Condensation of thiophenols with aryl halides using metallic copper as a reactant. Intermediation of cuprous thiophenolates

1984 ◽  
Vol 62 (8) ◽  
pp. 1544-1547 ◽  
Author(s):  
Takakazu Yamamoto ◽  
Yasuhiro Sekine
Keyword(s):  
Temperature Dependence ◽  
Time Course ◽  
Metallic Copper ◽  
Aryl Halides ◽  
Copper Oxides ◽  
Alkyl Aryl ◽  
Aryl Iodides ◽  
Dehydrogenative Coupling ◽  
Alkyl Iodides ◽  
Aryl Sulfides

The reaction of thiophenol (PhSH) with metallic copper affords CuSPh and H2 through Cu-catalyzed dehydrogenative coupling of PhSH to PhSSPh and ensuing addition of PhSSPh to Cu. Condensation between thiophenols (ArSH) and aryl iodides or bromides (Ar′X) in the presence of Cu affords diaryl sulfides (ArSAr′) in good or moderate yields (ArSH + Ar′X + Cu → ArSAr′ + CuX + 1/2H2). Use of alkyl iodides (RI), instead of Ar′X, affords alkyl aryl sulfides (ArSR) in good yields. These condensations are considered to proceed mainly through (1) copper-catalyzed dehydrogenative coupling of ArSH to ArSSAr with evolution of H2, (2) addition of ArSSAr to Cu giving CuSAr, and (3) coupling of CuSAr with Ar′X giving ArSAr′ and CuX; temperature dependence of products, time course of the reaction, the reaction of PhSSPh with Cu, and the reaction of Ar′X with CuSPh support this view. Use of copper oxides (Cu2O and CuO), instead of Cu, also affords diaryl sulfides in good or moderate yields.

scholarly journals Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

2013 ◽  
Vol 9 ◽  
pp. 467-475 ◽  
Author(s):  
Silvia M Soria-Castro ◽  
Alicia B Peñéñory
Keyword(s):  
Microwave Irradiation ◽  
Microwave Heating ◽  
Catalytic System ◽  
Low Cost ◽  
One Pot ◽  
Alkyl Aryl ◽  
One Pot Synthesis ◽  
Aryl Iodides ◽  
The One ◽  
Aryl Sulfides

S-aryl thioacetates can be prepared by reaction of inexpensive potassium thioacetate with both electron-rich and electron-poor aryl iodides under a base-free copper/ligand catalytic system. CuI as copper source affords S-aryl thioacetates in good to excellent yields, by using 1,10-phenanthroline as a ligand in toluene at 100 °C after 24 h. Under microwave irradiation the time was drastically reduced to 2 h. Both procedures are simple and involve a low-cost catalytic system. This methodology was also applied to the “one-pot” synthesis of target heterocycles, such as 3H-benzo[c][1,2]dithiol-3-one and 2-methylbenzothiazole, alkyl aryl sulfides, diaryl disulfides and asymmetric diaryl sulfides in good yields.

A Novel Method for the Direct Synthesis of Symmetrical and Unsymmetrical Sulfides and Disulfides from Aryl Halides and Ethyl Potassium Xanthogenate

Synlett ◽  
2018 ◽  
Vol 29 (07) ◽  
pp. 986-992 ◽  
Author(s):  
M. Soleiman-Beigi ◽  
Z. Arzehgar
Keyword(s):  
Direct Synthesis ◽  
Aryl Halides ◽  
New Method ◽  
Alkyl Aryl ◽  
Novel Method ◽  
Aryl Sulfides ◽  
Bunte Salts

An efficient and new method for the synthesis of disulfides and sulfides via the reaction of aryl halides with ethyl potassium xanthogenate in the presence of MOF-199 is described. O-Ethyl-S-aryl ­carbonodithioate has a key role as an intermediate in this procedure; it was converted into symmetrical diaryl disulfides in DMF. Additionally, this could be applied to the synthesis of unsymmetrical aryl alkyl(aryl′) disulfides by the reaction with S-alkyl(aryl) sulfurothioates (Bunte salts) as well as unsymmetrical aryl alkyl(aryl′) sulfides in DMSO.

Copper-Catalyzed Three-Component Coupling Reaction of Aryl Iodides, a Disilathiane, and Alkyl Benzoates Leading to a One-Pot Synthesis of Alkyl Aryl Sulfides

Synthesis ◽  
2019 ◽  
Vol 51 (11) ◽  
pp. 2323-2330
Author(s):  
Norio Sakai ◽  
Hiromu Maeda ◽  
Yohei Ogiwara
Keyword(s):  
Coupling Reaction ◽  
Sulfur Source ◽  
Diphenyl Diselenide ◽  
One Pot ◽  
Alkyl Aryl ◽  
One Pot Synthesis ◽  
Aryl Iodides ◽  
Alkyl Moiety ◽  
Aryl Sulfides ◽  
Three Component Coupling

A copper-catalyzed three-component coupling reaction of aryl iodides, hexamethyldisilathiane and alkyl benzoates leading to alkyl aryl sulfides has been demonstrated. A disilathiane acted as both a sulfur source and a promoter of the sulfidation, and the alkyl moiety of the alkyl benzoate was effectively introduced on one side of the sulfide. Moreover, we found that the protocol can be expanded to the preparation of ethyl phenyl selenide with diphenyl diselenide.

One-Pot Synthesis of Symmetrical and Unsymmetrical Aryl Sulfides by Pd-Catalyzed Couplings of Aryl Halides and Thioacetates

2011 ◽  
Vol 76 (11) ◽  
pp. 4371-4378 ◽  
Author(s):  
Namjin Park ◽  
Kyungho Park ◽  
Mihee Jang ◽  
Sunwoo Lee
Keyword(s):  
Aryl Halides ◽  
One Pot ◽  
One Pot Synthesis ◽  
Aryl Sulfides

Nickel-catalyzed direct formation of the C–S bonds of aryl sulfides from arylsulfonyl chlorides and aryl iodides using Mn as a reducing agent

2017 ◽  
Vol 4 (1) ◽  
pp. 31-36 ◽  
Author(s):  
Yang Wang ◽  
Xiaofeng Zhang ◽  
Haixiong Liu ◽  
Hui Chen ◽  
Deguang Huang
Keyword(s):  
Reducing Agent ◽  
Aryl Iodides ◽  
Direct Formation ◽  
Aryl Sulfides

Unsymmetrical aryl sulfides were synthesized by nickel-catalyzed arylsulfonyl chlorides and aryl iodides via intermediate disulfides using Mn as a reducing agent.

A Facile One-Pot Synthesis of Alkyl Aryl Sulfides from Aryl Bromides

2004 ◽  
Vol 69 (9) ◽  
pp. 3236-3239 ◽  
Author(s):  
Jungyeob Ham ◽  
Inho Yang ◽  
Heonjoong Kang
Keyword(s):  
One Pot ◽  
Alkyl Aryl ◽  
One Pot Synthesis ◽  
Aryl Bromides ◽  
Aryl Sulfides

Synthetic reactions by complex catalysts. XII. Copper-catalyzed reaction of isocyanide with alcohol

1969 ◽  
Vol 47 (7) ◽  
pp. 1217-1222 ◽  
Author(s):  
Takeo Saegusa ◽  
Yoshihiko Ito ◽  
Shiro Kobayashi ◽  
Kiwami Hirota ◽  
Nobuyuki Takeda
Keyword(s):  
Allyl Alcohol ◽  
Ternary Complex ◽  
Catalyst Activity ◽  
Metallic Copper ◽  
Copper Oxides ◽  
Metal Compounds ◽  
Alkyl Isocyanide ◽  
Unsaturated Alcohols ◽  
Synthetic Reactions ◽  
The Difference

The reaction of alkyl isocyanide with alcohol to produce alkyl formimidate requires catalysis by metal compounds. The catalysts are classified into two groups. The first group includes metallic copper, and the oxides of copper (Cu (I) and Cu (II)), silver, and mercury, which induce the isocyanide reactions of various alcohols including saturated and unsaturated alcohols and amino-alcohol. The second group catalysts are the chlorides of copper (Cu (I)), silver, zinc, and cadmium, which cause the reactions of isocyanide only with special alcohols having strong coordinating tendencies toward the catalyst, as being exemplified by allyl alcohol and β-N,N-dimethylaminoethanol. Among these catalysts, metallic copper and copper oxides are the most effective and give the products almost quantitatively. The difference in catalyst activity between the two groups of catalysts has been explained by assuming a ternary complex consisting of the catalyst, isocyanide, and alcohol as the site of reaction.

Sign in / Sign up

Export Citation Format

Share Document