Method of producing farnesyl acetone

Patent metadata

Field	Value
Publication number	US-10093606-B2
Application number	US-201515307081-A
Country	US
Kind code	B2
Filing date	Apr 29, 2015
Priority date	Apr 30, 2014
Publication date	Oct 9, 2018
Grant date	Oct 9, 2018

Abstract

The present invention relates to a process for preparing farnesyl acetone.

First claim

The invention claimed is:

1. A process for preparing keto compounds of the general formula (I)

where
R 1 is hydrogen or a —C(O)OR 3 radical, where
R 3 is C 1 -C 4 -alkyl;

R 2 is C 1 -C 4 -alkyl;
X 1 and X 2 are both hydrogen or together are the second bond of a double bond between the carbon atoms to which they are bound;
X 3 and X 4 are both hydrogen or together are the second bond of a double bond between the carbon atoms to which they are bound;
X 5 , X 6 , X 7 and X 8 are each hydrogen;
where one of the combinations of the radicals X 5 and X 7 , X 6 and X 7 or X 7 and X 8 can also be the second bond of a double bond between the carbon atoms to which they are bound, and isomers and mixtures thereof,
where
a) at least one farnesene compound of the general formula (II)

where
X 1 and X 2 together are the second bond of a double bond between the carbon atoms to which they are bound;
X 3 and X 4 together are the second bond of a double bond between the carbon atoms to which they are bound;
X 5 and X 7 together are the second bond of a double bond between the carbon atoms to which they are bound, with the proviso that X 6 is hydrogen; or
X 6 and X 7 together are the second bond of a double bond between the carbon atoms to which they are bound, with the proviso that X 5 is hydrogen, and
X 8 is hydrogen;
is subjected to a reaction with a β-keto ester of the general formula (III)
R 2 —CO—CH 2 —R 1   (III)

where
R 1 is a —C(O)OR 3 radical,
where R 3 is C 1 -C 4 -alkyl

R 2 is C 1 -C 4 -alkyl;
in the presence of a catalyst wherein the catalyst is a compound or complex of a transition metal of group 9 of the Periodic Table and a solvent/water mixture, where the reaction mixture is subjected to dispersing using at least one mixer at a Reynolds number of greater than 10 4 ,
to give a compound of the formula (I-a),

where
R 1 is a —C(O)OR 3 radical,
where R 3 is C 1 -C 4 -alkyl;

R 2 is C 1 -C 4 -alkyl;
X 1 and X 2 together are the second bond of a double bond between the carbon atoms to which they are bound;
X 3 and X 4 together are the second bond of a double bond between the carbon atoms to which they are bound;
one of the combinations of the radicals X 5 and X 7 , X 6 and X 7 or X 7 and X 8 together is the second bond of a double bond between the carbon atoms to which they are bound and the remaining radicals X 5 , X 6 , X 7 and X 8 are each hydrogen;
and isomers and mixtures thereof;

b) the reaction mixture obtained in step a) is optionally subjected to a decarboxylation to give a compound of the formula (I-b),

where
R 2 is C 1 -C 4 -alkyl;
one of the combinations of the radicals X 5 and X 7 , X 6 and X 7 or X 7 and X 8 together is the second bond of a double bond between the carbon atoms to which they are bound and the remaining radicals X 5 , X 6 , X 7 and X 8 are each hydrogen;
and isomers and mixtures thereof;

c) the reaction mixture obtained in step b) is optionally subjected to a hydrogenation to give a compound of the formula (I-c)

where
R 2 is C 1 -C 4 -alkyl.

2. The process according to claim 1 for preparing farnesyl acetone of the formula (I-aA),

where
one of the combinations of the radicals X 5 and X 7 , X 6 and X 7 or X 7 and X 8 together is the second bond of a double bond between the carbon atoms to which they are bound and the remaining radicals X 5 , X 6 , X 7 and X 8 are each hydrogen,
and isomers and mixtures thereof,
wherein the process comprises the steps a) and b).

3. The process according to claim 1 for preparing hexahydrofarnesyl acetone (6,10,14-trimethyl-2-pentadecanone) of the formula (I-bB),

wherein the process comprises the steps a), b), and c).

4. The process according to claim 1 , wherein the solvent of the solvent/water mixture in step a) is selected from among C 1 -C 5 -alkanols, C 2 -C 6 -dialkanols, saturated cyclic ethers, saturated acyclic ethers, nitriles, saturated ketones, lactams, esters of saturated C 1 -C 6 -monocarboxylic acids with C 1 -C 6 -alkanols, C 1 -C 6 -alkylamides and di-C 1 -C 6 -alkylamides of saturated C 1 -C 6 -monocarboxylic acids and mixtures thereof.

5. The process according to claim 1 , wherein the solvent/water mixture in step a) is present in a volume ratio of from 1:5 to 5:1 calculated as pure material.

6. The process according to claim 1 , wherein the solvent/water mixture in step a) is present in a volume ratio of from 2:1 to 1:2 calculated as pure material.

7. The process according to claim 1 , wherein the solvent/water mixture in step a) is present in a volume ratio of 1:1 calculated as pure material.

8. The process according to claim 1 , wherein dispersing in step a) is carried out at a power input in the range from 0.1 to 5000 W/1.

9. The process according to claim 1 , wherein dispersing in step a) is carried out at a power input in the range from 10 to 600 W/1.

10. The process according to claim 1 , wherein dispersing in step a) is carried out at a power input in the range from 20 to 100 W/1.

11. The process according to claim 1 , wherein dispersing in step a) is carried out using a stirrer at a circumferential velocity in the range from 1 to 80 m/s.

12. The process according to claim 1 , wherein dispersing in step a) is carried out using a stirrer at a circumferential velocity in the range from 1.8 to 30 m/s.

13. The process according to claim 1 , wherein dispersing in step a) is carried out at a temperature in the range from 50 to 200° C.

14. The process according to claim 1 , wherein dispersing in step a) is carried out at a temperature in the range from 60 to 150° C.

15. The process according to claim 1 , wherein dispersing in step a) is carried out at a temperature in the range from 70 to 120° C.

16. A process for preparing vitamin E, isophytol, dehydroisophytol, hexahydrofarnesyl acetone or tetrahydrofarnesyl acetone which comprises utilizing the farnesyl acetone obtainable by the process as defined in claim 1 .

17. The process according to claim 1 , wherein the catalyst is a rhodium compound or a rhodium complex.

18. The process according to claim 1 , wherein the catalyst is rhodium(I), rhodium(II), rhodium(III) chloride, rhodium(III) bromide, rhodium(III) nitrate, rhodium(III) sulfate, rhodium(II) or rhodium(III) oxide, rhodium(II) or rhodium(III) acetate, rhodium(II) or rhodium(III) carboxylate,

Assignees

• Basf Se
• Basf Se Reitstoetter Kinzebach & Partner

Inventors

• Schelwies Mathias
• Paciello Rocco
• Eckhardt Heinz
• Dehn Martine

Classifications

• C07C45/54 Primary

  of compounds containing doubly bound oxygen atoms, e.g. esters · CPC title

• C07C45/62 Primary

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C07C45/69 Primary

  by addition to carbon-to-carbon double or triple bonds · CPC title

• C07C49/04

  Saturated compounds containing keto groups bound to acyclic carbon atoms · CPC title

• C07C49/203

  with only carbon-to-carbon double bonds as unsaturation · CPC title