 and R2 are vinyl, and hydrogenating the compound of the general formula 1cc with hydrogen.

31. A method of imparting or modifying a scent or a flavor to a composition comprising incorporating a cyclohexane derivative into a composition in an amount that imparts or modifies the scent or the flavor of the composition, wherein the cyclohexane derivative has a structure according to formula 1c ##STR00050## wherein the substituents on the cyclohexyl ring may be in cis or trans position to one another, and R3 to R6 are hydrogen, and R1 and R2 independently of one another are selected from the group consisting of C.sub.2-C.sub.6-alkyl, C.sub.5-alkenyl, C.sub.3-C.sub.6-cycloalkenyl and C.sub.3-C.sub.6-cycloalkyl, or at least one radical from R3 to R6 is not methyl or hydrogen, and the other radicals R3 to R6 independently of one another are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, C.sub.2-C.sub.6-alkenyl and hydrogen, and R1 and R2 independently of one another are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.5-alkenyl, C.sub.3-C.sub.6-cycloalkenyl and C.sub.3-C.sub.6-cycloalkyl, or at least one radical from R1 and R2 is not methyl or ethyl, R3 and R4 are methyl, R5 and R6 are hydrogen, and also R1 and R2 independently of one another are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, and C.sub.2-C.sub.6-alkenyl, or R1 and R2 independently of one another are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, and C.sub.2-C.sub.6-alkenyl, and at least one radical from R3 to R6 is not hydrogen, with the exception of compounds of the formula 1c in which R1 and R2 are methyl or ethyl and at the same time R3 and R4 are each methyl and R5 and R6 are each hydrogen, and if R1 is hydrogen, R2 is not methyl, C.sub.4-alkyl, or vinyl, with the proviso that the summed total number of the carbon atoms in all radicals R1 to R6 is only a whole numerical value from 2 to 20.

32. The method according to claim 31, wherein the cyclohexane derivative is selected from 1,2-bis(ethoxymethyl)cyclohexane and 1,2-bis(tert-butoxymethyl)cyclohexane.

33. The method according to claim 31, wherein the cyclohexane derivative is selected from the group consisting of compounds of the formula 1c having a cis/trans ratio of at least 70:30.

34. The method according to claim 31, wherein the cyclohexane derivative is selected from the group consisting of compounds of the formula 1c having a trans/cis ratio of at least 70:30.

35. A fragrance dispenser comprising a composition comprising the fragrance, flavor, or formulation auxiliary according to claim 5.

Description

EXAMPLES

(1) Compound A (cis/trans ratio 30:70)

(2) ##STR00011##
Compound B (cis/trans ratio 30:70)

(3) ##STR00012##
Compound I (cis/trans ratio 30:70)
Compound I-trans (trans/cis ratio >95:5)

(4) ##STR00013##
Synthesis Procedure for the Preparation of cyclohexanedimethanol divinyl ether (Compound B)

(5) ##STR00014##

(6) In a 20 L autoclave rendered inert with nitrogen, 10.8 kg of cyclohexanedimethanol were introduced together with 330 g of potassium hydroxide, melted and heated to a temperature of 160 C. with stirring. Acetylene was then injected to a total pressure of 20 bar and the amount of acetylene required to maintain the pressure was continuously topped up. After a reaction time of 9 h or a gas absorption >3000 L, the acetylene introduction was ended, and the apparatus was cooled to room temperature, decompressed and flushed with nitrogen. The crude product was analyzed by gas chromatography and comprised, according to area percent evaluation, 0.2% of starting material, 2.9% of cyclohexanedimethanol monovinyl ether and 93.9% of cyclohexanedimethanol divinyl ether. To purify the crude product, a part amount of 4 kg was distilled over a silver-plated 100 cm column, filled with 30 mm Sulzer DX packings, at a pressure of 10 mbar and a bottom temperature of 130 C. During this, 2.6 kg of divinyl ether were obtained in a purity of more than 98%, which corresponds to a distillation yield of 70%.

(7) Synthesis Procedure for the Preparation of cyclohexanedimethanol mono- and divinyl ethers and Derivatives (Structures A and B)

(8) ##STR00015##

(9) In a 20 L autoclave rendered inert with nitrogen, 10.8 kg of cyclohexanedimethanol were introduced together with 330 g of potassium hydroxide and 1500 g of isopropanol and heated to a temperature of 160 C. with stirring. Acetylene was then injected to a total pressure of 20 bar and the amount of acetylene required to maintain the pressure was continuously topped up. After a reaction time of about 3 h or a maximum gas absorption of 1800 L, the acetylene introduction was ended, and the apparatus was cooled to room temperature, decompressed and flushed with nitrogen.

(10) The crude product was analyzed by gas chromatography and comprised, according to area percent evaluation, in the case of the compounds where R3 to R6 are hydrogen, 10.6% of starting material, 40.9% of cyclohexanedimethanol monovinyl ether, 37.4% of cyclohexanedimethanol divinyl ether. To purify the crude product, a part amount of 3.5 kg was distilled over a silver-plated 100 cm column filled with 30 mm Sulzer DX packings. After removing the isopropanol, this was carried out at a pressure of 10 mbar and a bottom temperature of 130-140 C. During this, 0.6 kg of monovinyl ether was obtained in a purity >98%, which corresponds to a distillation yield of 40%.

(11) Synthesis of cyclohexanedimethanol monovinyl ether: Distillation

(12) Used: 132 g

(13) TABLE-US-00001 Fraction Amount GC purity 1 13.1 g 96.5% 2 44.3 g 99.0% 3 36.3 g 99.2% 4 19.0 g 99.1% Bottom 21.8 g 71.2%

(14) Cold trap: 0.6 g

(15) The synthesis and purification of 1,2- and 1,3-cyclohexanedimethanol mono- and divinyl ethers and of substituted 1,2-, 1,3- and 1,4-cyclohexanedimethanol derivatives with at least one radical from R3 to R6 not being hydrogen can take place analogously; here, the corresponding molar amount of cyclohexanedimethanol or derivative is used as starting material.

(16) Hydrogenation of cyclohexanedimethanol divinyl ether (Compound B) for the Preparation of cyclohexanedimethanol diethyl ether (Compound I/I-trans)

(17) ##STR00016##

(18) A 300 mL steel autoclave was filled with 150 g of cyclohexanedimethanol divinyl ether, 10 g of H0-22 catalyst (palladium on aluminum oxide) were placed in a suspended basket within the autoclave. The hydrogenation was carried out at 30 C. and 20 bar hydrogen for 12 hours with stirring (700 rpm). During this, 34.8 liters of hydrogen were injected in. The hydrogen absorption stopped after just 10 hours. The autoclave was cooled and decompressed, the product was filtered and gave 130 g of a clear liquid, the purity of which, according to GC, was 98.0%. By means of distillation, it was possible to obtain fractions with a purity of 99.7% (GC) (boiling point 98 C. at 4 mbar).

(19) Synthesis of cyclohexanedimethanol diethyl ether: Distillation

(20) Used: 130 g

(21) TABLE-US-00002 Fraction Amount GC purity 1 9.5 g 99.4% 2 46.2 g 99.6% 3 42.7 g 99.7% 4 9.6 g 99.7% Bottom 19.0 g 87.4%

(22) Cold trap: 0.6 g

(23) The synthesis and purification of 1,2- and 1,3-cyclohexanedimethanol mono- and divinyl ethers and of substituted 1,2-, 1,3- and 1,4-cyclohexanedimethanol derivatives with at least one radical from R3 to R6 not being hydrogen can take place analogously; here the corresponding molar amount of cyclohexanedimethanol or derivative is used as starting material.

(24) The syntheses are known to the person skilled in the art from the prior art and/or can be carried out without further inventive skill in accordance with the known synthesis routes and also the synthesis routes disclosed here.

(25) Further Synthesis Routes (for Procedure, See Instructions Above)

(26) Synthesis Routes According to the Invention to Give Inventive diethyl and divinyl ethers of 1,2- and 1,3-cyclohexanedimethanol (According to the Invention):

(27) TABLE-US-00003 Ethers of 1,2- and 1,3-cyclohexanedimethanol: vinyl, ethyl; cis-trans isomers; the divinyl ethers can be isolated in high purity Target structures: 0 Synthesis routes:

(28) The preparation of the other alkenyl ethers with C3- to C6-alkenyl takes place analogously to this.

(29) Synthesis Route to 1,4-cyclohexanedimethanol diethyl ether (Structures I and I-trans) (the Second Reaction Step is Comprised by the Present Invention):

(30) TABLE-US-00004 cis-trans isomers of 1,4-cyclohexanedimethanol diethyl ether
The preparation of the other inventive alkenyl ethers with C3- to C6-alkenyl takes place analogously to this.
Synthesis Routes to Inventive Non-Vinylic Ethers (Procedure According to General Specialist Knowledge):

(31) TABLE-US-00005 Other ethers of 1,4-cyclohexanedimethanol; ethers of 1,2- and 1,3-cyclohexanedimethanol: analogous

Synthesis of Inventive Trans-1,4-Cyclohexanedimethanol Diethyl Ether (Structure I-Trans) (Trans Fraction Greater than 95%)

1. Vinylation of trans-1,4-cyclohexanedimethanol

(32) ##STR00030##

(33) In a 250 mL flask, 120 g of trans-1,4-cyclohexanedimethanol were introduced together with 3.6 g of potassium hydroxide, melted and heated to a temperature of 180 C. with stirring. The mixture was poured warm into a 0.3 L autoclave rendered inert with nitrogen, and the temperature was adjusted to 160 C. Acetylene was then injected to a total pressure of 19 bar, and the amount of acetylene required to maintain the pressure was continuously topped up. After a reaction time of 23 h or a gas absorption of 33 L, the acetylene introduction was ended, and the apparatus was cooled to room temperature, decompressed and flushed with nitrogen. The crude product was analyzed by gas chromatography and comprised, according to area percent evaluation, 99.8% of trans-1,4-cyclohexanedimethanol divinyl ether and in each case <0.1% of starting material and monovinyl ether. For the purification, the crude product was distilled at a pressure of 1 mbar and a bottom temperature of 96 C. During this, 130 g of divinyl ether were obtained in a purity of more than 99%, which corresponds to a yield of 80%.

2. Hydrogenation of trans-1,4-cyclohexanedimethanol divinyl ether

(34) ##STR00031##

(35) A 300 mL steel autoclave was filled with 120 g of cyclohexanedimethanol divinyl ether, and 8 g of H0-22 catalyst (palladium on aluminum oxide) were placed in a suspended basket within the autoclave. The hydrogenation was carried out at 30 C. and 20 bar hydrogen for 10 hours with stirring (700 rpm). During this, 27.8 liters of hydrogen were injected in. The autoclave was cooled and decompressed, and the product was filtered and gave 130 g of a clear liquid, the purity of which was 98.1% according to GC. By means of distillation, it was possible to obtain fractions with a purity of 99.9% (GC) (boiling point: 91 C. at 2 mbar).

3. Distillation

(36) Used: 110 g

(37) TABLE-US-00006 Fraction Amount GC purity 1 5.6 g 99.36% 2 7.0 g 99.93% 3 4.5 g 99.94% 4 54.2 g 99.91% 5 9.1 g 99.68% 6 19.8 g 99.68% 7 4.9 g 99.10% Bottom 3.8 g 67.74%

(38) Cold trap: 0.6 g

Synthesis of cis-1,2-cyclohexanedimethanol diethyl ether

(39) ##STR00032##

(40) Sodium hydride (2.5 g, 62 mmol) was introduced as 60% strength (% by weight) suspension in mineral oil in a 250 ml flask and washed twice with tetrahydrofuran (THF). Cis-1,2-cyclohexanedimethanol (9.0 g, 62 mmol), dissolved in 15 ml of THF, was added, and ethyl iodide (19.3 g, 124 mmol), dissolved in 15 ml of THF, was slowly added dropwise. The reaction mixture was heated at reflux for 24 hours. After cooling, 90 ml of acetic ester and 15 ml of water were added. The organic phase was washed three times with 50 ml of saturated sodium chloride solution. The organic phase was then dried over sodium sulfate and purified by distillation. This gave 10.6 g of a pale yellow liquid.

(41) The product was analyzed by gas chromatography and comprised, according to area percent evaluation, 91% cis-1,2-cyclohexanedimethanol diethyl ether, 5% monoethyl ether, and other impurities, which in each case correspond to less than 1%. This corresponds to a yield of about 78%.

(42) Purification takes place by distillation analogously to the preceding examples.