Organic reactions carried out in aqueous solution in the presence of a hydroxyalkyl(alkyl)cellulose or an alkylcellulose

Patent metadata

Field	Value
Publication number	US-10836688-B2
Application number	US-202016742523-A
Country	US
Kind code	B2
Filing date	Jan 14, 2020
Priority date	Jan 29, 2016
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

Abstract

The present invention relates to a method of carrying out an organic reaction in aqueous solution in the presence of a hydroxyalkyl(alkyl)cellulose or an alkylcellulose.

First claim

We claim:

1. A method of carrying out an organic reaction in a solvent containing at least 90% by weight, based on the total weight of the solvent, of water, which method comprises reacting the reagents in said solvent in the presence of a cellulose derivative as a surfactant which is selected from the group consisting of cellulose modified with one or more alkylene oxides or other hydroxyalkyl precursors, and alkylcellulose;
where the organic reaction is not a polymerization or oligomerization reaction of olefinically unsaturated compounds.

2. The method as claimed in claim 1 , where the cellulose derivative has a viscosity of from 1 to 150000 mPa·s, determined as a 2% by weight aqueous solution, relative to the weight of water.

3. The method as claimed in claim 1 , where in the cellulose derivative 5 to 70% of the hydrogen atoms in the hydroxyl groups of the cellulose on which the cellulose derivative is based are replaced by a hydroxyalkyl and/or alkyl group.

4. The method as claimed in claim 1 , where the cellulose modified with one or more alkylene oxides or other hydroxyalkyl precursors is selected from the group consisting of hydroxyalkylcelluloses which are celluloses in which a part of the hydrogen atoms of the OH groups is replaced by a C 2 -C 4 -hydroxyalkyl group; hydroxyalkylalkylcelluloses which are celluloses in which a part of the hydrogen atoms of the OH groups is replaced by a C 2 -C 4 -hydroxyalkyl group and a part of the hydrogen atoms of the OH groups is replaced by a C 1 -C 3 -alkyl group; and alkylcelluloses which are celluloses in which a part of the hydrogen atoms of the OH groups is replaced by a C 1 -C 3 -alkyl group.

5. The method as claimed in any claim 4 , where the cellulose derivative is selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, ethylhydroxyethylcellulose, hydroxyethylcellulose, methylcellulose and ethylcellulose.

6. The method as claimed in claim 5 , where the cellulose derivative is hydroxypropylmethylcellulose.

7. The method as claimed in claim 1 , where the cellulose derivative is used in an amount of from 0.01 to 15% by weight, based on the weight of the solvent, or, alternatively, based on the weight of water.

8. The method as claimed in claim 1 , where the weight ratio of the cellulose derivative and all reagents is from 1:1 to 1:200.

9. The method as claimed in claim 1 , where at least one of the reagents has a water solubility of at most 100 g per 1 l of water, at 20° C.+/−20% and 101325 Pascal+/−20%.

10. The method as claimed in claim 1 , where the organic reaction is a transition metal catalyzed reaction in which a transition metal catalyst is used.

11. The method as claimed in claim 10 , where the transition metal catalyst is not a catalyst supported on the cellulose derivative.

12. The method as claimed in claim 10 , where the transition metal is selected from the group consisting of Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Zn.

13. The method as claimed in claim 10 , where the transition metal catalyzed reaction is a transition metal catalyzed reaction involving C-N bond formation.

14. The method as claimed in claim 13 , where the transition metal catalyzed reaction involving C-N bond formation is a Buchwald-Hartwig reaction in which an aryl or heteroaryl halogenide or sulfonate is reacted with a primary or secondary amine, carboxamide, sulfonamide, imide, urea or urethane in the presence of a transition metal catalyst and optionally also of base,
where the aryl or heteroaryl halogenide or sulfonate is a compound of the formula R 2 -(Z) n , where R 2 is an aryl or heteroaryl group, Z is a halogen atom or a sulfonate group and n is 1, 2, 3 or 4, and
the primary or secondary amine, carboxamide, sulfonamide, imide, urea or urethane is a compound of the formula H-N(R 1 )R 3 , where R 1 is H, alkyl, alkenyl, alkapolyenyl, alkynyl, alkapolyynyl, mixed alkenyl/alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, mixed cycloalkenyl/cycloalkynyl, polycarbocyclyl, aryl, heterocyclyl, heteroaryl or R 4 -C(O)-, and R 3 is H, alkyl, alkenyl, alkapolyenyl, alkynyl, alkapolyynyl, mixed alkenyl/alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, mixed cycloalkenyl/cycloalkynyl, polycarbocyclyl, aryl, heterocyclyl, heteroaryl, R 4 —C(O)—, R 4 —S(O) 2 —, R 4 —O—C(O)— or R 5 (R 4 )N—C(O)—, where R 4 and R 5 are independently of each other H, alkyl, alkenyl, alkapolyenyl, alkynyl, alkapolyynyl, mixed alkenyl/alkynyl, cycloalkyl, mixed cycloalkenyl/cycloalkynyl, polycarbocyclyl, aryl, heterocyclyl or heteroaryl, or R 4 and R 5 in the group R 5 (R 4 )N—C(O)- form together with the nitrogen atom they are bound to a mono- bi- or polycyclic heterocyclic ring; or R 1 and R 3 form together with the nitrogen atom they are bound to a mono-, bi- or polycyclic heterocyclic ring;
where the alkyl, alkenyl, alkapolyenyl, alkynyl, alkapolyynyl, mixed alkenyl/alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, mixed cycloalkenyl/cycloalkynyl, polycarbocyclyl, heterocyclyl, aryl or heteroaryl groups R 1 , R 2 , R 3 , R 4 , and R 5 can carry one or more substituents.

15. The method as claimed in claim 1 , where the organic reaction is a carboxamide or sulfonamide bond formation reaction, where a carboxylic acid or a carboxylic acid derivative or a sulfonic acid or a sulfonic acid derivative is reacted with a primary or secondary amine, where in case that a carboxylic acid is used, the reaction is optionally carried out in the presence of a coupling reagent.

16. The method as claimed in claim 1 , where the organic reaction is a Michael addition.

17. The method as claimed in claim 1 , where the organic reaction is the introduction of protective groups, or the organic reaction is the removal of protective groups.

18. The method as claimed in claim 1 , which is additionally carried out in the presence of a surfactant different from the cellulose derivative as defined in claim 1 , where the surfactant is selected from the group consisting of anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof.

19. The method as claimed in claim 18 , where the surfactant is a polyoxyethanyl-α-tocopheryl succinate derivative.

20. The method as claimed in claim 1 , where after completion of the organic reaction the cellulose derivative is precipitated by heating or by adding an inorganic salt, where the inorganic salt is selected from the group consisting of sodium sulfate, potassium sulfate, magnesium sulfate, ammonium sulfate, sodium phosphate, potassium phosphate, sodium hydrogenphosphate, potassium hydrogenphosphate and sodium chloride; where precipitation of the cellulose derivative can be carried out before or after removing the reaction product and, if present, unreacted starting compounds, and where the precipitated cellulose derivative, after a reactivation step, can be reused in the method as claimed in claim 1 .

Assignees

• Abbvie Deutschland
• Abbvie Inc

Inventors

• Braje Wilfried
• Britze Katarina
• Dietrich Justin D
• JOLIT Anais
• KASCHEL Johannes
• Klee Johanna
• Lindner Tanja

Classifications

• C07F5/025

  Boronic and borinic acid compounds · CPC title

• C07F5/02

  Boron compounds · CPC title

• C07D495/04

  Ortho-condensed systems · CPC title

• C07D471/04

  Ortho-condensed systems · CPC title

• C07D409/04

  directly linked by a ring-member-to-ring-member bond · CPC title