Bamford

Rice S A 1985 Diffusion-limited reactions Oomprehensive Ohemical Kinetics vol 25, ed C H Bamford, C F H Tipper and R G Compton (Amsterdam Elsevier)... 

C. H. Bamford and G. E. Eastmond, "Acrylonitrile Polymers" iu N. M. Bikales, ed., Engclopedia of Polymer Science andTechnology, Vol. 1, Interscience Publishers, a Division of John Wiley Sons, Inc., New York, 1964, pp. 374—425. 

C. R. Bamford, Colour Generation and Control in Glass, Elsevier Scientific Publishing Co., New York, 1977, pp. 141—164. 

Okfm Syntheses. Conversion of aldehydes and ketones to olefins by the base-catalyzed decomposition of -toluenesulfonic (Ts) acid hydrazones (10) is known as the Bamford-Stevens reaction (54,55). 

C. H. Bamford, in J. 1. Kroschwitz, ed., Enyclopedia ofiPolymer S cience and Engineering, Vol. 13, Wdey-lnterscience, New York, 1988, pp. 708—867. Ketone Peroxides, Product Bulletin, Organic Peroxide Division, Elf Atochem North America, Inc., Philadelphia, Pa., Nov. 1991. 

Bamford and Tipper (eds.), Comprehensive Chemical Kinetics, Elsevier, 1969-date,... 

Exothermic Decompositions These decompositions are nearly always irreversible. Sohds with such behavior include oxygen-containing salts and such nitrogen compounds as azides and metal styphnates. When several gaseous products are formed, reversal would require an unlikely complex of reactions. Commercial interest in such materials is more in their storage properties than as a source of desirable products, although ammonium nitrate is an important explosive. A few typical exampes will be cited to indicate the ranges of reaction conditions. They are taken from the review by Brown et al. ( Reactions in the Solid State, in Bamford and Tipper, Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980). 

A. K. Galwey, Reactions in the Sohd State, in Bamford and Tipper, eds.. Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980. Galwey, A. K., Chemistry of Solids, Chapman and Hall, 1967. Sohn, H. Y, and W. E. Wadsworth, eds.. Rate Frocesses of Extractive Metallurgy, Plenum Press, 1979. Szekely, J., J. W. Evans, and H. Y. Sohn, Gas-Solid Reactions, Academic Press, 1976. Uhmann, ed., Enzyklopaedie der technischen Chemie, Uncatalyzed Reactions with Solids, vol.. 3, 4th ed., Verlag Chemie, 1973, pp. 395-464. 

BAMFORD - STEVENS - CAGUOTI- SHAPIRO Olelinalwn Conversion o( ketones to olelins via tosyl hydrazones with NaOR, LAH, LDA or BuLi... 

Methyl acrylate [96-33-3 M 86,1, b 80 , d 0.9535, n 1.4040. Washed repeatedly with aqueous NaOH until free from inhibitors (such as hydroquinone), then washed with distd water, dried (CaCl2) and fractionally distd under reduced pressure in an all-glass apparatus. Sealed under nitrogen and stored at 0° in the dark. [Bamford and Han J Chem Soc, Faraday Trans 1 78 855 1982.]... 

The Bamford-Stevens decomposition of tosylhydrazones by base has been applied to steroids, although not extensively. It has been demonstrated that the reaction proceeds via a diazo compound which undergoes rapid decomposition. The course of this decomposition depends upon the conditions in proton-donating solvents the reaction has the characteristics of a process involving carbonium ions, and olefins are formed, often accompanied by Wagner-Meerwein-type rearrangement. In aprotic solvents the diazo compound appears to give carbene intermediates which form olefins and insertion products ... 

The alkyl lithium method gives high yields of -olefins from 17-ketones via the tosylhydrazones. A -Olefins are formed from 6- and 7-ketones. (Compare with the Bamford-Stevens reaction which gives A - and A -olefins, respectively.) In the presence of an excess of alkyl lithium, alkylation may occur. 

In the preparation of C-nor-D-homosteroid hormone analogs Mitsuhashi and Harada extended the Bamford-Stevens rearrangement to the cholanic acid series. Treatment of 3a-hydroxy-12-oxocholanic acid /j-toluene-... 

Baeyer-Villager oxidation, 10, 151, 433 Bamford-Stevens reaction, 402 Barton reaction, 253 Beckmann rearrangement, 140 Benzilic acid rearrangement, 418, 435 3 -Benzoyloxy-7-methylenecholest-5-ene, 60 Benzylmagnesium chloride, 64 3-Benzyloxycholesta-3,5-diene, 342... 

From 5 the formation of alkene 2 is possible through loss of a proton. However, carbenium ions can easily undergo a Wagner-Meerwein rearrangement, and the corresponding rearrangement products may be thus obtained. In case of the Bamford-Stevens reaction under protic conditions, the yield of non-rearranged olefins may be low, which is why this reaction is applied only if other methods (e.g. dehydration of alcohols under acidic conditions) are not practicable. 

A more promising procedure for the formation of alkenes from tosylhydrazones is represented by the Shapiro reaction It differs from the Bamford-Stevens reaction by the use of an organolithium compound (e.g. methyl lithium) as a strongly basic reagent ... 

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