Dimethylformamide startg

A soln. of the startg. active ester in dimethylformamide treated with 2 moles Na-p-toluenesulfonamide, and allowed to stand 12 hrs. at room temp., if necessary with stirring crude product. Y 79%. F. e. s. K. Hohenlohe-Oehringen and L. Call, M. 99, 1301, 1289 (1968) cf. M. 99, 1313... 

A mixture of acrylonitrile (stabilized by hydroquinone), powdered manganese, cobaltous chloride, and dimethylformamide shaken 20 hrs. at 20° adiponitrile. Y 95% based on startg. m. consumed. G. Agnes, G. P. Chiusoli, and G. Cometti, Chem. Commun. 1968, 1515. 

Na-5-Chloro-2-(N-methyliodomethanesulfonamido)benzophenone - a - oximate (obtained by evaporation of the soln. of the startg. oxime in the calculated amount of methanolic Na-methoxide) heated 15 min. in dimethylformamide on a steam bath 8-chloro-l-methyl-6-phenyl-lH,3H-4,2,l,5-benzoxathiadiazocine 2,2-di-oxide. Y 41%. O. Hromatka, M. Knollmuller, and D. Binder, M. 100, 1434 (1969). 

A soln. of l-pyrrolidino-cw-3,5-dimethylcyclohexene and the startg. nitrone in dimethylformamide stirred 48 hrs. at room temp. 4-pyrrolidinoisoxazolidine deriv. Y 66%. Y. Nomura, F. Furusaki, and Y. Takeudii, Bull. Chem. Soc. Japan 43, 1913 (1970) normal addition cf. Synth. Meth. 22, 709. 

AIM soln. of chlorine in propionic acid added at -30° to a soln. of the startg. m. in dimethylformamide... 

A soln. of the startg. m. in r rr-butanol-dimethylformamide stirred and treated under Og with K- r/-butoxide, stirring continued until Og-absorption ceases, and the resulting mixture of acids esterified with methanol and 12 N HCl -> methyl 23,24-bisnor-5/ -diolanate. Y 70%. F. e. s. M. Fetizon, F. J. Kakis, and V. Igna-tiadou-Ragoussis, Tetrahedron 30, 3981 (1974). 

Startg. m. treated with K-r rNbutoxide in dimethylformamide, which causes rapid intramolecular elimination product. Y 76%. M. J. Robins and E. M. Trip, Tetrah. Let. 1974, 3369. 

Startg. m. heated 5 hrs. at 200° in dimethylformamide product. Y almost 100%. - Acid hydrolysis of the product gives high yields of l,l-dicarboxy-2-/ -ketocycloalkanes. F. e. s. P. G. Sammes and R. A. Watt, Chem. Commun. 1975, 502. 

Isoflavones. Startg. m. in dimethylformamide treated cautiously with 4 equivalents BFj-etherate, whereupon a vigorous reaction occurs, then a soln. of 3 equivalents methanesulfonyl diloride in dimethylformamide added at 50°, and heated 1.5 hrs. on a steam bath in an open beaker -> product. Y 82%. F. e. s. R. J. Bass, Chem. Commun. 1976, 78. 

Polyenes. Ethanolic Na-ethoxide added dropwise to a cold soln. of all-trans-3,1-dimethyl -1 - (p-phenoxyphenylsulf onyl) -9- (2,6,6- trimethy Icyclohexen -1 -yl) -2,4,6,8-nonatetraene and the startg. bromo ester in dimethylformamide, stirring continued 5 hrs. at 0° under Ng, then poured into aq. acetic acid ethyl all-trans-2,6,11,15-... 

Startg. amide and 5 eqs. copper powder in dimethylformamide heated at 130-35 for 20-50 min - product. Y 85%. The NH-acidity of the startg. amide and stability of the azetidinone largely determine the yield. An ultrasonic probe could be used as an alternative to the high temp., but the procedure lacks reproducibility. F.e.s. R. Joyeau et al., Tetrahedron Letters 30, 337 0 (1989). 

Startg. m. dissolved in anhydrous dimethyl sulfoxide anisaldehyde and 2,4-dinitrobenzoic acid. Y ca. 100% of each. - Dimethylformamide or an amine may be used instead of dimethyl sulfoxide. F. e. s. R. M. Ellam and J. M. Padbury, Chem. Commun. 1971, 1094. 

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). 

Startg. bromide added dropwise at 15-20° to a stirred soln. of 2 moles Na-nitrite in dimethylformamide, and stirring continued 4 hrs. at room temp, after heat evolution has subsided 3-nitro-5-phenylisoxazole. Y 63%. F. e. with lower yields s. S. Rossi and E. Duranti, Tetrah. Let. 1973, 485. 

Ethyl thallio(I)methylacetoacetate allowed to react at room temp, with a suspension of the startg. thiophanium bromide in dimethylformamide product. Y almost 100%. D. G. Martin, L. J. Hanka, and L. M. Reineke, Tetrah. Let. 1971, 3791. 

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. 

A stirred mixture of the startg. m. and sym-collidine treated under Ng with a soln. of LiCl in a minimum amount of dry dimethylformamide, cooled to 0°, treated dropwise with methanesulfonyl chloride, and stirring continued 1-1.5 hrs. at 0° -> product. Y 82%. - No allyl rearrangement occurs, and only allylic alcohols undergo this conversion under the above conditions. F. e. s. E. W. Collington and A. I. Meyers, J. Org. Chem. 36, 3044 (1971). 

A stirred mixture of the startg. vic-dinitro compd. and Na2S 9H20 in dimethylformamide exposed 12 hrs. to two 20 w. fluorescent lights under Ng product. 

A suspension of the startg. lactam and 1.1 moles PCI5 in anhydrous toluene refluxed 4 hrs. under Ng, then the solvent, the resulting HCl and POCI3 removed completely, the residue dissolved in dimethylformamide, added dropwise to a supsension of 2 moles each of NaNg and LiCl in dimethylformamide, and heated 18 hrs. at 100° product. Y 87%. F. e. s. L. S. Crawley and S. R. Safir, J. Heterocyclic Chem. 12, 1075 (1975). 

Vilsmeier reagent derived from dimethylformamide and SOCI2 allowed to react 1 hr. at 0° with the startg. m. in tetrahydrofuran product. Y almost 100%. S. Karady et al., Tetrah. Let. 1976, 2401. 

A soln. of the startg. m. in dimethylformamide treated with triethylamine, and allowed to stand 2 hrs. at room temp. l-benzyl-4-methoxy-3-phenyl-lH-l,4-benzodiazepine-2,5(3H,4H)-dione. Y 60%. F. e. and ring closures s. E. Wolf and H. Kohl, A. 1975, 1245. 

A 5% soln. of the startg. m. in dimethylformamide heated at 130° benzal-dehyde and benzyl cyanide. Y ca. 100%. - This is part of a method for the cleavage of carbon-carbon double bonds. F. e. s. J. Kalvoda and H. Kaufmann, Chem. Commun. 1976, 209 cf. ibid. 1976, 210. 

Diselenium dichloride added dropwise to a stirred soln. of the startg. m. in abs. dimethylformamide 2-n-butyl-3-chloro-l-benzoselenophene. Y 41%. F. e. and products s. W. Ried and G. Sell, Synthesis 1976, 447. 

The startg. cis-cis- or trans-trans-his(allylic bromide) in dimethylformamide added at 50° during 12 hrs. by motor-driven syringe to a soln. of nickel carbonyl in the same solvent under argon rans-frans-1,5-cyclooctadecadiene. Y 76-... 

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