Addition of sulfur dichloride

C/760 mmHg) sulfur dichloride After the addition stirring v/as stopped and the flask was allowed to stand for 15 h in the ice-bath. The condenser was replaced with a drying tube containing CaCl (refluxing of the vinyl chloride had stopped completely after the addition of sulfur dichloride). 

V. Bridged Sulfides by Addition of Sulfur Dichloride to Dienes... 

A unique reaction for the preparation of a fused cyclic system containing the thietane ring is the addition of sulfur dichloride to norbornadicne to give 93. This reaction, however, failed to produce similar results with other cyclic 1,4-dienes. 

AH- Thiopyrans are directly accessible only in relatively poor yield, and then only by condensation of a suitable 1,5-dicarbonyl compound with sulfide (690PP21). As has been described earlier, this particular reaction is bedevilled with the problem of disproportionation to tetrahydrothiopyrans and thiopyrylium compounds. Thiopyran-4-ones may be prepared in a related manner by addition of sulfur dichloride to divinyl ketones, followed by base treatment (76MI22500). 

Thiiranes can be formed directly and stereospecifically from 1,2-disubstituted alkenes by addition of trimethylsilylsulfenyl bromide, formed at -78 C from reaction of bromine with bis(trimethylsilyl) sulfide (Scheme 7).12 A two-step synthesis of thiiranes can be achieved by addition of succinimide-A/-sulfe-nyl chloride or phthalimide-A -sulfenyl chloride to alkenes followed by lithium aluminum hydride cleavage of the adducts (Scheme 8).13 Thiaheterocycles can also be formed by intramolecular electrophilic addition of sulfenyl chlorides to alkenes, e.g. as seen in Schemes 914 and 10.13 Related examples involving sulfur dichloride are shown in Schemes 1116 and 12.17 In the former case addition of sulfur dichloride to 1,5-cyclooctadiene affords a bicyclic dichloro sulfide via regio- and stereo-specific intramolecular addition of an intermediate sulfenyl chloride. Removal of chlorine by lithium aluminum hydride reduction affords 9-thiabicyclo[3.3.1]nonane, which can be further transformed into bicyclo[3.3.0]oct-1,5-ene.16... 

Addition of sulfur dichloride to bicyclo[2.2.1]heptadienes gives tricyclic thietanes such as 52 and In a related reaction, the episulfide 54 yields... 

An intermediate of type 41b is probably involved in the formation of compound 44a from the reaction of bis(2-chloro-l,2-diphenylvinyl) sulfone with sodamide the sulfone was prepared by the addition of sulfur dichloride to diphenylacetylene followed by oxidation of the adduct with hydrogen peroxide. 

The addition of sulfur dichloride and 1,5-cyciooctadiene to produce (1a,2a,5a,6a)-2,6-dichloro-9-thiabicyclo[3.3.1]nonane (1) has been described by several workers. - Determination of the stereochemistry of the product has been carried out using H NMR methods, and by means of the X-ray crystal structure of the corresponding sulfone derivative. The procedure described here as step A is that due to Corey and Block.3... 

Substituted 2-chloroalkanesulfenyl chlorides can be prepared analogously by addition of sulfur dichloride to methacrylonitrile or methacrylic esters.42... 

By transannular addition of sulfur dichloride to 9-oxabicyclo[3.3.1]nonan-2,6-diene... 

Transannular addition of sulfur dichloride to 9-azabicyclo[3.3.1]nona-2,6-dienes (42 N-formyl 9l 44 N-phenylsulfonyl 94 and 62 N-tolylsulfonyl p 3i, 32)j applied as an entry to the 2-thia-6-aza-adamantane system. The chlorine atoms in 91 were easily exchangeable with sodium iodide in boiling diethyl ketone (-> 92, 82%)" or with silver acetate in acetic acid (- 93, 70%)" resp. Under analogous reaction conditions the dichloride 94 was transformed into the diacetate 95 (95%) " LiAlH4-reduction of the diacetate 93 yielded 74% of N(6)-methyl-4 8 -dihydroxy-2-thia-6-aza-adamantane (97). The C(4) and C(8)... 

It is interesting to note that trans isomers, whereas, a ratio of 1 9 is obtained from c s,sulfur dichloride may be attributable to a concerted 1,4-addition followed by chlorine migration to the double bond. The high... 

Without additional reagents Addition of sulfur dichloride to acetylene derivatives... 

The effect on the Bergman cycloaromatization of sulfur-containing substituents in the acetylene branch was studied for simple models, such as butyl-2-(triisopropylsilylethynyl)phenylethynylsulfide 3.922 (Scheme 3.133) [411]. The starting sulfide 3.922 was synthesized by treatment of the mono-trisopropylsilyl-protected orf o-diethynylbenzene 3.921 with butyllithium excess followed by the addition of sulfur dichloride [411]. Cyclization of compound 3.922 (benzene, 200°C, 6 M of 1,4-cyclohexadiene) gave butyl-2-naphthylsulfide 3.923 in 53% yield. Comparison of the parameters of this reaction with the cyclization of ortho-diethynylbenzene showed that the presence of the sulfur atom increases the cyclization barrier although the yield from compound 3.922 is much less than that from ort/ o-diethynylbenzene. These studies are consistent... 

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