78725-88-9

Upstream product

• 541-41-3 chloroformic acid ethyl ester 
• 106-45-6 para-thiocresol 
• 64-17-5 ethanol 
• 32315-10-9 bis(trichloromethyl) carbonate 
• 623-73-4 diazoacetic acid ethyl ester 
• 224043-75-8 O-ethyl S-(4-methylphenyl) monothiooxalate 
• 201230-82-2 carbon monoxide 
• 103-19-5 di(p-tolyl) disulfide 

Downstream Products

• 51172-60-2 ethyl (4-chlorobenzyl)carbamate 
• 35573-36-5 N-(4-methoxyphenylmethyl)carbamic acid ethyl ester 
• 2621-78-5 ethyl N-benzylcarbamate 
• 17101-98-3 (4-methyl-benzyl)carbamic acid ethyl ester 
• 444901-21-7 ethyl 3-chlorobenzylcarbamate 
• 108-88-3 toluene 

Relevant academic research and scientific papers

Preparation method of thioether

The invention relates to a preparation method of thioether, which comprises the following steps: adding mercaptan/phenol and alpha-diazoacetate into an acetonitrile-water mixed solvent, stirring at room temperature under the irradiation of visible light u

Convenient route to thiocarbonates from alcohols, thiols, and triphosgene

An efficient and simple one-pot, three-component procedure has been introduced for the preparation of various thiocarbonates from thiols, alcohols, and triphosgene in dichloromethane. Copyright Taylor & Francis Group, LLC.

A new method for synthesis of S-aryl-O-alkyl thiolcarbonates: Selenium-catalyzed reaction of alcohols with carbon monoxide and diaryl disulfides

A unique catalytic ability of selenium has been developed. When alcohols were allowed to react with diaryl disulfides in the presence of a catalytic amount of selenium under a pressurized carbon monoxide, S-aryl-O-alkyl thiolcarbonates were obtained in moderate to good yields.

Kinetics and mechanism of the aminolysis of O-ethyl S-aryl thiocarbonates in acetonitrile

The Kinetics and mechanism of the reactions of O-ethyl S-(Z)aryl thiocarbonates with (X)benzylamines in acetonitrile at 45.0 °C are studied. Relatively small values of βx (βnuc) = 0.6 to approximately 0.8 and βz (βlg) = -0.5 to approximately -0.7 together with a negative cross-interaction constant ρxz (= -0.47) and failure of the reactivity-selectivity principle (RSP) are interpreted to indicate a concerted mechanism. The normal kinetic isotope effects (kH/kD = 1.3 to approximately 1.8) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-center-type transition state.

Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 15. Generation of alkoxycarbonyl(sulfenyl)carbenes and their intramolecular insertion to give alkenyl sulfides

A range of 18 alkoxycarbonyl sulfinyl phosphorus ylides 9 have been prepared and their behaviour upon flash vacuum pyrolysis (FVP) at 600 deg C examined. For R1 = H, Me and Et they lose Ph3PO and in some cases Ph3P to give mixtures of products including the alkenyl sulfides 10, the sulfides 11, the disulfides 12 and the thioesters 14. The alkenyl sulfides 10 most likely arise from intramolecular insertion of the alkoxycarbonyl sulfenyl carbenes resulting from loss off Ph3PO to produce β-lactones which then lose CO2 and this is supported by the results from 13C labelled ylides. Possible mechanisms for the formation of 11 and 14 are also presented and the feasibility of various steps has been examined by preparation and pyrolysis of the proposed intermediates. In contrast, pyrolysis of the ylides 9 where R1 = Ph and the tert-butoxycarbonyl ylides 30 leads mainly to complete fragmentation with loss of Ph3PO and benzyl alcohol or 2-methylpropan-2-ol and does not give any useful sulfur-containing products. Four alkoxy-carbonyl sulfonyl diazo compounds 33 have been prepared and in three cases they give the alkenyl sulfones 34 upon FVP at 400 deg C, probably by an intramolecular insertion and decarboxylation process analogous to the formation of 10 from 9. On the other hand the alkoxycarbonyl carbenes produced by FVP of the amino acid-derived diazo compounds 35 undergo alternative proocesses with no sign of β-lactone formation. Fully assigned 13C NMR data are presented for 13 of the ylides.

The Mechanism of Thermal Eliminations. Part 19. Rate Data for Pyrolysis of S-Aryl O-Ethyl Thiocarbonates: the Relative Abilities of Oxygen and Sulphur to Transmit Electronic Effects

Rates of thermal decomposition of a range of S-aryl O-ethyl thiocarbonates have been measured over a 50 degree C range for each compound, between 722.6 and 671.4 K.The compounds are less reactive than the corresponding aryl ethyl carbonates by a factor of ca. 2.0 at 679 K, owing to the smaller -I effect of SAr relative to OAr.This provides further conformation that the reactivity of esters towards thermal elimination parallels the extent of electron withdrawal by the group attached to the acyl carbon atom.The reaction gives a good Hammet correlation with ?0 values, and ρ is 0.26 at 700 K, significantly greater than the value for the corresponding aryl ethyl carbonates.Thus sulphur is a better transmitter of electronic effects than is oxygen, and this transmission order, previously observed in studies in solution, is not a result of solvation phenomena.The ortho-methoxy substituent deactivates in thiocarbonate pyrolysis in contrast to its activation in carbonates.This probably arises from through-space p? --> d? bonding in the former compounds.An improved gold-plated stainless steel pyrolytic reactor is described.