77069-61-5

Upstream product

• 13522-38-8 thiobenzoic acid O-(4-nitrophenyl) ester 
• 18803-44-6 sodium p-chlorothiophenolate 
• 4906-35-8 S-(4-chlorophenyl) benzothioate 
• 34220-01-4 di-(4-chlorophenyl)iodonium chloride 
• 3682-36-8 dithiobenzoic acid sodium salt 

Downstream Products

• 2168-78-7 methyl dithiobenzoate 
• 100-68-5 methyl-phenyl-thioether 
• 123-09-1 4-chlorophenyl methyl sulfide 
• 5373-55-7 N-(4-methylphenyl)thiobenzamide 
• 5310-28-1 N-(4-chlorophenyl)thiobenzamide 
• 636-04-4 N-Phenylbenzothioamide 
• 501-65-5 diphenyl acetylene 
• 5310-26-9 N-(4-methoxyphenyl)benzothioamide 

Relevant academic research and scientific papers

Effect of modification of the electrophilic center on the α effect

We report on a nucleophilic study of esters R-C(=X)-Y-Ar in which the electrophilic center has been modified by replacing O by S in the leaving group or carbonyl center: 4-nitrophenyl acetate (1), S-4-nitrophenyl thioacetate (2), 4-nitrophenyl benzoate (3), and O-4-nitrophenyl thionobenzoate (4). The studies include O- and S- nucleophiles as well as α nucleophiles in H2O at 25.0 ± 0.1°C. The sulfur nucleophile (4-chlorothiophenoxide, 4-ClPhS-) exhibits significant enhanced reactivity for the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. On the contrary, the common nucleophile OH- is much less reactive towards 2 and 4 compared with 1 and 3. The effect of changing both the electrophilic center and the nucleofugic center on the reactivity of the other oxygen nucleophiles is not so significant: 4-chlorophenoxide (4-ClPhO-) is four to six times more reactive in the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. The α effects exhibited by butan-2,3-dione monoximate (Ox-) and HOO- are strongly dependent on the nature of the electrophilic center of the substrates, indicating that the difference in the ground-state solvation energy cannot be fully responsible for the α effect. Our results clearly emphasize the strong dependence of the α effect on the substrate structure, notably, the nature of the electrophilic center. The impact of change in the nucleofuge (1-→2) and the electrophilic center (3-→4) on reactivity indicates that anucleophiles will need to be "purpose built" for decontamination and nucleophilic degradation of specific biocides.

Kinetics and mechanism of the aminolysis of phenyl dithiobenzoates

The kinetics and mechanism of the reactions of phenyl dithiobenzoates with anilines in acetonitrile at 55.0 deg C have been studied.The large magnitude of βx(βnuc) and the signs of cross-interaction constants, ρeXY > 0, ρYZ XZ > 0, are all consistent with the carbonyl addition mechanism in which the breakdown of the tetrahedral intermediate, T+/-, is rate limiting.The thiocarbonyl group (C=S) is found to favour amine expulsion in contrast to the carbonyl group (C=O) which favours the S-bonded nucleofuge expulsion from T+/-.The signs of cross-interaction constants, ρXY, ρYZ and/or ρXZ, are shown to provide useful mechanistic criteria for distinguishing, especially, the carbonyl addition mechanism involving the rate-limiting breakdown of the tetrahedral intermediate (T+/- from the concerted SN2 mechanism.

Polyvalent Iodine in Synthesis; 3. An Efficient Method for the Synthesis of Aryl Arenedithiocarboxylates

A new method for the synthesis of aryl arenedithiocarboxylates consists of the S-arylation of sodium arenedithiocarboxylates with diaryliodonium chlorides or bromides in tert-butyl alcohol.