Zn dust

ZnS204. Made SO2 on aqueous suspension of Zn dust. Used in bleaches and the vat dyeing process. 

Nitrosation in the 5-position has been reported with compounds 185 and 186 (Scheme 118) (165, 241). which are then reducible to the 5-aminothiazoles by Zn dust in AcOH. An old report (164) describing the nitrosation product of 2-methylaminothiazole as 2-(N-methylimino)-3-nitroso-2,3-dihydrothiazole (187) (Scheme 118) has been recently corrected by Ref. 314. 

C CBr2F2-Ph3P(l equiv), Zn dust (1 equiv), DMAA D CBr2F2-(Me2N)3P (1 equiv), Zn dust (1 equiv), DMAA, E CFlF2l-Ph3P (1 equiv), Zn (Cu), mglyme GLC yield 36% Yield in TFH... 

The parent acid has no independent existence and has not been detected in aqueous solution either. Sodium dithionite is widely used as an industrial reducing agent and can be prepared by reduction of sulfite using Zn dust, Na/Hg or electrolytically, e.g. ... 

It is then precipitated by adding Zn dust. Electrolytic refining may then be used to provide gold of 99.99% purity. ... 

Reductive N-O bond cleavage of perhydropyrido[l,2-6][l,2]oxazine 10 with Zn dust furnished 2-(3-hydroxypentyl)piperidine 11 (96JCS(P1)1113). Similarly, 2/S,4u S,5Q ,7/0,8yS-H-5-benzyloxy-7-(tert-butyldiphenylsilyloxy)-2-[2-(methoxymethoxy)ethyl]-8-methylperhydropyrido[l,2-6][l,2]oxazine gave the respective ring-opened piperidine (OOOL2955, 01JOC3338). 

Chemical Reactions. It burns with a luminous flame and is readily expld (Ref 2). It is reduced with Zn dust and Na hydroxide to dimethyl hydrazine (Ref 2). Action of coned HC1 forms methylhydrazine and formaldehyde (Ref 2). Treatment in anhyd eth with Na metal forms a solid adduct which gives dimethylhydrazine on addn of w (Ref 4). For a review of thermal and photochem reactions see Ref 8 Explosive Limits. In mixts with air the crit press at which exp] occurs varies inversely with temp betw 350 and 380° (Ref 6)... 

Recently, the required heteroaromatic organozinc halides for the Negishi reaction have also been prepared using microwave irradiation [23]. Suna reported that a Zn - Cu couple (activated Zn), prepared using a slightly modified LeGoff procedure from Zn dust and cupric acetate monohydrate, allowed the smooth preparation of (3-pyridinyl)zinc iodide and (2-thienyl)zinc iodide... 

Because of the many examples of such activation of metal powders by TCS 14 only a limited and arbitrary number will be discussed here. The Clemmensen-type reduction of ketones such as cyclohexanone with Zn powder in the presence of TCS 14 affords, via 2082, 2084, and 2085, cyclohexene and, via 2082, O-silylated pinacol 2083 [19, 20]. Ketones such as 5a-cholestan-3-one 2086 are reduced by Zn dust-TCS 14 in TFIF, in ca 65-70% yield, to give 5a-cholest-2-ene 2087 and ca 5% 5a-cholest-3-ene [21] (Scheme 13.8). 

Fx Zn dust/NH4Cl (30%)/THF/reflux Fz When 3-chloromethyl-Fx derivative was submitted to these reduction conditions a fcisfurazan was generated as a reductive dimerization Zn-promoted process [38]... 

Asymmetric Allylation. One of the recent new developments on this subject is the asymmetric allylation reaction. It was found that native and trimethylated cyclodextrins (CDs) promote enantiose-lective allylation of 2-cyclohexenone and aldehydes using Zn dust and alkyl halides in 5 1 H2O-THF. Moderately optically active products with ee up to 50% were obtained.188 The results can be rationalized in terms of the formation of inclusion complexes between the substrates and the CDs and of their interaction with the surface of the metal. 

Reduction of 3-benzyl-8-chloro-4-oxo-4//-pyrido[l,2- ]pyrimidine-2-carboxylate <2004W004/064741> and 2-methyl-4-oxo-4//-pyrido[l,2-tf]pyrimidine-3-carboxylate <2003T4123> with DIBAL-H afforded 2- and 3-formyl derivatives, respectively. Reduction of /V-(4-fluorobenzyl)-3-hydroxy-8-[methoxy(methyl)amino]-4-oxo-6,7,8,9-tetra-hydro-4//-pyrido[l,2- ]pyrimidine-2-carboxamide with Zn-dust in aqueous AcOH afforded the 8-methylamino derivative, which was acylated with AcOH in the presence of Hiinig s base, HOBt, and l-(3-dimethylaminopro-pyl)-3-ethylcarbodiimide-HCl <2004W004/058756>. 3-(Perhydropyrido[l,2- ]pyrimidin-2-yl)propylamine was obtained by catalytic hydrogenation of 2-(perhydropyrido[l,2- ]pyrimidin-2-yl)propionitrile over a Pt02 catalyst <2003FRP1275647>. 

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