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PF3, (CH3)3SiCl -> (CH3)3SiF, and RC(O)Cl -> RC(O)F. Others
include the conversion of (C6H5)3P into (C6H5)3PF2 and of
(R3NC(S)S)2 into R2NCF3, R=alkyl. In organic chemistry, fluorides
are easily accessible from alcohols, geminal fluorides RR'CF2 from
the respective aldehydes or ketones, and acyl fluorides RC(O)F from
carboxylic acides by using DAST. Because DAST is easy to handle and
gives clean reactions in syntheses, this Gmelin volume devotes much
space to the description of the chemical and physical properties od
DAST.
The present volume describes acyclic Sulfur-nitrogen compounds with
sulfur of the oxida- tion number II. The first chapter deals with
sulfur imide (S=NH), N-organyl-sulfur imides (S=NR, R = or- ganyl),
and metal complexes of sulfur imides. N-Organyl-sulfur imides have
not been isolated, but they can be trapped, for example, by
cycloaddition and stabilized by coordination to transi- tion
metals. 11 The following chapter present a detailed survey of other
8 -N compounds with one- coordinate sulfur, e.g., dithionitrous
acid (S=N-SH) and derivatives, the salts of the dithionitryl ion (1
+) ([S=N=S]+), and N-thionitroso-diorganyl-amines (S=NNR , R =
organyl). Only the reac- 2 tions of [S=N=S]+ AsF5, among the known
[S=N=S]+ salts, have been extensively studied. Cycloadditions with
alkenes and triple bonded compounds produce 1 ,3,2-dithiazolium
salts and their derivatives. S=NN(CH )z and S=NN(C H )z form
transition metal complexes. The 3 6 5 Iigand is coordinated via the
S atom in a monodentate manner.
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