New process for preparing biphenyl compounds

Patent metadata

Field	Value
Publication number	US-2017240937-A1
Application number	US-201515516318-A
Country	US
Kind code	A1
Filing date	Oct 5, 2015
Priority date	Oct 3, 2014
Publication date	Aug 24, 2017
Grant date	—

Abstract

The present invention relates to a process for preparing a compound having the formula (I), said process comprising the following steps: a) the addition of an oxygen source into a solution of a compound of formula (II), in a water-miscible solvent, b) the addition of a laccase in the solution obtained after step a); and c) the possible recovering of the compound of formula (I) thus obtained.

First claim

1 . A process for preparing a compound having the formula (I):

wherein:
R 1 is H or OH;
R 2 is a (C 1 -C 6 )alkoxy group;
R 3 is H or forms a C═O group with the carbon atom carrying it;
R 4 is R or R’;
R being chosen from the group consisting of: —CHO, —CN, —COR a , —COOR a , —R a , and (C 2 -C 6 )alkenyl groups, R a being a (C 1 -C 6 )alkyl group;
R′ being a (C 1 -C 6 )alkoxy group;

and wherein, when the bond ‘a’ linking the cores A and B is a single bond, then the compound of formula (I) has the following formula (I-1):

and when the bond ‘a’ linking the cores A and B is a double bond, then the compound of formula (I) has the following formula (I-2):

said process comprising the following steps:
a) the addition of an oxygen source into a solution of a compound of formula (II) in a water-miscible solvent, said compound of formula (II) having the following formula:

wherein R 1 , R 2 , and R 4 are as defined above in formula (I),
and R′ 3 is H when R 1 is OH and R′ 3 is OH when R 1 is H,

said water-miscible solvent being chosen from the group consisting of: dioxane, DMSO, acetone, and mixtures thereof;
b) the addition of a laccase in the solution obtained after step a); and
c) the recovering of the compound of formula (I) thus obtained, in particular by centrifugation or filtration.

2 . The process of claim 1 , wherein the water-miscible solvent is acetone.

3 . The process of claim 1 or 2 , wherein the laccase is from Trametes versicolor.

4 . The process of claim 1 , wherein the amount of laccase for one gram of compound of formula (II) is from 1.5 mg to 75 mg, preferably from 3 mg to 15 mg.

5 . The process of claim 1 , wherein the solution of the compound of formula (II) in a water-miscible solvent is prepared by adding said compound of formula (II) in said water-miscible solvent, and adding a buffer solution.

6 . The process according to claim 5 , wherein the amount of water-miscible solvent is comprised between 5% and 10% of volume in comparison with the total volume of the mixture formed by said solvent and the buffer solution.

7 . The process of claim 1 , wherein the addition of an oxygen source according to step a) is carried out for a sufficient time to saturate the solution in dissolved oxygen.

8 . The process of claim 1 , wherein the solution of the compound of formula (II) in the water-miscible solvent used for step b) is saturated in oxygen.

9 . The process of claim 1 , wherein the pH of the solution of the compound of formula (II) in the water-miscible solvent is comprised between 4 and 7.

10 . A process for the preparation of a compound having the following formula (III):

R and R 2 being as defined in claim 1 , and
R 5 being a (C 1 -C 6 )alkyl group;
said process comprising the steps of:
preparing a compound of formula (I-1 ) using the process according to claim 1 ,
alkylating the compound of formula (IA) with a compound R 5 X, X being a halogen atom, preferably I,
and the possible recovering of the compound of formula (III).

11 . The process of claim 10 , wherein R is —CHO, —CH 2 —CH═CH 2 or COOR a , R a being a (C 1 -C 6 )alkyl group.

12 . A process for the preparation of a compound having the following formula (IV):

R 2 being as defined in claim 1 , and
R 6 being H or a (C 1 -C 6 )alkyl group,
said process comprising the steps of:
preparing a compound of formula (I-1) with R being CHO, using the process claim 1 ,
reacting the compound of formula (I-1) with a hydrogenation agent, in order to obtain a compound of formula (IV) wherein R 6 ═H,
and, if necessary, alkylating the compound of formula (IV) wherein R 6 ═H with a compound R 5 X, X being a halogen, preferably 1, and R 5 being a (C 1 -C 6 ) alkyl group, in order to obtain a compound of formula (IV) wherein R 6 ═(C 1 -C 6 ) alkyl,
and the possible recovering of the compound of formula (IV).

13 . A process for the preparation of a compound having the

following formula (V):
R 2 being as defined in claim 1 , and
R 6 being H or a (C 1 -C 6 )alkyl group, said process comprising the steps of:
preparing a compound of formula (I-1) with R being COOR a , using the process of claim 1 ,
reacting the compound of formula (I-1) with methanol in the presence of a base, in order to obtain a compound of formula (V) wherein R 6 ═H,
and, if necessary, alkylating the compound of formula (V) wherein R 6 ═H with a compound R 5 X, X being a halogen and R 5 being a (C 1 -C 6 ) alkyl group, in order to obtain a compound of formula (V) wherein R 6 ═(C 1 -C 6 ) alkyl,

and the possible recovering of the compound of formula (V).

14 . A process for the preparation of a compound having the following formula (VI):

R 2 being a (C 1 -C 6 ) alkoxy group,
R 7 being a (C 2 -C 10 )alkenyl group, and
R 8 being a (C 1 -C 6 )alkyl group,
said process comprising the steps of:
preparing a compound of formula (V) with R 6 being a (C 1 -C 6 )alkyl group, using the process according to claim 13 ,
reacting the compound of formula (V) with an alcohol R 7 OH in the presence of a catalyst and of N,N′-diisopropyl carbodiimide, in order to obtain a compound of formula (VI),

and the possible recovering of the compound of formula (VI).

15 . A process for the preparation of a compound having the following formula (VII):

R 2 being as defined in claim 1 , and
R 8 being a (C 1 -C 6 )alkyl group,
said process comprising the steps of:
preparing a compound of formula (I-1) with R being CHO, using the process according to claim 1 ,

alkylating the compound of formula (I-1) with a compound R 8 X, X being a halogen for obtaining a compound having the following formula (III-1):

R 2 and R 8 being as defined above in formula (VII),
reacting the compound of formula (III-1) with a Wittig reagent, in order to obtain a compound having the formula (VII),
and the possible recovering of the compound of formula (VII).

16 . A process for the preparation of a compound having the following

R′ and R 2 being as defined in claim 1 , and
n being an integer varying from 1 to 6,
said process comprising the steps of:
preparing a compound of formula (I-2), using the process of claim 1 ,
reacting the co

Assignees

• Univ Bordeaux
• Inst Polytechnique Bordeaux
• Centre Nat De La Rech Scient (C N R S)

Inventors

• Grelier Stéphane
• Cramail Henri
• Llevot Audrey
• Carlotti Stéphane
• Grau Etienne

Classifications

• C07D303/27

  having all hydroxyl radicals etherified with oxirane containing compounds · CPC title

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C12P7/66

  containing the quinoid structure · CPC title

• C07C45/71

  being hydroxy groups · CPC title

• C12P7/24

  containing a carbonyl group · CPC title