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Dimeric N-Chloroiminosulfur Tetrafluoride a Cyclodiaza-6-thiane with Hexacoordinated Sulfur.

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[ I ] a) E. JZgers, W.Steglich. Liebigs Ann. Chem., in press. b) W.Steglich. W.
Furtner. A. Prox. Z. Naturforsch. 8 2 5 . 557 (1970).
121 G . Pattenden. Fortschr. Chem. Org. Naturst. 35. 133 (1978).
[3] (2a): M.p.=28O0C (decomp.); UV (MeOH): L,,,=272 (Ig&=4.10), 290
(4.04), 360 (4.04). 450 nm (4.12); IR (KBr): 1785, 1745, 1650, 1629 c m - ' ;
'H-NMR ([D6]DMSO): 6 = 5.85, 6.65, 7.25 (each s, 3 H), 10.25 (br., OH);
MS: m / r 262 (75%. M + , Ci2H6O7),192 (100, CUH,05); (3): L , = 2 6 9
(Igs=3.99), 288 (4.02). 361 (4.15). 450 (3.73).
[4] Cf. H. Endres. 2. Anal. Chem. 181,331 (1961).
[5] T. Posternak. R. G. Huguenin. W. Alcalay. Helv. Chim. Acta 39. 1564
(1956). Rearrangement of the dibenzoquinones was performed under
conditions of acid catalysis.
[6] Cf. e . g . H. W. Moore. R . J. Wickholm in S. Patai: The Chemistry of Quinonoid Compounds, Part 1, Wiley, London 1974.
[7] C . G. Swain. J. F. Brown. Jr., J. Am. Chem. SOC. 74, 2538 (1952); H . C.
Beyerman. W . M . van den Brink. Proc. Chem. SOC.1963.266; H . T. Openshow. N. Whittaker, J. Chem. SOC.C 1969, 89.
[8] P. C. Beaumont. R . L. Edwards. J. Chem. SOC. C 1969. 2398.
191 Reaction time and yield apply to synthetic (16) with a sterically nonuniform side chain. Interestingly, natural boviquinone-4 with a n all-(Q-geranylgeranyl side chain is dimerized much more slowly by polyamide.
Dimeric N-Chloroiminosulfur Tetrafluoride,
a Cyclodiaza-k6-thiane with Hexacoordinated
Sulfur[**]
By Alfred Waterfeld and Riidiger Mews[']
Dedicated to Professor Oskar Glemser on the occasion
of his 70th birthday
The previously known cyclodiaza-h6-thianes"1 contain
exclusively tetracoordinated sulfur atoms. However, by
reacting NSF, and CIF we were able to isolate the novel
cyclodiaza-h6-thiane (I) with hexacoordinated sulfur
atoms, in addition to the previously described product of
this reaction, N,N-dichloroaminosulfur pentafluoride
(2)[2'.
K S F 3 + C1E'
CIF
{C1N=SF4)
I
Cl,N-SF,
12)
c1
C1
Whether the four-membered heterocycle is formed by
direct dimerization of the N-chloroaminosulfur tetrafluoride or via ionic intermediates is still at present not clear.
N-alkylaminosulfur tetrafluorides, such as e. g . CH,NSF,,
do not dirnerize"].
The colorless compound (I) melts at 4"C, and its vapor
pressure at 20 " C is 7 torr. Whereas (I) decomposes in glass
vessels at room temperature, it appears to be stable in passivated metal flasks.
(I) was characterized by elemental analysis and spectroscopic methods. Apart from the molecular ion at m / z 314
(36%), the EI mass spectrum (70 eV, cold source) shows
peaks from the fragments (M-CIF)* 260 (20), CINSF:
157 (85), CINSF: 138 /34), SF: 127 (40), NSF: 103 (12),
SF: 89 (100). In the FI mass spectrum, a peak for
(M-CIF)+ was found in addition to that of M + . The IR
and Raman spectra exhibit no coincidences[41,and hence
1'1 Prof. Dr. R. Mews, Dr. A. Waterfeld
p
'
]
Anorganisch-chemisches lnstitut der Universitat
Tammannstrasse 4, D-3400 GBttingen (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft.
Angew. Chem. Int Ed. Engl. 20 (1981) No. 12
the molecule is probably centrosymmetric with a transorientation of the two chlorine atoms. The NMR data can
be interpreted using an A2B2 system as a simplification:
6(F,)=76.1, 6(FB)=49.4, J(AB)= 140.8 Hz.
Procedure
CIF (22.9 g, 0.42 mol) and NSF, (21.8 g, 0.212 mol) are
condensed into a Monel cylinder at - 196°C. The reaction
mixture is slowly warmed up to - 78 " C ,and then to room
temperature (Care! Warming too rapidly leads to violent
explosions). Fractional condensation ( - 50, - 95,
- 196 "C) using an oil-pump vacuum yields (I) (1.2 g, 3.6%
yield) in the first cold trap and (2) (5.3 g, 1 1.8%)'21, together
with small amounts of impurities['], in the second.
Received: June 2, 1980 [Z 910 IE]
German version: Angew. Chem. 93, 1075 (1981)
CAS Registry numbers:
(1): 79593-52-5, (2): 22650-46-0, CIF: 7790-89-8, NSF,: 15930-75-3.
[ I ] K . D. Schmidt. R. Mews. 0. Glemser, Angew. Chem. 88, 646 (1976); Angew. Chem. Int. Ed. Engl. I S . 614 (1976); F. M. Tesky. R. Mews, B. Krebs.
ibid. 91. 231 (1979); 18. 235 (1979); H. W. Roesky. M.Aramaki. L. Schonfelder. Z . Naturforsch. 8 3 3 , I072 (1978).
121 A . F. Cli/ford, G. R. Zeilenga. Inorg. Chem. 8, 979 (1969).
[31 R. Mews. Angew. Chem. 90. 561 (1978); Angew. Chem. Int. Ed. Engl. 17.
539 (1978).
[4] Spectra were recorded in various phases [IR (gas): 970 (s), 930 (vw), 889
(vs), 854 (vw). 81 1 (s), 777 (m),617 (w). 578 (sh), 568 (m);Raman (liquid):
665 (m), 61 1 (w), 536 (w). 463 (w). 369 (vw), 350 ( s ) , 293 (w), 207 (w). 182
(w)l.
[5j SF,NSF, and (SF,),NH are more readily accessible by other routes (A.
Waterfed, R. Mews. unpublished results).
Cyanation of Tertiary Alkyl Chlorides:
A Novel Method for the Geminal Dialkylation of
Ketones[**I
By Manfred T. Reetz and Ioannis Chatziiosifidisl"
The ambidentate cyanide ions"' react with SN2-active
primary and secondary alkyl halides at the C atom to form
nitrilesf4] in accord with the Kornblum ruleL2]and the
HSAB principle[31.In the case of tertiary alkyl halides only
elimination of HX is observed"]. Under SN1 conditions, Nalkylation occurs via the Ritter reaction[61.In order to solve
the classic problem of the cyanation of tertiary alkyl halides [(1)+(3)], we reacted these with the readily accessible
trimethylsilyl cyanide[71(2) in the presence of catalytic
amounts of SnCI,.
R3C-C1 + (CH3)3SiCN
(1)
(2)
SKI,
R3C-CN
13)
+ (CH3)3SiC1
14)
As shown in Table 1, the desired tertiary nitriles are
readily obtained. Noteworthy is the CC coupling reaction of
exo-2-chloro-2-methylnorbornane(lj). which leads to the
exo-nitrile (3j) with 100% stereoselectivity. Furthermore,
the strict chemoselectivity in the reaction of (5) is notable:
the tertiary nitrile (6) is formed exclusively.
The present CC coupling reaction is of synthetic interest, because the products can be variously modified e. g . by
Grignard addition or reduction, leading to the otherwise
[*I Prof. Dr. M. T. Reetz, Dipl.-Chem. I. Chatziiosifidis
[**I
Fachbereich Chemie der Universitat
Hans-Meerwein-Strasse, D-3550Marburg (Germany)
This work was supported by the Fonds der Chemischen Industrie.
0 Verlag Chemie GmbH. 6940 Weinheim. 1981
0570-0833/81/1212-1017 S 02.50/0
1017
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sulfur, hexacoordinated, dimeric, cyclodiaza, chloroiminosulfur, thiane, tetrafluorides
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