V-Dimethylhydrazine

Methyl 2-formyl-4-methylfuro[3,2-6]pyrrole-5-carboxylate (86) with 2,6-dialkylphenylhydrazines and a catalytic amount of 4-methylbenzenesulfonic acid in refluxing toluene gave the hydrazones (248)-(250). Analogously (V,A-dimethylhydrazone (251) was made from (V,(V-dimethylhydrazine. 

Ajmaline (14) was chosen as a starting material because its total synthesis and absolute configuration were already established (14-16), and furthermore, the equilibrium isomer 17 from ajmaline chemically corresponds to the hypothetical intermediate 13. Ajmaline (14) was first converted into the hydrazone derivative by treatment with A,)V-dimethylhydrazine and a catalytic amount of sulfuric acid. After protection of the resulting secondary amine with methyl carbamate, the hydrazone was hydrolyzed with cop-per(II) chloride in aq. tetrahydrofuran (pH 7) to afford the aldehyde 19 in 75% yield. The hydroxy group in compound 19 was protected with the methoxyethoxymethyl (MEM) ether, and then bromine was selectively... 

Synonyms 1,1-dimethylhydrazine, unsymmetrical- dimethylhydrazine, asymmetrical- dimethylhydrazine UDMH, V,V-dimethylhydrazine, Dimazine 1,2- dimethylhydrazine, symmetrical dimethylhydrazine, SDMH, V,V-dimethylhydrazine Budavari et al. 1989... 

U/ .f-dimethylhydrazine is employed as a fuel in space appHcations. /V,/V-r)ichloroalkylamines can be converted to nitriles in basic media or by treatment with CsF in acetonitrile (69). 

Witkin (1956) reported intravenous (i.v.), i.p., and oral LD50 (lethal dose for 50% of the animals) values for mice and rats, and i.v. LD50 values for dogs. Similar to hydrazine, the route of administration had minimal effect on the LD50 within species. Generally, monomethylhydrazine and 1,2-dimethylhydrazine appeared to be somewhat more potent in mice and rats than was hydrazine. Results of this study showed that the 1,1-dimethylhydrazine was less acutely toxic than hydrazine or the other hydrazine derivatives. 

V-Nitrosodimethylamine was the major product of ozonation of 1,1-dimethylhydrazine in the dark. Hydrogen peroxide, methyl hydroperoxide, and methyl diazene were also identified (HSDB, 1989). 

V-nitramines too were reduced to disubstituted hydrazines. Electrolysis in 10% sulfuric acid over copper or lead cathodes reduced AT-nitrodimethylamine to. /V,JV-dimethylhydrazine (yield 69%), 7V-nitro-JV-methylaniline to N-methyl-JV-phenylhydrazine (yield 54%), W-nitropiperidine to JV,A -penta-methylenehydrazine (yield 52%) [734], and nitrourea to semicarbazide (yield 61-69%) [755]. 

Augusto, O., Du Plessis, L.R., Weingrill, C.L. V (1985) Spin-trapping of methyl radieal in the oxi-dative metabolism of 1,2-dimethylhydrazine. Biochem. biophys. Res. Commun., 126, 853-858... 

Cameron, I.L., Ord, V.A., Hunter, K.E., Padilla, G.M. Heitman, D.W. (1989) Suppression of a carcinogen (1,2-dimethylhydrazine dihydrochloride)-induced increase in mitotic activity in the colonic crypts of rats by addition of dietary cellulose. Cancer Res., 49, 991-995... 

Mayer, D., Trocheris, V., Hacker, H.J., Viallard, V., Murat, J.C. Bannasch, P. (1987) Sequential histochemical and morphometric studies on preneoplastic and neoplastic lesions induced in rat colon by 1,2-dimethylhydrazine. Carcinogenesis, 8, 155-161... 

Netto, L.E., RamaKrishna, N.V.S., Kolar, C., Cavalieri, E.L., Rogan, E.G., Lawson, T.A. Augusto, O. (1992) Identification of C -methylguanine in the hydrolysates of DNA from rats administered 1,2-dimethylhydrazine. Evidence for in vivo DNA alkylation by methyl radicals. J. biol. Chem., 267, 21524-21527... 

Reddy, B.S., Weisburger, J.H., Narisawa, T. Vender, E.L. (1974) Colon carcinogenesis in germ-free rats with 1,2-dimethylhydrazine and A-methyl-V -nitro-A-nitrosoguanidine. Cancer Res., 34, 2368-2372... 

Smirnova, I.O. Turusov, V.S. (1988) 1,2-Dimethylhydrazine carcinogenesis in neonatally androgenized CBA mice. Carcinogenesis, 9, 1927-1929... 

Sykora, I., Vortel, V. Tretinik, P. (1986) Postnatal carcinogenic study of 1,2-dimethylhydrazine dihydrochloride in rats. Neoplasma, 33, 273-282... 

Turusov, V.S. (1992) Nephroblastoma in a strain CBA male mouse treated with 1,2-dimethylhydrazine. Exp. Oncol., 14, 20-22... 

Turusov, V.S., Linnik, A.B. Morozova, O.V. (1980) Stimulation of 1,2-dimethylhydrazine-induced uterine sarcomagenesis by estradiol dipropionate. Bull. exp. Biol. Med., 11, 599-600... 

Turusov, V.S., Chemeris, GY Parfenov, Y.D. (1985) Pararenal angiosarcoma induced in male mice by 1,2-dimethylhydrazine—a model for studying the role of androgens in chemical carcinogenesis. Carcinogenesis., 6, 325-331... 

Turusov, V.S., Lanko, N.S., Parfenov Y.D. Chemeris, GL (1990) 1,2-Dimethylhydrazine induction of epithelial tumors of the kidneys in CBA strain mice. Eksp. Onkol., 12,71-74 (in Russian)... 

Turusov, V.S., Morozova, O.V. Samoilov, D.V (1994) Estrogen modification of 1,2-dimethylhydrazine carcinogenesis in C3HAmice. Cancer Lett., 83, 51-58... 

Similarly, side-chain alcohols such as those in compounds 251244 and 252167 can give chlorides, and these can react with piperazines244 or thiophos-phates.147 The side-chain phosphorus derivatives 2S3247 and 2S4248,249 are prepared by nucleophilic displacement, respectively, of hydroxide and chloride ions. The dichloromethyl derivative 255 gives the dimethyl-aminomethyl derivative 256 on treatment with /V.Af-dimethylhydrazine.250... 

Fiber was shown to inhibit carcinogenicity of 2-acetylaminofluorene more than thirty years ago (7,17). A recent review (18) has pointed out the lack of consistency in studies of fiber effects on experimental colon carcinogenesis. Investigators use different strains of rat, stock or semipurified diets, and different carcinogens administered orally, subcutaneously or intrarec-tally (Table v). Ward et al. (19) found cellulose to have no effect on the carcinogenicity of azoxymethane (AOM) in male Fisher rats fed a semipurified diet. Freeman et al. (20), on the other hand, found cellulose to protect male Wistar rats from colon cancer induced by subcutaneous injection of 1,2-dimethylhydrazine (DMH). 

Manju, V. and N al i n i, N. (2005) Chemopreventive efficacy of ginger, a naturally occurring anti carcinogen during the initiation, post-initiation stages of 1,2-dimethylhydrazine induced colon cancer. Clinica Chimica Acta 358(1-2), 60-67. 

The tris(hydrazino)silane 114 was formed by treating 112 with lithiated /V,jV-dimethylhydrazine according to Eq. (30) ... 

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