Chemistry of .alpha.,.alpha.-dichlorosulfenyl chlorides

Phillips, W. Gary; Ratts, K. W.

doi:10.1021/jo00975a014

Cited by 30 publications

(11 citation statements)

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“…Reactions of 2 and 3 with O Nucleophiles. Some reactions of chlorosulfanyl compounds with O nucleophiles, in most cases aliphatic alcohols [28 -30] or phenols [31], are described to occur via substitution of Cl. For the reactions with 2 and 3, we chose some alcohols and phenols, as well as AcOH and H 2 O.…”

Section: Methodsmentioning

confidence: 99%

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Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles

Majchrzak

Mlostoń

Linden

et al. 2006

Helvetica Chimica Acta

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The reactions of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (2) with N, O, S, and P nucleophiles occur by substitution of Cl at the S-atom. Whereas, in the cases of secondary amines, alkanols, phenols, thiols, thiophenols, and di-and trialkyl phosphates, the initially formed substitution products were obtained, the corresponding products with allyl and propargyl alcohols undergo a [2,3]-sigmatropic rearrangement to give allyl and allenyl sulfoxides, respectively. Analogous substitution reactions were observed when 3-chloro-3-(chlorodisulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (3) was treated with N, O, and S nucleophiles. The reaction of 3 with Et 3 A C H T U N G T R E N N U N G P led to an unexpected product via cleavage of the SÀS bond (cf. Scheme 13). In the reactions of 2 with primary amines and H 2 O, the substitution products react further via elimination of HCl to yield the corresponding thiocarbonyl S-imides and the thiocarbonyl S-oxide, respectively. Whereas the latter could be isolated, the former were not stable but could be intercepted by MeOH (Scheme 4) or adamantanethione (Scheme 5). The structures of some of the substitution products were established by X-ray crystallography.

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Section: Methodsmentioning

confidence: 99%

“…TLC (SiO 2 ; CH 2 Cl 2 /hexane 1 : 1). Subsequent recrystallization from hexane yielded 18 (67 mg, 79%) [31].…”

Section: -{[(Tert-butyl)amino]disulfanyl}-3-chloro-2244-tetramethmentioning

confidence: 99%

Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles

Majchrzak

Mlostoń

Linden

et al. 2006

Helvetica Chimica Acta

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“…4,11 The properties of dichloroacetamides 2, 14 21, 15 and 22, 16 trichloroacetamide 23, 17 and compounds 13 18 …”

Section: Scheme 10mentioning

confidence: 99%

Transformations of N-ethylamines into amide derivatives under the action of sulfur monochloride

2007

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Tertiary N ethylamines were converted into amide derivatives by reactions with sulfur monochloride and DABCO at 0 °C. Depending on the nature of the substituents in the amine, the reaction can be accompanied by unexpected transformations.Reactions of N substituted diisopropylamines, espe cially commercial and inexpensive N ethyl N,N diiso propylamine (1a) (Hünig base), with sulfur monochloride have been intensively studied by us for more than 10 years. It was believed for a long period of time that such reac tions involve only the isopropyl groups of these com pounds, which allowed the synthesis of complex S,N con taining heterocycles, e.g., bis[1,2]dithiolo[1,4]thiazines, 1 bis[1,2]dithiolopyrroles, 2 and bis[1,2]dithiolylamines. 3 In our further investigations in this field, we found the con ditions for the reaction to stop at the formation of mono cyclic 1,2 dithioles. 4 Tests of these compounds for anti cancer activity at the US National Cancer Institute have revealed their appreciable effects against certain types of cancer. 5 Recently, 6 we have demonstrated that the pathway of the reaction of Hünig base 1a with S 2 Cl 2 and 1,4 di azabicyclo[2.2.2]octane (DABCO) dramatically changes at a lower temperature (0 °C) so that the transformation selectively occurs at the N ethyl group to give N,N di isopropyldichloroacetamide (2), the isopropyl groups re maining intact (Scheme 1). Scheme 1The discovered transformation of the N ethyl group into a dichloroacetamido one has not been documented hitherto and opens up new possibilities for functionaliza tion of N alkyl groups in compounds that can be of inter est for fine organic synthesis.Here we studied reactions of tertiary amines contain ing ethyl or β substituted ethyl groups with sulfur mono chloride and the influence of the structures of the starting reagents on the reaction outcome. Results and DiscussionA study of a reaction of N ethyl N,N diisopropylamine (1a) with S 2 Cl 2 and DABCO in chloroform (Scheme 2) and an analysis of the previous results (Table 1) showed that amide 2 is formed on keeping the reaction mix ture at 0 °C. At room temperature, tricyclic bis[1,2]di thiolo [1,4]thiazines 4 were the major reaction products, while at -20 °C, the reaction proceeded slowly to give dithiolothiazines 5 and 6 in low yields. The amounts of S 2 Cl 2 and DABCO have no substantial effect on the reac tion pathway; with an increase in their amounts, the yield of amide 2 decreased only slightly. Selected data on opti mization of the synthesis of amide 2 from the Hünig base are given in Table 1. Scheme 2i. 1) S 2 Cl 2 , DABCO; 2) HCO 2 H. X = Y = O (4); X = S, Y = O (5); X = Y = S (6)The best conditions for the synthesis of amide 2 are as follows: chloroform as a solvent, 0 °C, 3 days, further

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“…The mixture of (3) and (4, which is also readily accessible in larger quantities, is thus a valuable starting material for products which presumably would be formed from the still unknown (21. be seen in this light. The surprisingly uniform thermolysis, however, is preparatively not without interest, for it leads practically in one step from methyl ketones to acyl chlorides in acceptable yields.…”

mentioning

confidence: 99%

Are α‐Oxothioacyl Chlorides Formed in the Reaction of Methyl Ketones with Thionyl Chloride?

Adiwidjaja

Günther

Voß

1980

Angew. Chem. Int. Ed. Engl.

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Chemistry of .alpha.,.alpha.-dichlorosulfenyl chlorides

Abstract: Takeshima for their kind advice. Thanks are also due to Dr. Haruo Homma and his staff for their microanalyses, to Mr. Jun Uzawa for his measurements of the nmr spectra, and to Mr. Hironori Ogawa for his measurements of the ir spectra.

Cited by 30 publications

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Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles

Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles

Transformations of N-ethylamines into amide derivatives under the action of sulfur monochloride

Are α‐Oxothioacyl Chlorides Formed in the Reaction of Methyl Ketones with Thionyl Chloride?

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