1005-56-7

Basic information

• Product Name: Phenyl chlorothionocarbonate
• Synonyms: Phenyl thiochloroformate.;Phenoxythiocarbonyl chloride;Phenyl chlorothionoformate, 98+%;Formic acid, chlorothio-, O-phenyl ester;O-Phenyl carbonochloridothioate;(Phenoxy)thioformyl chloride;Chloridothiocarbonic acid O-phenyl ester;Chloridothiocarbonic acid phenyl ester
• CAS NO: 1005-56-7
• Molecular Formula: C₇H₅ClOS
• Molecular Weight: 172.63
• EINECS: 213-736-4
• Product Categories: Sulfur Compounds (for Synthesis);Synthetic Organic Chemistry;Building Blocks;Chemical Synthesis;Organic Building Blocks;Sulfur Compounds;Thiocarbonyl Compounds
• Mol File: 1005-56-7.mol

Chemical Properties

• Melting Point: 51 °C
• Boiling Point: 81-83 °C6 mm Hg(lit.)
• Flash Point: 179 °F
• Appearance: Clear yellow/Liquid
• Density: 1.248 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.166mmHg at 25°C
• Refractive Index: n20/D 1.581(lit.)
• Storage Temp.: 0-6°C
• Solubility: Chloroform, Ethyl Acetate
• Water Solubility: decomposes
• Sensitive: Moisture Sensitive
• BRN: 774830
• CAS DataBase Reference: Phenyl chlorothionocarbonate(CAS DataBase Reference)
• NIST Chemistry Reference: Phenyl chlorothionocarbonate(1005-56-7)
• EPA Substance Registry System: Phenyl chlorothionocarbonate(1005-56-7)

Safety Data

• Hazard Codes: C
• Statements: 34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3265 8/PG 2
• WGK Germany: 3
• F: 10-21
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 1005-56-7(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
Phenyl chlorothionocarbonate is used as a reagent for the preparation of bicyclic thymidine analogs, which serve as selective inhibitors of Thymidine monophosphate kinase Mycobacterium tuberculosis (TMPKmt). This application is crucial in the development of treatments for tuberculosis.
Used in Organic Synthesis:
Phenyl chlorothionocarbonate is used as a key reagent in the stereodirected synthesis of optically active (+)薄荷内酯, which are valuable compounds in the field of organic chemistry.
Used in Peptide Synthesis:
In the field of peptide synthesis, Phenyl chlorothionocarbonate is used for the synthesis of peptide α-thioesters with a variety of C-terminal amino acids. This contributes to the development of novel peptide-based therapeutics and other applications.
Used in Carbohydrate Chemistry:
Phenyl chlorothionocarbonate is employed in the synthesis of scyllo-inositol derivatives, which are important compounds in carbohydrate chemistry and have potential applications in various industries.
Used in Nucleoside Chemistry:
Phenyl chlorothionocarbonate is used for the thionocarbonylation of unprotected thymine nucleosides, a process that is essential in the synthesis of modified nucleosides with potential applications in antiviral and anticancer therapies.
Used in Ribonucleoside Derivatives:
Phenyl chlorothionocarbonate is utilized in the preparation of phenoxythiocarbonyl esters of protected ribonucleosides, which are vital intermediates in the synthesis of various ribonucleoside analogs with potential applications in medicinal chemistry and drug development.

Purification Methods

Purify it by dissolving in CHCl3, washing with H2O, drying (CaCl2), filtering, evaporating and distilling twice under a vacuum to give a clear yellow liquid. It is reactive and POISONOUS—work in a fume cupboard. Store it in sealed ampoules under N2. A possible impurity is O,O'-diphenyl thiocarbonate which has m 106o and remains behind in the distilling flask. [B.gemann et al. in Methoden Der Organischen Chemie (Houben-Weyl) 4th edn (E. Müller Ed.) Vol 9 Schwefel-Selen-Tellur Verbindungen pp. 807-808 1955, Rivier & Schalch Helv Chim Acta 6 612 1923, Kalson Chem Ber 20, 2384 1987, Rivier & Richard Helv Chim Acta 8 490 1925, Sch.nberg & Varga Justus Liebigs Ann Chem 483 176 1930, Sch.nberg & Vargha Chem Ber 64 1390 1931, Beilstein 6 III 609.]

InChI:InChI=1/C7H5ClOS/c8-7(10)9-6-4-2-1-3-5-6/h1-5H

Upstream product

• 463-71-8 thiophosgene 
• 108-95-2 phenol 
• 56-23-5 tetrachloromethane 
• 67-66-3 chloroform 
• 7732-18-5 water 

Downstream Products

• 74-87-3 methylene chloride 
• 16241-04-6 O-phenyl N,N-dimethylthiocarbamate 
• 2423-29-2 N-phenyl-O-phenylthiocarbamate 
• 20351-71-7 O-phenyl N-methyl-N-phenylthiocarbamate 
• 500312-07-2 O-(2-naphthyl) O-phenyl thiocarbonate 
• 302577-06-6 ((4-cyanophenyl)amino)phenoxymethane-1-thione 
• 20333-68-0 phenyl O‐(4‐nitrophenyl) thiocarbonate 
• 116849-48-0 O-ethyl O'-phenyl thiocarbonate 
• 102813-17-2 N-[4-(2-diethylamino-ethoxy)-phenyl]-N'-(4-isobutoxy-phenyl)-thiourea 
• 13509-34-7 diphenylthiocarbonate 
• 412300-68-6 2-chloro-2-phenoxy-3,3-diphenyl-thiirane 
• 857823-04-2 (chloro-fluoren-9-ylidene-methyl)-phenyl ether 
• 824-88-4 O-phenyl carbamothioate 
• 98273-25-7 dichloro-phenoxy-methanesulfenyl chloride 

Relevant articles and documents

NITROXIDE CHEMISTRY XXI. REACTIONS OF BIS(BISTRIFLUOROMETHYLAMINO-OXY)-MERCURY(II) AND NN-BIS(TRIFLUOROMETHYL)NITROXIDE WITH THIOCARBONYL COMPOUNDS

Thiobenzophenone, 9-thiocarbonylfluorene and carbonyl sulphide react with the mercurial, Hg2, to form HgS and the compounds Ph2C2, (C6H4)2C2 and 2CO respectively.The last compound is also formed as the major product on mixing the mercurial with carbon disulphide.With thiophosgene, reaction occurs to form HgCl2 and a mixture of the compounds (CF3)2NSCOCl and (CF3)2NSCOON(CF3)2, which are thought to arise by rearrangement of the intermediates (CF3)2NOC(S)Cl and 2CS.A similar rearrangement may also occur during the reactions of thiobenzoyl chloride and aryl chlorothionoformates with the mercurial but the product mixtures from these reactions are more complex and pure compounds have not been isolated.Reaction between thiophosgene dimer and the mercurial results in a simple chlorine exchange to afford the 1,3-dithietane 2cyclo2S>.The low temperature reaction of thiophosgene with (CF3)2NO gives a thermally unstable product believed to be (CF3)2NOCCl2S(O)ON(CF3)2, while the similar reaction with thiobenzophenone appears to give (CF3)2NOCPh2SON(CF3)2, which decomposes above 0 deg C.

A synthesis of 5'-amino-3',5'-dideoxyuridine

The synthesis of 3',5'-dideoxy-5'-aminouridine starting from uridine is described.

BORON CONTAINING COMPOUNDS AND THEIR USES

The present disclosure contemplates novel boron-containing compounds and their uses as active agents that exhibit pesticidal activity such as antimicrobial, insecticidal, arachnicidal, and/or anti parasitic activity. An agrochemical composition containing such a compound and its use in, animal health, agriculture, or horticulture is also contemplated. A method for promoting plant performance and/or controlling, reducing, preventing, ameliorating, or inhibiting microbes, insects, arachnids, and/or parasites on or in an animal, a plant, a plant part, plant propagation material, and/or harvested fruits or vegetables is also contemplated.

Bare-minimum fluorous mixture synthesis of a stereoisomer library of 4,8,12-trimethylnonadecanols and predictions of NMR spectra of saturated oligoisoprenoid stereoisomers

All four diastereomers of a typical saturated oligoisoprenoid, 4,8,12-trimethylnonadecanol, are made by an iterative three-step cycle with the aid of traceless thionocarbonate fluorous tags to encode configurations. The tags have a minimum number of total fluorine atoms, starting at zero and increasing in increments of one. With suitable acquisition and data processing, each diastereomer exhibits characteristic chemical shifts of methyl resonances in its 1H and 13C NMR spectra. Together, these shifts provide a basis to predict the appearance of the methyl region of the spectrum of every stereoisomer of higher saturated oligoisoprenoids.

Cysteine as a sustainable sulfur reagent for the protecting-group-free synthesis of sulfur-containing amino acids: Biomimetic synthesis of l-ergothioneine in water

Biomass-derived cysteine was used as a sustainable sulfur source for the synthesis of rare sulfur-containing amino acids, such as l-ergothioneine (4), which might be a new vitamin, and various l- or d-2-thiohistidine compounds. Key in this simple, one-pot two-step procedure in water is a bromine-induced regioselective introduction of cysteine followed by a novel thermal cleavage reaction in the presence of thiols, a safer alternative to hazardous red phosphorus. Besides avoiding hazardous sulfur reagents, the new protecting-group-free approach reduces drastically the total number of steps, compared to described procedures. The main drawback, i.e. handling of liquid bromine as an activating and oxidizing reagent in water, was addressed by evaluating four alternative methods using in situ generation of bromine or HOBr, and first encouraging results are described.

Radical OfC transposition: A metal-free process for conversion of phenols into benzoates and benzamides

We report a metal-free procedure for transformation of phenols into esters and amides of benzoic acids via a new radical cascade. Diaryl thiocarbonates and thiocarbamates, available in a single high-yielding step from phenols, selectively add silyl radicals at the sulfur atom of the CdS moiety. This addition step, analogous to the first step of the Barton-McCombie reaction, produces a carbon radical which undergoes 1,2 OfC transposition through an O-neophyl rearrangement. The usually unfavorable equilibrium in the reversible rearrangement step is shifted forward via a highly exothermic C-S bond scission in the O-centered radical, which furnishes the final benzoic ester or benzamide product. The metal-free preparation of benzoic acid derivatives from phenols provides a potentially useful alternative to metal-catalyzed carbonylation of aryl triflates.

DIRECT CONVERSION OF PHENOLS INTO AMIDES AND ESTERS OF BENZOIC ACID

A method is provided for the preparation of an aromatic carboxylic acid aryl ester or an N-aryl aromatic carboxamide. The method comprises contacting an O,O-diaryl thiocarbonate or an O-aryl-N-aryl thiocarbamate with a reactant that regioselectively reacts with sulfur, which contact causes an O-neophyl rearrangement, thereby forming either the aromatic carboxylic acid aryl ester or the N-aryl aromatic carboxamide, respectively.

Radical 1,2-o→c transposition for conversion of phenols into benzoates by o-neophyl rearrangement/fragmentation cascade

Figure Presented Radical merry-go-round! Diaryl thiocarbonates, available in a single step from phenols, can be directly transformed into benzoates by a new radical cascade that transposes O and C atoms at the aromatic core. The cascade bypasses the common Barton McCombie fragmentation in favor of the usually unfavorable O-neophyl rearrangement, which is rendered irreversible and efficient by a highly exothermic C-S bond scission in the O-centered radical (see scheme; FG = functional group).

Aminolysis of aryl chlorothionoformates with anilines in acetonitrile: Effects of amine nature and solvent on the mechanism

The aminolysis of aryl chlorothionoformates (7, YC6H 4OC(=S)Cl) with anilines (XC6H4NH2) in acetonitrile at 5.0 °C has been investigated. The rates are slower than those for the corresponding reactions of aryl chloroformates (6, YC 6H4OC(=O)Cl). This rate sequence is a reverse of that for alkyl chloroformates (1 4) in water, for which rate-limiting formation of a tetrahedral intermediate, T±, is predicted. On the basis of the large negative cross-interaction constant, ρXY = -0.77, failure of the reactivity-selectivity principle, normal kH/k D values involving deuterated nucleophiles (XC6H 4ND2), and low ΔH≠ with large negative ΔS≠ values, a concerted mechanism with a four-membered hydrogen bonded cyclic transition state (11) is proposed for the title reaction series. It has been shown that the solvent change from water to acetonitrile for the aminolysis of 6 and 7 causes a mechanistic change from stepwise to concerted.

Episulfidation of strained cycloalkenes in the thermolysis of 5-aryloxy-1,2,3,4-thiatriazoles

The thermolysis of 5-aryloxythiatriazoles 1 in the presence of norbornene (2a) and trans-cyclooctene (trans-2b) affords the corresponding thiiranes 3a and trans-3b in moderate yields. First-order kinetics are observed, suggesting that a sulfur intermediate, presumably dinitrogen sulfide, is generated in the fragmentation process of 1, which then serves as the active sulfur atom donor.