Method for synthesizing dissymmetric sulfoether

Patent metadata

Field	Value
Publication number	US-2018201576-A1
Application number	US-201615537400-A
Country	US
Kind code	A1
Filing date	Aug 16, 2016
Priority date	Jun 15, 2016
Publication date	Jul 19, 2018
Grant date	—

Abstract

A method for synthesizing dissymmetric sulfoether includes the following step: a) under the condition of tetrabutylammonium halide catalysis, compounds having a structure of formula (I), compounds having a structure of formula (II) and salts having sulfur and oxygen are reacted in a solvent to give dissymmetric sulfoether having a structure of formula (III).

First claim

1 . A method for synthesizing dissymmetric sulfoether, comprising:
a) under the condition of tetrabutylammonium halide catalysis, compounds having a structure of formula (I), compounds having a structure of formula (II) and salts having sulfur and oxygen are reacted in a solvent to give dissymmetric sulfoether having a structure of formula (III);

wherein, R1 is selected from phenyl, substituted phenyl, naphthyl, substituted naphthyl, thienyl or substituted thienyl; R2 is selected from hydrogen, phenyl, substituted phenyl, naphthyl, substituted naphthyl, thienyl or substituted thienyl; or R1, R2 form fluorene ring or thioxanthone ring with the C to which it is attached;
R3 is selected from hydrogen or alkyl;
R4 is selected from hydrogen, phenyl, substituted phenyl, naphthyl, substituted naphthyl, thienyl or substituted thienyl; R5 is selected from hydrogen; or R4, R5 form fluorene ring or thioxanthone ring with the C to which it is attached;
R6 is selected from alkyl or substituted alkyl;
X is selected from Cl, Br or I;
said salts having sulfur and oxygen include sodium thiosulfate and/or sodium sulfite.

2 . The method according to claim 1 , wherein,
R1 is selected from phenyl, C1˜C5 alkyl-substituted phenyl, C1˜C5 alkoxy-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5 alkyl-substituted naphthyl, C1˜C5 alkoxy-substituted naphthyl, halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl, C1˜C5 alkoxy-substituted thienyl or halogen-substituted thienyl; R2 is selected from hydrogen, phenyl, C1˜C5 alkyl-substituted phenyl, C1˜C5 alkoxy-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5 alkyl-substituted naphthyl, C1˜C5 alkoxy-substituted naphthyl, halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl, C1˜C5 alkoxy-substituted thienyl or halogen-substituted thienyl; R3 is selected from hydrogen and C1˜C5 alkyl; R4 is selected from hydrogen, phenyl, C1˜C5 alkyl-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5 alkyl-substituted naphthyl, halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl or halogen-substituted thienyl.

3 . The method according to claim 1 , wherein said R6 is selected from C1˜C30 alkyl, cyano-substituted C1˜C20 alkyl, cyano-substituted C1˜C20 benzyl, C1˜C5 alkyl-substituted benzyl, halogen-substituted benzyl, fluorenyl and any of the structural substituents represented in formulas (a-1)˜(a-9):

in formulas (a-3)˜(a-9), m 1 , m 2 , m 3 , n, q, p 1 , p 2 , r 1 , r 2 and e are integer from 0 to 5, respectively.

4 . The method according to claim 1 , wherein structural compound of formula (I) is 1,1-diphenylpropyl-2-enyl-1-ol, 1,1-bis (4-fluorophenyl) prop-2-enyl-1-ol, 1,1-bis (4-chlorophenyl) prop-2-enyl-1-ol, 1,1-bis (4-bromophenyl) prop-2-enyl-1-ol, 1,1-bis (4-methylphenyl) prop-2-enyl-1-ol, 1,1-bis (4-methoxyphenyl) prop-2-enyl-1-ol, 1-phenyl-1-p-methylphenyl-2-en-1-ol, 1-(3,4-dimethylphenyl)-1-phenylprop-2-enyl-1-ol, 1-phenyl-1-p-bromophenyl-2-enyl-1-ol, 1-phenyl-1-o-fluorophenylprop-2-enyl-1-ol, 1-(naphthalen-2-yl)-1-phenylprop-2-enyl-1-ol, 2-methyl-1,1-diphenylprop-2-enyl-1-ol, 9-alkenyl-9H-fluorenyl-9-ol, 9-alkenyl-9H-thioxanthen-9-ol, 1-phenylprop-2-enyl-1-ol, (E)-1,3-diphenylprop-2-enyl-1-ol, (E)-1,3-bis (4-fluorophenyl) prop-2-enyl-1-ol, (E)-1,3-bis (4-chlorophenyl) prop-2-enyl-1-ol, (E)-1,3-bis (4-bromophenyl) prop-2-enyl-1-ol, (E)-1,3-bis (naphthalen-2-yl) prop-2-enyl-1-ol, (E)-1,3-bis (thiophen-2-yl) prop-2-enyl-1-ol or (E)-2-methyl-1,3-diphenylprop-2-enyl-1-ol.

5 . The method according to claim 1 , wherein structural compound of formula (II) is p-cyanobenzyl chloride, m-cyanobenzyl chloride, p-trifluoromethylbenzyl chloride, o-bromobenzyl chloride, p-methylbenzyl bromide, 9-bromofluorene, (4-(chloromethyl) phenyl) (1H-indol-1-yl) methanone, ((3aR, 5S, 5aS, 8aS, 8bR)-2,2,7,7-tetramethyltetrahydroxy-3aH-bis [1,3] dioxo [4,5-b: 4′,5′-d] pyran-5-yl) methyl 4-(chloromethyl) phenyl ester, chloroacetonitrile, 1-bromoacetoacetate, 2-bromo-N, N-diethylpropionamide, bromopropyne, (3-chloropropyl-1-ynyl) benzene, ethyl 4-bromocrotonate, geranyl bromide, iodine iodobutane, and iodine n-decane, 4-chlorobutyronitrile or ethyl 4-bromobutyrate.

6 . The method according to claim 1 , wherein said molar ratio of structural compounds of formula (I):structural compounds of formula (II):salts having sulfur and oxygen is 1:(1.5˜3):(2˜4).

7 . The method according to claim 1 , wherein temperature of said reaction is 20˜90° C.

8 . The method according to claim 1 , wherein time of said reaction is 3˜8 h.

9 . The method according to claim 1 , wherein in step a), after the completion of reaction having structural compounds of formula (I), structural compounds of formula (II) and salts having sulfur and oxygen, extraction, drying and column chromatography are performed successively to give dissymmetric sulfoether having a structure represented in formula (III).

10 . The method according to claim 1 , wherein said solvent is water.

Assignees

• Univ Soochow

Inventors

• Ji Shunjun
• Chu Xueqiang
• Xu Xiaoping
• Cao Wenbin

Classifications

• C07F11/005

  compounds without a metal-carbon linkage · CPC title

• C07C319/28

  Separation; Purification · CPC title

• C07C2527/12

  Fluorides · CPC title

• C07C321/18 Primary

  of an acyclic unsaturated carbon skeleton · CPC title

• C07C319/14 Primary

  of sulfides · CPC title