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N-Halosulfinylamines.

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Bis(sulfiny1amido)mercury(r1)
By W. Verbeek and W. Sundermeyer[*l
Not only many organic N-sulfinylamines [ I ] but also N-(trimethylsilyl)sulfinylamine[zl are known, the reactions of the
latter being very similar to those of silyl pseudohalides.
We have obtained bis(sulfinylamido)mercury(II) ( I ) as the
first sulfinylamide of a metal by reaction of mercury(i1)
fluoride with N-(trimethylsily1)sulfinylamine. The reaction
proceeds quantitatively.
Tetrahydrofuran is a particularly suitable solvent as ( I ) dissolves readily in it and can be recrystallized from it. 23 g of
HgFz reacts with 27 g of (CH&SiNSO in 40-60 ml of boiling, stirred, dry T H F within 30 rnin in a strongly exothermic
reaction.
The amide ( I ) crystallizes as colorless needles, m.p. 128 "C
(decomp.), but, if heating is too slow, decomposition sets in
below the melting point. In contrast t o most organic sulfinylamines, it is surprisingly stable to hydrolysis and alcoholysis.
Compound ( I ) was identified by analysis and its mass spectrumr31 [with reference t o the isotope 202Hg: m / e = 326,
Hg(NS0)2; 264, Hg(NS0); 202, Hg; 48, SO; 46, NS; 32, S].
The I R spectrum (Nujol) shows bands at 1250s, 1217s,
1078 s, 604 rn, 590 m, 561 m, 313 s, and 280 w cm-1.
Received: January 30, 1969
I 2 965a I€]
German version: Angew. Chem. 81, 330 (1969)
[*I Dr. W. Verbeek and Prof. Dr. W. Sundermeyer
Anorganisch-chemisches Institut der Universitat
69 Heidelberg, Tiergartenstr. 2 (Germany)
[l] G. Kresze, A. Maschke, R . Albrecht, K . Bederke, H. P .
Patzschke, H . Smalla, and A . Trede, Angew. Chem. 74, 135
(1962); Angew. Chem. internat. Edit. I , 89 (1962); G. Kresze and
W. Wucherpfennig, Angew. Chem. 79,109 (1967); Angew. Chem.
internat. Edit. 6, 149 (1967).
[2] 0. J. Scherer and P . Hornig, Angew. Chem. 78, 776 (1966);
Angew. Chem. internat. Edit. 5 , 729 (1966).
[3] We are very grateful to Dr. Seidl, Badische Anilin- und SodaFabrik, for measurement and discussion of the mass spectrum.
N-Halosulfinylamines
By W. Verbeek and W. Sundermeyer[*l
In connection with our studies of the reaction of silyl pseudohalides with the halides of various elements we have treated
N-(trimethylsi1yl)sulfinylamine
with halogens. The reaction with chlorine led to an almost quantitative yield of Nchlorosulfinylamine ( I ) , in contrast to the reactions of organic N-sulfinylamines which afford thionyl chloride and the
corresponding amine with scission of the N = S bond [21.
(CH3)3SiNSO + Clz + CI-N=S=O
+ (CH3)3SiCI
(1)
Liquid chlorine (15.8 g) is added dropwise t o (CH&SiNSO
(30 g) with stirring at -76 O C , a smooth reaction giving compound (1) which, however, can be obtained pure and free
from the accompanying chlorotrimethylsilane only by preparative gas chromatography. Alternatively, the reaction
mixture may be converted by partial fluorine exchange with
HgFz into fluorotrimethylsilane and unchanged ( I ) , and the
latter then separated by fractional distillation.
( I ) is a clear liquid (b.p. 65.5 O C , m.p. -80 "C) with a suffocating odor; it can be distilled under a n inert gas at atmospheric pressure without decomposition; the vapor-pressure
curve is represented by log p = -1784/T + 8.15. (Trouton
376
constant 24.1 cal/deg). I t was identified by analysis and its
mass spectrum[31 which contains fragments at m/e = 49
(NCI), 48 (SO), 46 (NS). 35 (Cl), and 32 (S), as well as the
molecular ion at m / e = 97 (referred to 35C1). The IR spectrum
(gas) showed the six bands required for a linear tetraatomic
molecule (with tentative assignments) a t 1248 vs (vS=O),
995 w (vN=S), 676 s (vN-Cl), 532 s (SNSO), 359 s (y), and
187 s cm-1 (SCINS).
Compound ( I ) reacts vigorously with mercury and explosively with water. When heated in air it deflagrates with a
bluish-white flame.
The analogous reaction of N-(trimethy1silyl)sulfinylamine
with bromine gives a difficultly separable mixture that
contains N-bromosulfinylamine (2). However, (2) is formed
quantitatively o n treatment of stoichiometric amounts of
bis(sulfinylamido)mercury[41 with bromine in trichlorofluoromethane a t room temperature.
Hg(NSO)Z
+ 2 Brz
+
2 Br-N=S=O
+ HgBr2
(2)
(2) is a colorless liquid (b.p. 12"C/12 torr, m.p. -48OC)
which becomes yellow at room temperature owing t o loss of
bromine. It was identified by its I R spectrum and its mass
spectrum [ m / e = 141 (BrNSO), 93 (NBr), 79 (Br), 48 (SO),
46 (NS), and 32 (S), referred to 79BrI. There are six I R bands
also in this case (with tentative assignments) at 1245 vs
(vS=O), 1003 w (vS=N), 621 s (vN-Br), 456 s (SNSO),
335 s (y), and 161 s cm-1 (8BrNS).
Reaction of N-(trimethylsi1yl)sulfinylamine with fluorine
gives a poor yield of N-fluorosulfinylamine (3).
+
(CH3)3SiNS0 F:!
-+ F-N=S=O
+ (CH&SiF
(3)
Fluorine, diluted with nitrogen, is passed into a solution of
(CH&SiNSO in trichlorofluoromethane at -80 O C . ( 3 ) is
obtained from the reaction mixture by preparative gas
chromatography but tends t o explode on crystallization
(at -196 "C); it was characterized by its mass spectrum [m/e=
81 (FNSO), 48 (SO), 46 (NS), 33 (NF), and 32 (S)]. I R spectrum: 1246 vs (vS=O), 1007 vs (vN=S), 834 s (vN-F),
606 s (SNSO). 394 s (y), and 228 s cm-1 (SFNS).
The IgF-NMR spectrum [51 a t room temperature shows a
triplet ( N F coupling), 6 = -123.3 ppm, referred to CFC13 as
internal standard, with JFN = 112 Hz.
Received: February 5 , 1969: revised: March 28, 1969 [Z 965b El
German version: Angew. Chem. 81, 331 (1969)
[ * ] Dr. W. Verbeek and Prof. Dr. W. Sundermeyer
Anorganisch-chemisches Institut der Universitat
69 Heidelberg, Tiergartenstr. 2 (Germany)
[l] 0.J. Scherer and P. Hornig, Angew. Chem. 78, 776 (1966);
Angew. Chem. internat. Edit. 5 , 729 (1966).
[21 G. Kresze, A . Maschke, R . Albrecht, K . Bederke, H. P.
Patzschke, H . Smalla, and A . Trede, Angew. Chem. 74, 135
(1962); Angew. Chem. internat. Edit. I , 89 (1962).
(31 We thank Dr. Seidf, Badische Anilin- und Soda-Fabrik, and
Dr. Krauss, Universitat Heidelberg, for measurement and discussion of the mass spectra.
[41 W. Verbeek and W. Sundermeyer, Angew. Chem. 81, 330
(1969); Angew. Chem. internat. Edit. 8, 376 (1969).
151 We thank Professor Dr. Fluck, Universitat Stuttgart, and Dr.
Lafscha, Universitat Heidelberg, for measurements and discussions.
Synthesis of Testosterones from Estrogens111
By H. D . Berndt and R. Wiechert[*I
The development of industrially applicable syntheses of
estrones [*I aroused interest in effective methods for the introduction of a n angular 10P-methyl group into 19-nor steroids.
Angew. Chem. internat. Edit. / Vol. 8 (1969) 1 NO. 5
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