Transition-metal-free N-arylation of tertiary amines using arynes

Patent metadata

Field	Value
Publication number	US-9650329-B2
Application number	US-201414901111-A
Country	US
Kind code	B2
Filing date	Jun 24, 2014
Priority date	Jun 25, 2013
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

The present invention relates to transition-metal-free process for the synthesis of tertiary arylamines comprises coupling reaction between arynes and N,N-dimethyl aniline compounds in presence of 18-crown-6, KF and THF.

First claim

We claim:

1. A transition metal-free synthesis of tertiary arylamines compounds of general formula (I)

wherein

R 1 =ethyl, methyl or
R 2 =H, alkyl (C 1 -C 5 ), C 6 -C 8 -aryl, halogen (F, Cl, Br, I), —C(O)(OCH 3 ), —C(O)(OCH 2 CH 3 ), CHO, CN, OH, CH═CH—COOEt, CH═CH—C 6 H 4 NO 2 , OCH 3 , OPh,

R 3 =H, CH3, halogen (F, Cl, Br, I),
R 4 =H or D;
or R 2 +R 3 =—O—CH2-O—, —CH═CH—CH═CH—; —C(SO2Cl)=CH—CH═CH—;
comprising the steps of:
i. mixing 2-trimethylsilylaryl trifluoromethyl sulphonate of formula (II) and tertiary amine compounds of formula (III) in the ratio ranging between 2:1 to 1:2 in presence of 18-crown-6, KF and solvent (THF)

wherein R 1 , R 2 and R 3 is as defined above.

2. The process according to claim 1 , wherein the 2-trimethylsilylaryl trifluoromethyl sulphonate are selected from the group consisting of 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate, 4,5-difluoro-2-(trimethylsilyl)phenyl tri-fluoromethanesulfonate, 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 2-methoxy-6-(trimethylsilyl)phenyl trifluoromethanesulfonate, 2-(trimethylsilyl)-naphthalen-1-yl trifluoromethanesulfone, 4-methyl-2-(trimethylsilyl)-phenyl trifluoromethanesulfonate.

3. The process according to claim 1 , wherein the tertiary amine compounds are selected from the group consisting of N, N-diethylaniline, N-methyl-N-phenylaniline, N,N-dimethylaniline, N,N,4-trimethylaniline, 3-(dimethylamino)phenol, 4-bromo-N,N-dimethylaniline, 4-iodo-N,N-dimethyl aniline, 4-(dimethyl amino) benzonitrile, ethyl 4-(dimethylamino)benzoate, 4-(dimethylamino) benzaldehyde, N,N,3-trimethylaniline, 3-bromo-N,N-dimethylaniline, methyl 2-(dimethylamino)benzoate, N,N,3,5-tetramethyl aniline, diethyl (4-(dimethylamino)benzyl)phosphonate (E)-N,N-dimethyl-4-(2-(thiophen-2-yl)vinyl)aniline, N,N-dimethyl-4-(phenyl ethynyl)aniline, N,N-dimethyl naphthalene-1-amine, 5-(dimethyl-amino) naphthalene-1-sulfonyl chloride, 4,4′-(phenylmethylene)bis(N,N-dimethylaniline), ethyl (E)-3-(4-(dimethylamino)phenyl)acrylate, (E)-N,N-dimethyl-4-(4-nitrostyryl)-aniline, 5-(4-(dimethylamino)phenyl)thiophene-2-carbaldehyde, and 3-(dimethylamino)phenol.

4. The process according to claim 1 , further comprises addition of 1.0 equiv ammonium bicarbonate (NH 4 HCO 3 ) to increase the yield of tertiary arylamines.

5. The process according to claim 1 , wherein the reaction is carried out at a temperature in the range of 58 to 62° C. for period in the range of 11 to 12 hours.

6. The process according to claim 1 , wherein the coupling reaction is carried out under argon atmosphere.

Assignees

• Council Scient Ind Res
• Council Scient Ind Res

Inventors

• Biju Akkattu Thankappan
• Bhojgude Sachin Suresh
• Kaicharla Trinadh

Classifications

• C07C309/88

  containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton · CPC title

• C07D333/20

  by nitrogen atoms (nitro, nitroso radicals C07D333/12) · CPC title

• C07F9/4056

  Esters of arylalkanephosphonic acids (C07F9/4025 takes precedence) · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07D333/22

  Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom · CPC title