Process for preparing 3-methylcyclopentadecane-1,5-diol

Patent metadata

Field	Value
Publication number	US-10196332-B2
Application number	US-201615761699-A
Country	US
Kind code	B2
Filing date	Sep 20, 2016
Priority date	Sep 22, 2015
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

Abstract

The present invention relates to a process for preparing 3-methylcyclopentadecane-1,5-diol (I) by hydrogenolysis of 14-methyl-16,17,18-trioxatricyclo[10.3.2.1]octadecane (II). The invention further relates to a process for preparing 3-methylcyclopentadecane-1,5-diol is a macrocyclic diol that can serve as precursor for a macrocyclic odorant, such as muscone and muscenone.

First claim

The invention claimed is:

1. A process for preparing a diol of formula (I)

which comprises hydrogenolysis of an ozonide of formula (II)

in the presence of a base and a catalyst comprising molybdenum-doped Raney nickel.

2. The process of claim 1 , wherein hydrogenolysis is carried out at a hydrogen pressure of 5 MPa or less and at a temperature of 120° C. or less.

3. The process of claim 1 , wherein the molybdenum-doped Raney nickel is used in an amount of at least 8 wt-% relative to the mass of the ozonide of formula (II).

4. The process of claim 1 , wherein hydrogenolysis is performed in the absence of a liquid organic solvent or diluent.

5. The process of claim 1 , wherein hydrogenolysis is carried out with the ozonide of formula (II) being dispersed in a liquid phase comprising the base, an organic solvent selected from C 1 -C 4 -alkanols, and optionally water.

6. The process of claim 5 , wherein the ozonide of formula (II) is used in an amount of from 2 to 200 g/l relative to the solvent.

7. The process of claim 1 , wherein the base is selected from alkali metal hydroxides.

8. The process of claim 1 , wherein the concentration of the base is in the range of from 5 mM to 50 mM.

9. The process of claim 1 , wherein hydrogenolysis is carried out at temperatures in the range of from 50° C. to 120° C., and at hydrogen pressures of from 1 to 5 MPa.

10. The process of claim 1 , wherein the conditions for hydrogenolysis are applied over a period of for up to 36 h.

11. The process of claim 1 , wherein hydrogenolysis is carried out continuously or batchwise.

12. The process of claim 1 , further comprising the preparation of the ozonide of formula (II) by ozonization of a compound of formula (III)

13. The process of claim 1 , wherein the molybdenum-doped Raney nickel contains aluminum and from 75 to 95 wt-% nickel and from 0.5 to 2.0 wt-% molybdenum based on the total mass of the molybdenum-doped Raney nickel.

14. A process for preparing a macrocyclic odorant of the formulae (V) or (VI) comprising the steps of:
(i) preparing a diol of formula (I)

 by carrying out the process of claim 1 ;
(ii) dehydrogenating and dehydrating the diol of formula (I) so as to form an enol-ether of formula (IV)

 and
(iii) treating the enol-ether of formula (IV) with an acidic agent so as to form a compound of formula (V)

 and optionally the step of
(iv) hydrogenating the compound of formula (V) so as to form a compound of formula (VI)

15. The process of claim 1 , wherein hydrogenolysis is carried out with the ozonide of formula (II) being dispersed in a liquid phase comprising the base, an organic solvent selected from the group consisting of methanol, ethanol or isopropanol, and mixtures thereof, and optionally water.

16. The process of claim 5 , wherein the ozonide of formula (II) is used in an amount of from 10 to 50 g/l relative to the solvent.

17. The process of claim 1 , wherein the base is selected from the group consisting of NaOH and KOH.

18. The process of claim 1 , wherein hydrogenolysis is carried out at temperatures in the range of from 55° C. to 110° C., and at hydrogen pressures of from 1.5 to 4 MPa.

19. The process of claim 1 , wherein the conditions for hydrogenolysis are applied over a period of 2 to 36 h.

Assignees

• Basf Se

Inventors

• Bru Roig Miriam
• Rüdenauer Stefan

Classifications

• C07C2601/18

  with a ring being at least seven-membered · CPC title

• C07C45/57

  with oxygen as the only heteroatom · CPC title

• C07C2602/32

  the ring system containing at least eleven carbon atoms · CPC title

• C07C45/62

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

• C07C29/132 Primary

  by reduction of an oxygen containing functional group · CPC title