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Bis-(1 2 3 4-thiatriazol-5-yl)thio Compounds with High-Explosive Properties.

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Bis-(1,2,3,4-thiatriazol-5-yl)thio Compounds with
High-Explosive Properties
By Dr. K . Pilgram and Prof. Dr. F. Korte
Shell Grundlagenforschungs-Gesellschaft m.b.H.,
SchloB Birlinghoven/Siegkreis (Germany)
Sodium I ,2,3,4-thiatriazol-5-thiolate (2), which can be
prepared readily from sodium azide and carbon disulfide [I],
reacts with z,o-dihalogenoalkanes ( I ) in acetone/water
(3:l v/v) within several hours at about 10°C to form
~,c+bis-[(1,2,3,4-thiatriazol-5-yl)thioJalkanes(3).
(3/, R = -(CH2)"-, n = 1 - 4
pound. The diastereoisomer (-)-[Si(PN0)3]HBT is less
soluble than the other and precipitates preferentially from
aqueous solution. A saturated aqueous solution of this
precipitate gave a negative rotation which decreased
with time (became more positive) as the asymmetric
silicon complex decomposed, and finally reached a constant
negative value due to the monohydrogen (-)-dibenzoyl-(L)tartrate anion. The filtrate from the precipitation reaction
gave a high positive rotation, which decayed according to
first order kinetics at pH 1.8--1.9 and 2S°C with a half-life
of about 70 minutes.
2-Hydroxypyridine N-oxide thus resembles acetylacetone in
forming a cationic complex with silicon, in which the central
silicon atom is octahedrally surrounded by six oxygen atoms
[2]. However, whereas HPNO forms a complex with silicic
acid even in aqueous solution, acetylacetone does not react
~inderthe same conditions.
HPNO also forms complexes analogous to those already
known for acetylacetone with other elements, e.g. Al(PNO),,
Fe(PNO)3 or [Sn(F"0)3]2SiiC!6 (cf. CJ.!S~ [3,4]).
Received: Febiiiary 17111, 1965
[Z 9201741 IFJ
German version: Angew. Chem. 77. 341 (1965)
[ I ] A. Weiss and 11. R. H a r v e y , Angew. Cheni. 76, 81s (1961);
Angew. Chcn. internat. Edit. 3 , 698 (1964).
[ 2 ] S. !C. Dhar, V . Doroil, and S . Kirschtier, J. Amer. chem. SOC.
R1.p. [ C ] [a1
82 rbj, 99
92
81, 6372 (1959).
[3] G. T. Newholdand F. S. Spriiig, J . chern. SOC. (London) 1948,
1864; E. Shax. J . Amer. chem. SOC.7 / , 67 (1349).
[ 3 ] A. Albert, C. W. Rers, and A . J . H . Toin/itiso/r, Recueil Trdv.
chim. Pays-Bas 75, 819 (1956).
85
75
l a ] With decomposition
[ b ] Nitrogen is evolved without melting of ihc wniple
I ,4-Bisiodomethylcyclohexane, 111.p. 76--77 " C , reacts analogously with (2) to form ( 4 ) [Z], m.p. 92°C (decomp.), i n
39.9
yield. Dichloromaleimide reacts with (2) at only -15
to -10°C in aqueous acetone to afford 58 "/, ( 5 ) , m.p. 9 2 ' C
(decomp.). The structures of (3), ( 4 ) , and ( 5 ) were confirmed
by elemental analysis, infrared spectroscopy, and thermoanalysis. Thermolysis of ( 3 ) between 50 and 7 5 ' T in inert
solvents affords nitrogen, sulfur, and z,o)-bisthiocyanatoalkanes (7), which absorb in the infrared at 4.6 p. The
formation of isothiocyanates was not observed.
Reactions of N-Sulfinylsulfonamideswith
Organophosphorus Compounds
x
N - C - - S -(CH2)n-S-C-N
(7)
Compounds (3) and ( 5 ) are stable a t room temperature, but
decompose when struck with a loud clear report. During
melting-point determinations in a Biichi apparatus, the temperature of decomposition also was often indicated by a
clear report.
By fil. lic. A. Senning
Kemisk Institut, Aarhus Universitet, Aarhus (Denmark)
A new type of reaction was discovered when N-sulfinyl compounds were treated with triphenylphosphine ( I ) . Reaction
of N-sulfinylmethanesulfonamideand ( I ) in a molar ratio
of 1 : 1 in refluxing benzene affords 95
methanesulfonyliminotriphenylphosphorane (2), R = CH3 ; analogously, N sulfinyl-p-toluenesulfonamideand ( I ) give rise to 50 of the
corresponding iminophosphorane (2) with R = p-CH3CsH4.
x,
R e c e i v d : February 16th, 1965 [ Z 9 1 9 / 7 4 4 IE]
German version: Angew. Cheni. 77, 348 (1965)
~.~
[ I ] L. F. Audrieth, Chem. Reviews IS, 169 (1934), where further
references are given.
[ 2 ] The stereochemistry of this compound has not yct been
investigated.
By Dr. D. R. Harvey and Prof. Dr. Armin Weiss
The reaction can be interpreted in terms of attack by the
coordinately unsaturated phosphorus atom (with expansion
of its valence shell) at the semipolar nitrogen-sulfur bond.
With triphenylphosphine sulfide, a quasi-Wittig reaction
takes place [I 1. Here, too, p-toluenesulfonyliminotriphenylphosphorane (2), R = P - C H ~ C ~ HisS ,formed in about 50
yield from N-sulfinyl-p-toluenesulfonamide.
Anorganiscll-Chemisches Institut
der Universitat Heidelberg (Germany)
RS02-N-S
Resolution of the Silicon Complex with
2-HydroxypyridineN-Oxide into Its Enantiomers
Evidence for Octahedrally Coordinated Silicon
--
Partial resolution of the complex of silicon with 2-hydroxypyridine N-oxide ( H P N O ) [ I ] into its optical enantiomers
(-)-dibcnzoyl-r-tartrate
by treatment with disodium
(NazBT) confirms that silicon is 6-coordinated in this comAtrgew. Chain. intcriiot. Edit.
/
V d . 4 (1965)
No. I
x
0
(CRI-Isj,P S - ( 2 )
-
S S 0
Received: February 22nd. 1965 [Z 9221746 IE]
German version: Angew. Cheni. 77, 379 (1965)
[ I ] A . Setriiitrg, Acta chern. scarid. 18, I958 ( 1964)
357
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properties, compounds, explosives, high, thiol, bis, thiatriazol
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