Sulfoxide, cyclopropyl phenyl

Under the same basic conditions /ra . -l-acetoxymethyl-1-methyl-2-tosylcyclopropane generated an a-sulfonyl anion, which attacked the ester group intramolecularly and afforded 2,5-dimethyl-l-tosyl-3-oxabicyclo[3.1.0]hexan-2-ol (22) in 50% yield.Stereoselective synthesis with a chiral cyclopropyl sulfoxide was experienced when ( )-4-tolylsulfinylcyclopropane was reacted first with butyllithium and then with methyl benzoate and gave 1-benzoyl-1-[(5)-4-tolylsulfinyl]cyclopropane (23a) in 62% yield. A useful reaction took place when 2-(hy-droxymethyl)cyclopropyl phenyl sulfide was treated first with an excess of butyllithium and then with dimethylformamide and gave 2-hydroxy-l-phenylsulfanyl-3-oxabicyclo[3.1.0]hexane (24), a lactol which has been used to carry out various useful synthetic transformations. Another useful reaction occurred when cyclopropyl phenyl sulfones were treated with butyllithium followed by an acyl imidazole to give acyl cyclopropanes in decent yield. 

Irradiation at 350 nm of 1,1-dibromocyclopropanes dissolved in liquid ammonia or dimethyl sulfoxide in the presence of sodium benzenesulfanate leads to l,l-bis(phenylsulfanyl)cyclo-propanes. The yields are in all cases below 50% which is due to both decomposition of the product on longer irradiation and formation of significant amounts of cyclopropyl phenyl sulfide. Most 1,1-dichlorocyclopropanes are unreactive, and no reaction occurs in the presence of oxygen, di- erf-butyl nitroxide and 1,3-dinitrobenzene, which supports the notion that the reaction is a radical process. The cleanest reaction took place during irradiation of 2,2-dichloro-1 -methylcyclopropanecarbonitrile, which gave no sulfide, little unreacted starting material, and 1-methyl-2,2-bis(phenylsulfanyl)cyclopropanecarbonitrile (4) in 47% yield. 

Efficient oxidation also results from treatment of cyclopropyl phenyl sulfide (7) with ( —)-camphorsulfonyloxaziridines 8. Due to the optical activity of the reagents, the product cyclopropyl phenyl sulfoxide 9 is optically active. The best results were obtained when (-)- , -dichlorocamphorsulfonyloxaziridine [( —)-8b] was used the sulfoxide was obtained in 90% yield with 92% ee of the 5 -isomer. Application of ( —)-camphorsulfonyloxaziridine ( —)-8a, on the other hand, lowered both the yield and the enantiomeric excess to 23%.Moderate optical purity was obtained when cyclopropyl phenyl sulfide was incubated with Mortierella isabellina, cyclopropyl phenyl sulfoxide was isolated in 58% yield with 66%ee of the (-1-)-sulfoxide, together with cyclopropyl phenyl sulfone (2% yield). Optically inactive cyclopropyl phenyl sulfoxide was obtained in 98% yield when the corresponding sulfide was treated with sodium metaperiodate. ... 

Cyclopropyl phenyl sulfoxide (1) reacted with sodium azide to give S-cyclopropyl-S-phenyl-sulfoximide (2). (7 )-Cyclopropyl 4-tolyl sulfoxide reacted similarly with tosyl azide to afford (/ )-S-cyclopropyl-5 -(4-tolyl)-Al-tosylsulfoximide in 63% yield.Formation of a S-N bond was also observed on reaction of cyclopropanesulfonyl chloride 3 with trimethylamine and triethylamine in a mixture of dichloromethane and isopropyl alcohol giving the corresponding A. A -dialkylcyclopropanesulfonamide 4 the yields were, however, low (< 27%). ... 

Formation of sulfide with concurrent ester hydrolysis was achieved when various Cj cyclopropyl cephalosporin 5-oxide 2,2,2-trichloroethyl esters were treated with phosphorus trichloride followed by zinc under acidic conditions. Sulfoxide reduction also occurred on treatment of cyclopropyl phenyl sulfoxide with a mixture of benzenethiol and chlorotrimethylsilane in chloroform to give cyclopropyl phenyl sulfide in 76% yield and on reaction of various substituted cyclopropyl phenyl sulfoxides with diisobutylaluminum hydride. ... 

A mixture of 3-benzoyldihydro-2(3H)-furanone and NaBr in dimethyl sulfoxide heated 6 hrs. at 160° under Ng cyclopropyl phenyl ketone. Y 91.5%. F. e., also with NaCl and in dimethylformamide, s. S. Takei and Y. Kawano, Tetrah. Let. 1975, 4389. 

Normal nucleophilic substitution occurred on treatment of 2-carbamoyl-3-chloropyrazine with alcoholic methylamine at 130° (423, 836) 2-chloro-3-(4 -morpholinocarbonyOpyrazine with morpholine at reflux in benzene (867) 2dimethyl sulfoxide at 65° (857) and cyclohexylamine in benzene at reflux (946) 3-chloro-2-methoxycarbonyl-5-phenylpyrazine with alcoholic methylamine at 140° (375) 2-carboxy-3-chloropyrazine with anhydrous ammonia at 100° for 5 hours (947) 2-carbamoyl-6-chloropyrazine with aqueous methylamine at reflux (940) 2-chloro-6-(4 -morpholinocarbonyl)pyrazine (and other amides) and 2-chloro-6-methoxycarbonylpyrazine with morpholine (and other amines) (870, 948, 949) and 2-chloro-6-methoxycarbonylpyrazine with liquid ammonia at 80° (870). 2-Chloro-3-methoxycarbonylpyrazine fused with guanidine carbonate gave 2-amino4-hydroxypteridine and its 7-methyl-, 7-phenyl, and 6,7-diphenyl analogues were prepared similarly (371,375). 

CONJUGATE ADDITION Alkylmethyl-magncsiocuprates. 2-Carboethoxyl-benzyl phenyl sulfoxide. Cyanodiethyl-aluminum chloride. 1-Cyclopropyl-l-tiimethylsilyloxyethylene. Lithium 1,3-butadiene-l-olate. Lithium dimethyl-cuprate. Magnesium ethyl malonate. Potassium carbonate. Tri-n-butyl-stannyllithium. Trimethylzinclithium. 

A soln. of phenacyl bromide in a little tetrahydrofuran added at -30 to -20° to dimethylsulfoxonium methylid prepared from trimethylsulfoxonium iodide and NaH in dimethyl sulfoxide, and stirred at room temp, overnight -> phenyl cyclopropyl ketone. Y 37%. Also with phenacyl tosylate and f. e. s. P. Bravo et al., G. 100, 566 (1970) Tetrahedron 27, 3563 (1971). 

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