Thiobenzoyl chloride

Formamidine disulfide (103) was also formed when 5-aminothiatriazole (10) was allowed to react with thiobenzoyl chloride in acetonitrile without addition of base (81BSB89>. Beer and Hart found that 5-aminothiatriazole (10) reacted with acetyl chloride or acetic anhydride to give 3,5-diace-tamido-l,2,4-thiadiazole (104 R = Me) while neither a thiapentalene (102) nor 5-acetamido-thi-atriazole was observed (Scheme 18) <77CC143). In contrast, L abbe and Vermeulen isolated 2,5-dimethyl-l,6-dioxa-6a-/, -thia-3,4-diazapentalene (102 R = Me) together with the 1,2,4-thiadiazole... 

An attempt has been made to obtain the elusive thiobenzoyl azide at low temperature.19 Ethanolic solutions of thiobenzoyl chloride and tetrabutylammonium azide were mixed at —115° directly in a low-temperature UV cell. On slight warming (to ca. —100°) a reaction took place with formation of thiatriazole, but no new absorptions due to thiocarbonyl chromophore were observed. This most probably means that the ring closure to thiatriazole, not unexpectedly, is more rapid than the bimolecular formation of thiocarbonyl azide. 

Attempts have been made to obtain 5-phenylthiatriazole-l-oxide (the 5-oxide) for thermal and photochemical studies.24 A nonoxidative route was investigated by mixing ethanolic solutions of either cis- or trans-thiobenzoyl chloride 5-oxide and ammonium or tetrabutylammonium azide. At room temperature a rapid evolution of gas takes place, and besides nitrogen, both sulfur and sulfur dioxide are formed in amounts approximately according to Eqs. (11) and (12). 

Likewise, thiobenzoyl chloride gives 3,4-diaza-l,6,6aA4-trithiapentalene (59) in low yield (11%), which may also be prepared from the above diazapentalene and P4Si0 (81BSB89). 

R = Ph) is also formed in the reaction between diazomethane and thiobenzoyl chloride, probably via a 1,3-dipolar addition of diazomethane to the thiocarbonyl group. Similar additions have been observed by Huisgen et The reaction between thioacyl chlorides and diazo compounds was first studied by Staudinger and Siegwart.i 3 (R = Ph) has been prepared by cyclization of 11 with triethylortho-formate, and also from 2-phenyl-1,3,4-oxadiazole and phosphorus pentasulfide. ... 

Triazoles can be acylated in the usual manner, e.g. with acyl halides and anhydrides. Isocyanates react with the formation of mixed ureas (139), which show characteristic short-wave carbonyl absorptions (1745, 1788 cm ) (61LA(648)72). Treatment of 1,2,3-triazole with thiobenzoyl chloride in the presence of triethylamine yields a mixture of 1-thiobenzoyl-lH- and 2-thiobenzoyl-2//-l,2,3-triazoles (73LA636). 

Acylation of benzotriazoles occurs in most instances on the 1- (or 3-)nitrogen atom. From 5-methylbenzotriazole and acetyl chloride or acetic anhydride, a mixture of l-acetyl-4-and -5-methylbenzotriazoles is obtained (13JCS1391). With acetic anhydride, benzoyl chloride or benzenesulfonyl chloride and 5,6-dimethylbenzotriazole, acylation on N-1 occurs (52JA4917) and no N-2 substitution product could be observed. Analogously, benzotriazole or 1-trimethylsilylbenzotriazole reacts with thiobenzoyl chloride to afford 1-thiobenzoyl-benzotriazole (73LA636). Similarly, with phenyl isocyanate 1-phenylcarbamoylbenzotriazole (143) is formed (49JA2297). 

Aryl thionoesters (54a) may be prepared by nucleophilic substitution reactions of aryl thiocarbonyl halides with alcohols or phenols for instance, thiobenzoyl chloride (58) condenses with phenol to yield the diaryl ester (54a) (Scheme 30). 

Brom-thiobenzoyl-chlorid und l-(Chlor-thiocarbonyl)-naphthalin sind auf diese Weise nicht zugang-lich24. 2-(Chlor-thiocarbonyl)-thiophen erhalt man unrein zu 8%24. 

Die so hergestellten aromatischen Thiocarbonsaure-chloride sind, im Kiihlschrank aufbewahrt, monatelang haltbar. Selbst das mit Thionylchlorid praparativ nicht herstellbare 4-Methoxy-thiobenzoyl-chlorid fallt sofort kristallin an. 

Analog erhalt man Thiobenzoyl-chlorid und 4-Methyl-thiobenzoyl-chlorid zu jeweils 40-50%34. 

Thiobenzoyl-chlorid kann dutch Spaltung von N-Thiobcnzoy 1 -imidazol mit Chlorwasserstoff in ether. L6 sung erhalten werden36 (s.a. Carbonsaure-chlorid-Synthese37v,L38) ... 

LaBt man Thiobenzoyl-chlorid an der Luft stehen, wird schon nach wenigen Stunden im IR-Spektrum die C = 0-Bande des Benzoylchlorids sichtbar und elementarer Schwefel abgeschieden56 ... 

Stark wirkende Halogen-Ubertrager wandeln Thiobenzoyl-chlorid in die entsprechenden Aryl-trihalogen-methane82-84 um. 

Naher untersucht sind Umsetzungen von Thiobenzoyl-chlorid mit aliphatischen Diazo-Verbindungen88 z. B. ... 

Preparation. Several methods of preparation have been reported, but the most convenient is probably the reaction of CS with phenylmagnesium bromide or phenyllithium to give dithiobenzoic acid this is converted into thiobenzoyl chloride with thionyl chloride. Oxygen must be rigorously excluded or benzoyl chloride is formed. The reagent reacts with alcohols in dry pyridine to... 

DEHYDRATION Diethoxyaluminum chloride. Lithium n-propylmercaptide. N-Methyl-N,N -di-r-butylcarbodiimidium tetrafluoroborate. o-Nitrobenzenesulfonyl chloride. Potassium acetate. Thiobenzoyl chloride. Triphenylphosphine ditriflate. Triphenyl-phosphine methiodide. 

Methyl dithiobenzoate added to a soln. of anhydrous NaHS in abs. methanol, stirred 2 hrs. at room temp, until homogeneous, allowed to stand overnight, and coned, in vacuo at 45° — dithiobenzoic acid (Y 67%) treated with SOClg in ether thiobenzoyl chloride (Y 61%). — It is not necessary to isolate the intermediate dithiobenzoic acid. E. J. Hedgley and H. G. Fletcher, Jr., J. Org. Chem. 30, 1282 (1965). 

A soln. of thiobenzoyl chloride in ethyl acetate dropped rapidly at room temp, during 2 min. to a soln. of Na-thiocyanate in the same solvent, and the product isolated after 1.5 hrs. thiobenzoyl thiocyanate. Y 82%. F. e. s. J. Goerdeler and W. Teller, Tetrah. Let. 1972, 1513. 

Thioacylation of Alcohols and Thiols. Thiobenzoyl chloride and Bu CHg-C(S)C1 have been used to prepare various thiono- and dithio-esters, e.g. the chiral (177). Dialkyl tetrafluorobis(thiono)succinates [CFgC(S)OR]a result from alcoholysis of - -CF2C(S)F]2, whereas the ortho-thioester (178) is obtained from -t-CF2C(S)F]2 and methanethiol. ... 

Adducts (186) were formed by the regiospecific, but nonstereospecific, reaction of diphenylnitrilimine with diaryl sulphines." Sulphines of the type (187) reacted with aromatic sulphenyl chlopdes in a thiophilic manner, yielding (188). The sulphenic acid (189), a tautomer of (187), was considered as the reactive species in the latter reaction. The nucleophilic attack of azide ions on thiobenzoyl chloride S-oxide gave the yellow, very unstable sulphine (190), which decomposed rapidly to ben-zonitrile at room temperature with the evolution of gas, but which at -80 C could be characterized by means of i.r. spectroscopy. 9-Thiofluorenone... 

Thiobarbituric acid, see D-00492 >Thiobenzoic acid, T-OOl55 >Thiobenzoyl chloride, in T-OOl55... 

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