Ortho-alkynyl anilines and process for preparation thereof

Patent metadata

Field	Value
Publication number	US-9758476-B2
Application number	US-201515321329-A
Country	US
Kind code	B2
Filing date	Jun 22, 2015
Priority date	Jun 25, 2014
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

The present invention relates to novel ortho alkynyl anilines of formula (I) which are useful in synthesis of drug intermediates and natural products and process for preparation of these ortho alkynyl anilines of formula (I) via copper catalyzed Multi Component Reactions (MCR).

First claim

The invention claimed is:

1. A compound of formula (I)

wherein,
R 1 is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and ester;
R 2 is selected from hydrogen, substituted or unsubstituted alkyl(C 1 to C 7 ), and substituted or unsubstituted aryl;
R 3 is selected from hydrogen, substituted or unsubstituted alkyl(C 1 to C 7 ), substituted or unsubstituted aryl, and alkoxy;
R 4 is selected from hydrogen, substituted or unsubstituted C 1 to C 7 alkyl, substituted or unsubstituted aryl, and alkoxy; and
R 3 and R 4 jointly represent 1,3-dioxolyl.

2. The compound as claimed in claim 1 , wherein said compound of formula (I) are selected from the group consisting of:
i. Dibenzyl1-(2-(3-ethoxy-3-oxoprop-1-yn-1-yl)phenyl)hydrazine-1,2-dicarboxylate;
ii. Dibenzyl1-(2-(3-ethoxy-3-oxoprop-1-yn-1-yl)-4,5-dimethoxyphenyl)hydrazine-1,2-dicarboxylate,
iii. Dibenzyl1-(6-(3-ethoxy-3-oxoprop-1-yn-1-yl)benzo[d][1,3]dioxol-5-yl)hydrazine-1,2-dicarboxylate and
iv. Dibenzyl1-(2-(3-ethoxy-3-oxoprop-1-yn-1-yl)-4,5-dimethylphenyl) hydrazine-1,2-dicarboxylate.

3. A one-pot process for the preparation of a compound of formula (I) comprising the steps of:
i. stirring a reaction mixture of (trimethylsilyl) aryl triflates with terminal alkyne and azodicarboxylate in the presence of a copper catalyst, cesium fluoride and solvent at a temperature in the range of 80 to 110° C. for a period ranging from 8 to 15 h to obtain a mixture;
ii. cooling the mixture as obtained in step (i) at room temperature in the range of 20 to 30° C. followed by filtering and purifying to obtain compound of formula (I),
wherein the compound of formula (I) is:

wherein,
R 1 is selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and ester;
R 2 is selected from hydrogen, substituted or unsubstituted alkyl(C 1 to C 7 ), and substituted or unsubstituted aryl;
R 3 is selected from hydrogen, substituted or unsubstituted alkyl(C 1 to C 7 ), substituted or unsubstituted aryl, and alkoxy;
R 4 is selected from hydrogen, substituted or unsubstituted C 1 to C 7 alkyl, substituted or unsubstituted aryl, and alkoxy; and
R 3 and R 4 jointly represent 1,3-dioxolyl.

4. The process as claimed in claim 3 , wherein said copper catalyst is a copper (I) salt selected from the group consisting of copper chloride, copper bromide, and copper iodide.

5. The process as claimed in claim 3 , wherein the (trimethylsilyl) aryl triflates are selected from the group consisting of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethoxy-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethane-sulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate.

6. The process as claimed in claim 3 , wherein the terminal alkyne is selected from the group consisting of ethyl propiolate, methyl propiolate and butyl propiolate.

7. The process as claimed in claim 3 , wherein said azodicarboxylate is selected from dibenzyl azodicarboxylate and dialkyl azodicarboxylate.

8. The process as claimed in claim 3 , wherein said solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, ethyl acetate, toluene, acetonitrile, and dimethylformamide.

Assignees

• Council Scient Ind Res

Inventors

• Suryavanshi Gurunath Mallappa
• Shelke Anil Maruti

Classifications

• C07C281/02 Primary

  Compounds containing any of the groups [IMAGE cpc-sch-C07C-0972.gif], e.g. carbazates · CPC title

• C07D317/66

  Nitrogen atoms not forming part of a nitro radical · CPC title

• C07D215/227

  only one oxygen atom which is attached in position 2 · CPC title