Ethanedithiol chloride

A new route to the tetrahydroTTF system is provided by reaction of oxalyl chloride with ethanedithiol followed by dehydration to give 35. When this is treated with aluminium chloride the salt 36 is formed and its X-ray structure is reported <00ZN(B)597>. The preparation of new simple benzoditelluroles 37 has been described <00MI1127>. Treatment of allyl dithiocarbamates 38 with bromine affords the 2-amino-l,3-dithiolanylium salts 39 <97MIP112282, 98MIP113243>. 

Mercaptoles of ketones are best prepared by treatment of ketones with ethanedithiol or 1,3-propanedithiol in the presence of anhydrous zinc chloride or boron trifluoride etherate. Many desulfurizations have been carried out with these cyclic mercaptoles, especially in steroids. Yields of the hydrocarbons range from 50 to 95% [797]. 

Cyclization by amidomercuration has been reported (391). Reaction of N-methoxycarbonyl-6-aminohept-l-ene (211) with mercuric acetate gave the organomercurial (212). Reductive coupling of 212 with l-decen-3-one in the usual way gave the cis and trans isomers (213). Successive treatment of 213 with ethanedithiol, Raney nickel, and ethanolic hydrogen chloride afforded ( )-sole-nopsin A (Id, 2 parts) and its isomer (Ic, 3 parts), which were separable by preparative gas chromatography (GC) (Scheme 5) (391). 

Ethylene chloride, 34, 85, 86 Ethylene chlorohydrm, 30, 11, 33, 11 Ethylene dibromide, 30, 35 reaction with disodium 1,2 ethanedithiol, 39, 23 Ethylene dnsothiuronium bromide,... 

Trithianes are rare but routes established for the 3-methyl derivative (226) could provide the basis of more general methods. These include the chlorination of diethyl disulfide and the reaction of the sulfenyl chloride (227) with 1,2-ethanedithiol (74MI22601). 1,2,4,5-Tetrathiane (228) has been prepared by the cyclization of two equivalents of the bis sulfenyl chloride CH2Y2 (229 Y = SCI) or the bis Bunte salt CH2Y2 (230 Y = SSQ3Na) using sodium... 

Cyclization of enone (9) in hexane with boron trifluorideetherate in presence of 1,2-ethanedithiol, followed by hydrolysis with mercury (II) chloride in acetonitrile, yielded the cis-isomer (10) (16%) and transisomer (11) (28%). Reduction of (10) with lithium aluminium hydride in tetrahydrofuran followed by acetylation with acetic anhydride and pyridine gave two epimeric acetates (12) (32%) and (13) (52%) whose configuration was determined by NMR spectroscopy. Oxidation of (12) with Jones reagent afforded ketone (14) which was converted to the a, 3-unsaturated ketone (15) by bromination with pyridinium tribromide in dichloromethane followed by dehydrobromination with lithium carbonate and lithium bromide in dimethylformamide. Ketone (15), on catalytic hydrogenation with Pd-C in the presence of perchloric acid, produced compound (16) (72%) and (14) (17%). The compound (16) was converted to alcohol (17) by reduction with lithium aluminium hydride. 

Treatment of a mixture of a carbonyl compound and 1,2-ethanedithiol in dry dichloromethane at room temperature with anhydrous zirconium(iv) chloride dispersed on silica gel gave excellent yields (96-99%) of the respective 1,3-dithiolanes. The high reactivity of this reagent was also observed in the case of less reactive aromatic ketones at room temperature and a,(3-unsaturated aldehydes such as cinnamaldehyde 556 (Equation 74) <1996TL4621>. 

The 2-phosphoryl-substituted 1,3-dithiolane 587 was prepared in 83% yield by treating triethyl phosphonacetate 586 with 1,2-ethanedithiol in the presence of diethylaluminium chloride in 83% yield (Equation 78) <1996JOC8132>. 

The two procedures are applicable to condensations of ketones with both ethanedithiol and -mercaptoethanol. Previous methods (see ref 3 for literature) include use of zinc chloride and sodium sulfate, hydrogen chloride in ether, p-toluenesulfonic acid in benzene with azeotropic distillation, and an exchange method. 

Cyclopropanecarbaldehydes, 1,1-dialkoxy-l-cyclopropylalkanes and cyclopropyl ketones reacted readily with ethanedithiol " " " and propanedithioP to give the corresponding 1,3-dithiolanes and 1,3-dithianes, respectively, in excellent yield. Boron trifluoride diethyl ether complex, in the presence or absence of acetic acid, has generally been used as the catalyst, but hydrogen chloride has also been utilized.An example of this reaction is the formation of the dithioacetal of cyclopropanecarbaldehyde 3. ... 

Preparation of a Polythioester by the Interfacial Condensation of Ethanedithiol and Terephtha-loyl Chloride [16]... 

Reagents i, B0C2O, DMF, EtsN, H2O ii, triisopropylbenzenesulfonyl chloride, pyr iii, 2-aminoethanethiol, EtOH, EtONa iv, 9-phenoxyacridine, phenol v, 4M HQ, dioxane, 1,2-ethanedithiol... 

Rapid, selective thioacetalisation of a variety of aldehydes in the presence of ketones can be achieved with 1,2-ethanedithiol using silica treated with sulfuryl chloride as a catalyst [167]. The reaction is carried out at room temperature within 5 h to give yields of more than 90% of the corresponding 1,3-dithiolanes. Acid-treated montmorillonite KSF has been used to catalyse the synthesis of thioenol ethers from cyclic ketones and butanethiol (e.g. equation 4.46) [168]. 

Early workers reacted the ketone with an excess of the thiol in the presence of an acid catalyst such as zinc chloride , hydrogen chloride or />-toluenesulphonic acid to prepare dithioacetals. The results were erratic and the yields often disappointing. The use of boron trifluoride etherate has led to consistently better results . This method is particularly effective when the thiol is used for the solvent of the ketone as the boron trifluoride etherate is added. Ethanedithiol and propanedithiol are usually the thiols of choice forming 1,3-dithiolanes and 1,3-dithianes respectively. For example, the 1,3-dithiolane of cholestane-3-one (equation 1) can be prepared in high yield by this method . Occasionally the choice... 

The nitroketone 118 (see Section IV,B,1) was treated with hydrogen chloride in ethanedithiol to afford the thioketal 119. Reduction of 119 with zinc and acetic acid and further treatment with Raney nickel in ethanol furnished lactam 120. Hydrolysis of 120 in aqueous methanol containing K2C03 gave 121, which on LAH reduction horded the amine 122. On treatment with sodium methoxide, the iV-chloro derivative of 122 gave verazine (123) (215). 

Physical Data 1,3-propanedithiol bis(/)-toluenesulfonate) mp 67°C l,2-ethanedithiolbis(/>toluenesulfonate) mp76°C. Preparative Methods treatment of potassium thiotosylate, itself made by the reaction of />-toluenesulfonyl chloride with potassium hydrogen sulfide, with 1,3-dibromopropane or 1,2-dibromoethane in the presence of potassium iodide affords 1,3-propanedithiol bis(/>-toluenesulfonate) and 1,2-ethanedithiol bis(p-toluenesulfonate), respectively. ... 

Remarkably, treatment of mixtures of the chlorides (78) and (79) with ethanedithiol leads to the production of only symmetrical bis-sulphides, no products of cross-over being detected the authors propose initial selective intermolecular association, mainly due to homotropic intermolecular hydrogen bonding giving (80) and (81), respectively. 

Donahue et al. (1998) presented a solution-based method for preparing ZnS through sol-gel processing (by route C). Ethanedithiol and zinc chloride were mixed and the resulting sol was heated in a three-step process, producing crystalline wurtzite. Analysis of the sol and its decomposition suggested the following reaction mechanism ... 

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