Tosyl startg

Indoline allowed to react 2 hrs. at 0° with N-methyl-N-tosylpyrrolidinium per-dilorate in methylene chloride N-tosylindoline. Y 96.7%. - Similarly selective N-tosylation Startg. aminoalcohol -> N-tosyl deriv. Y 80%. F. e. s. T. Oishi et al., Chem. Commun. 1972, 1148. 

A mixture of N-tosyl-/ -anilinopropionic acid and PC15 in dry thiophene-free benzene refluxed for 80 min., cooled to 0 in an ice-bath, anhydrous SnCl4 in thiophene-free benzene added, after 5 min. at 5° allowed to stand 12 hrs. at room temp., and the complex formed decomposed with dil. HC1 -> N-tosyl-4-keto-l,2,3,4-tetrahydroquinoline (startg. m. f. 30 a). Y 95%.—The inverse Friedel-Crafts procedure with A1C13 (s. 652) had to be used in other cases. (W. S. Johnson, E. L. Woroch, and B. Gr. Buell, Am. Soc. 71, 1901 (1949).)... 

Chlorenol tosylates. HCl bubbled through a soln. of startg. alkynyl tosylate in methylene chloride at —20° under argon for ca. 5 min 3,3-dimethyl-1-chloro-l-(tosyloxy)-l-butene. Y > 99%. F.e. inch ene-l,l-diol sulfonates (from sulfonic acids) and 1-acoxyenol tosylates (from carboxylic acids) s. P.J. Stang, K.A. Roberts, J. Org. Chem. 52. 5213-7 (1987). 

A mixture of startg. alkyne, paraformaldehyde, and tetraethylammonium tosylate in DMF electrolyzed in the cathode compartment of a cell fitted with a Pt electrode under a constant current density of 3.3 mA/cm until 0.75 F/mol passed - product. Y 81%. Reaction is facilitated by a basic species generated in situ from paraformaldehyde, which leaves sensitive functions (epoxides and tetrahydropyranyl ethers) unaffected. F.e.s. S. Torii et al., Chem. Letters 1988, 1977-8. 

Methyllithium in ether added to a suspension of Cul in the same solvent at —30°, when the soln. became transparent (12 min) a soln. of startg. silylenol phosphate in ether added dropwise, the mixture stirred for 4 h, and quenched with 1 1 satd. NH4Cl/ether - product. Y 90%. The method works best in acyclic systems with highly nucleophilic cuprates, and the regiochemistry complements that of the tosyl-hydrazone route (cf. Synth. Meth. 33, 595s36). F.e. inch cross-coupling with LiCuPh2 s. F.L. Koerwitz et al., J. Org. Chem. 54, 743-7 (1989). 

A soln. of NaOH in EtOH added slowly with stirring to an ice-cooled suspension of startg. aminothioenolether and tosyl azide in the same solvent, and stirred for 10 h at room temp. - 4-benzoyl-l-phenyl-5-tosylamino-l 7/-1,2,3-triazole. Y 57%. F.e. and detosylation with coned. H2SO4 s. R.T. Chakrasali et al.. Synthesis 1988, 851-4. 

A soln. of startg. 2-aza-1,3-diene and tosyl cyanide in benzene stirred at 20° for 30 min, and the mixture treated with methanol 6-tosyl-4(3//)-pyrimidinone. Y 93%. F.e. and with CI3CCN in place of TsCN, also prepn. of startg. dienes, s. P. Bayard et al.. Tetrahedron Letters 29, 3799-802 (1988). 

Tosylisocyanate added to the startg. enolether cooled to ca. 10°, and shaken under anhydrous conditions with water-cooling until the exothermic reaction has ceased 4-ethoxy-3,3-dimethyl-l-tosyl-2-azetidinone. Y 100%. F. e. and different course of the reaction s. F. Effenberger and R. Gleiter, B. 97, 1576 (1964). 

Startg. oxime tosylate added portionwise to an equimolar amount of Na dissolved in ethanol, and stirred 5 6 hrs. at room temp. 2-ethoxy-4,5,6,7-tetrahydro-lH-... 

Startg. m. in ether-hexamethylphosphoramide treated successively with 1 equivalent methyllithium, 1.05 equivalents tosyl chloride, and 1.05 equivalents Li-thio-phenoxide -> product. Y 93%. P. A. Grieco, Chem. Commun. 1972, 486. 

Stereospecific conversion. Startg. keto-15 -tosylate in acetone injected from a hypodermic syringe through a needle projecting into the heated zone of a silica tube at ca. 600° and 0.3-0.5 mm Ng, and the unchanged startg. m. recycled twice product. Y 77%. - Acetolysis (cf. Synth. Meth. 24, 920) gives a different product also obtained by pyrolysis of the epimer. J. P. Johnston and K. H. Over-ton, Soc. Perkin I 1972, 1490. 

Ring expansion. Startg. m. allowed to react with tosyl diloride in pyridine -> product. Y 52%. - This reaction provides entry to a class of azasteroids not accessible through the conventional Beckmann rearrangement of oximes. F. e. s. D.H.R. Barton et al., Chem. Commun. 1971, 945. 

Methyl-4(5)-nitroimidazole added to a soln. of Na in methanol, evaporated to dryness, and the resulting Na-salt refluxed 2 hrs. in a mixture of isopropyl iodide and dimethylformamide -> 12 g. l-isopropyl-2-methyl-4-nitroimidazole. - The 5-nitro isomer was obtained by refluxing the above startg. m. with 2-propyl tosylate in benzene. M. Hoffer et al., J. Med. Chem. 14, 993 (1971). 

A stirred 0.1 M soln. of the startg. di-Na-salt (prepared in almost 100% yield by addition of 2 equivalents Na-ethoxide to a stirred hot slurry of N,N-bis(tosyl-... 

Optically active compds. A 66%-NaH-oil dispersion added with cooling to a soln. of the (-)-startg. m. in dimethylformamide containing some water, and stirred 20-30 min. at 10-20° tosyl-L-azetidine-2-carboxylic acid. Y 95%. M. Miyoshi et al., Chem. Lett. 1973, 5. 

Glyoxal as startg. m. 27, 951 Glyoxalines s. Imidazoles Glyoxalyl chloride tosyl-... 

Startg. nitrone and an equimolar amount of hydroxylamine tosylate dissolved by heating in ethanol, and evaporated -> N-hydroxyglycine benzyl ester tosylate. Y 91%. F. e. and process s. T. Polonski and A. Chimiak, J. Org. Chem. 41, 2092 (1976). 

An ethereal soln. of LiAlH4 added dropwise with stirring to a soln. of 5-tosyl-D>arabinose diethyl mercaptal in ether-benzene, refluxed 8 hrs. with stirring, and allowed to stand overnight 5-deoxy-D-arabinose diethyl mercaptal (startg. m. f. 237). Y 56%. F. e. s. H. Zinner, K. Wessely, and H. Kristen, B. 92, 1618 (1959). 

A mixture of anthraquinone, Zn-dust, and ethanol treated with 20%-NaOH, refluxed 1 hr. until most of the startg. m. is dissolved, then methyl tosylate added portionwise with stirring until the color is discharged 9,10-dimethoxyanthra-cene. Y 92%. J. S. Meek, P. A. Monroe, and G. J. Bouboulis, J. Org. Ghem. 28, 2572 (1963). 

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