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Dimethyldiazidosilane.

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Triorganosilyldialkylaminoboranesof Type I are accessible
by one of the following routes:
Tri-irondodecacarbonyl (5 g) in liquid ammonia (100 ml) at
-78 "C and under oxygen-free nitrogen is converted to
NazFe(C0)4 by the addition of metallic sodium (1.37 g). The
ammonia is then evaporated in a stream of nitrogen and the
R3SiLi + CIBIN(CHs)zlz (a)\ -LiCI
+ R ~ S ~ - B [ N ( C H ~ ) Z ] ~ cooling bath (methanol/solid C02) removed. Compound I
(b)=
/CKCI
(5 g) in dry, peroxide-free ether (250 ml) is now added dropRnSiCl+ 2 K + CIB[N(CH3)z12 wise and the mixture reflwed, with stirring, for 24 hours.
The filtered solution is evaporated to dryness in vacuo, the
By route (a) Ph3Si-B[N(CH3)2]C4H9 can also be prepared,
residue taken up in benzene and chromatographed on a
but not however Ph3Si-B(C,,H9)2; this underlines the imcolumn (1.5 cm diameter, 50 cm long) of silica (Merck,
portances of the x-bonds for the stability of the Si-B bond.
0.02-0.05 mm diameter). A green, a red and a yellow-orange
The hydrolysis of Ph3Si-B[N(CH3)2]2 proceeds quantitatively
zone are eluted. The green compound is [Fe(CO)&; the
according to
yellow-orange the ferrole derivative (11), which is further
purified by vacuum sublimation (0.1 Torr) a t 50 "C. Yield:
Ph3Si-B[N(CH1)212 f 3 Hz0 + PhlSiH + B(OH)l + 2 HN(CH3)z.
80 mg (II), m.p. 57 "C.
Methanolic potassium hydroxide reacts with all silylboranes
with the evolution of hydrogen, i.e. with hydrolysis of the
initially formed Si-H bond. Silylboranes reduce silver salts
to silver.
HCI in ether attacks I only at the B-N bond, not at the Si-B
bond. Reaction in the molar proportions of 2 : l leads to
triorganosilyldimethylaminochloroboranesof Type I1 (X=Cl :
,N(CHi)z
+ 2HCI
RlSi-B
k(CH3h
,N(CH&
+ (CH3)zNH'HCl
.,Si-B
'Cl
The physical constants of the compounds which have been
characterised by analysis and infrared spectroscopy are:
Ph,Si-B[N(CH,)z]z
Ph3Si- B [N(CHp)z]CL
The trimethylsilyl compounds are spontaneously inflammable
in air.
Received, August 15th, 1962 [Z 331/160 IE]
[l] XIXth Communication on "Contributions to the Chemistry
of Boron".
[Z] A similar system exists in B-tris(triphenylsily1)-N-trimethylborazole; D. Seyferzh and H. P. Kogkr, J. inorg. nucl. Chem. 15,
99 (1960).
[3] Oil bath temperature. HV = high vacuum.
By Doz. Dr. Ernst Bayer, Dr. H. A. Brune,
and DipLChem. K. L. Hock
111 F. G. A. Stone, H. D. Kaesz, and R. B. King, J. Amer. chem.
SOC.82, 4749 (1960).
[21 M. L. H. Green, L. Pratt, and G. Wilkinson, J. chem. SOC.
(London) 1960, 989.
Derivatives of ferrole, i.e. of the 5-membered heterocycle
with iron as the hetero-atom, can be synthesised from sodium
iron carbonyl and 1,4-dichlorobutadiene derivatives. In .this
way dichlormuconic acid dimethyl ester (I) yields an orangeyellow tricarbonyl compound (11) of ferrole dicarboxylic
acid dimethyl ester.
NaZFe(C0)4
1
c1
.1
HC-
(1)
Dimethyldiazidosilane
By Dr. W. Sundermeyer
Anorganisch-wissenschaftlichesLaboratorium
der Farbenfabriken Bayer AG., Leverkusen (Germany)
The previously reported method for the preparation of
pseudo-halogen Fompounds of silicon from alkali pseudohalogenides and chlorosilanes in fused salts as solvents [l]
could also be used for the preparation of azides. Trimethylchlorosilane reacts with sodium azide, dissolved for example
in an anhydrous ZnC12-KCI melt, at 230-250°C to give a
good yield of trimethylazidosilane (I) [2] (b.p. 96 "C corr.).
(CH3)zSiCIz
Institut fur Organische Chemie
der Technischen Hochschule Karlsruhe (Germany)
yCH-"Y
'C-COOCH,
[Z 332/161 IEI
Similarly, an approximately 60 % yield of dimethyldiazidosilane (11) [3,4] was obtained.
Synthesis of Ferrole Derivatives
I
Received, August 15th, 1962
150--160/HV [3]
150--160/HV [3]
155-165/HV [3]
65/9 mm Hg
42/9 mm Hg
(CH3hSi- B"(CHdz1z
(CH3)3Si--B [N(CH3)21CI
HlCOOC-C
With its unsubstituted 8-C-atoms (11) is suitable for electron
distribution investigation, and is especially suited to answer
the problem of whether or not there is present in ferrole a
cyclic conjugation similar to that of the quasi-aromatic
heterocycles pyrrole and thiophen. In its NMR-spectrum
(Varian A 60) the proton bands of the p-CH-groups show a
chemical shift of 6 = 6.54 ppm. This value is in the region of
those found for analogous furan-, thiophen- and pyrrole
derivatives. In addition the iron complex prepared from
thiophen by Stone et al. [l] and claimed as a x-complex of
ferrole is found to have a value for 6 of 6.48 ppm [2].
H3COOC-8
CH
!-COOCH,
\F/
+ 2 NaN3
--f
(CH&Si(N&
I1
+ 2 NaCl
Whereas with phenylazidosilanes - analagous to the phenylsilylaminesand phenylsilanols - stability due to contributions
from mesomerism and the strong double bond character of
the Si-N bond would be expected, the existence of I1 is
surprising. The compound boils, without decomposition, at
144.3 OC (corr.) and is, like I and like triorganoazidosilanes
containing phenyl groups [5,6], remarkably stable thermally.
I1 is not sensitive to percussion, but in contrast to I burns
with deflagration.when ignited on an open spoon. Atmospheric moisture quickly hydrolyses the compound to dimethylpolysiloxanesand hydrazoic acid. Its infrared spectrum
resembles that of dimethyldichlorosilane and in addition
shows characteristic bands at 3436 (w), 2619 (w), 2146 (vs),
1322 (vs), 1157 (w), 1073 (w), and 1020 (w) cm-1 [*I.
I1 is also obtained in almost quantitative yield by the reaction
of I with dimethyldichlorsilane.
C'PC
(11)
552
2 (CH,),SiN,
AlCl
+ (CHs)zSiC12 -A
Angew. Chem. internat. Edit.
11
+ 2 (CH&SiCl
Vd. I (I962) I No. I 0
The reactants are heated with aluminium chloride under
reflux, and the trimethylchlorosilane formed is continuously
removed.
fZ333/162 IE]
Received, August 20th, 1962
[l] W. Sundermeyer, 2. anorg. allg. Chern. 313, 290 (1962).
[2] L. Birkofer, A. Ritter, and P. Richter, Angew. Chem. internat. Edit. 1 , 267 (1962); cf. [5].
[3] Cf. E. Wiberg and H . Michaud, 2. Naturforsch.9b, 500 (1954).
[4) During publication N. Wiberg, F. Ruschig, and R. Sustmann
reported the successful preparation of diphenyldiazidosilane:
Angew. Chem. internat. Edit. I, 551 (1962).
[ 5 ] R. West and J . S. Thayer, J. Amer. chem. SOC.84, 1763 (1962).
161 N . Wiberg and F. Raschig, Angew. Chem. internat. Edit. I,
335 (1962).
[ *] w = weak, vs = very strong.
N-Sulphonyliminodithiocarbonic esters and
N-Sulphonyldithiourethanes
By Doz. Dr. R. Gompper and Dipl.-Chem. W.. Hagele
Institut fur Organische Chemie und Organisch-chemische
Technologie der Technischen Hochschule Stuttgart (Germany)
The reaction of sulphonamides with carbon disulphide has not
been described previously. It may proceed in the following
manner :
RS02NH-C
111
RSOzNHz
+ CS2 + 2 M O H +
1
Isoselenazole and 3-Methylisoselenazole
RX
2. HCI ,S-
By Prof. Dr. F. Wille, A. Ascherl, G. Kaupp, and L. Capeller
RSOzN=C\
I
11
5 2
s-
Institut fur Anorganische Chemie der Universiat Munchen
(Germany)
RX
/SR'
RSOzN=C
1v
MOH = base
[l] Prepared by Badische Anilin- & Soda-Fabrik, Ludwigshafen/Rhein (Germany).
/SR'
AS
1.
celluloses with basic substituents used hitherto. This may be
mainly attributed to the fact that a considerably higher nitrogen content (and hence capacity) can be achieved by impregnation of the cellulose rather than by substitution.
For example, a strip of Whatman No. 1 paper is soaked for
1-2 sec. in a 1-5 % solution of polyethyleneimine neutralised
with hydrochloric acid, air-dried, washed with distilled
water, and dried in a current of warm air.
The anion-exchanger paper thus obtained is excellently suited
for separating nucleotides and other phosphoric esters, for
example, AMP, ADP, and ATP can be separated in 12 min.
on polyethyleneimine-paper with 0.8 M sodium chloride
solution. This takes 15 to 20 hrs. on untreated paper (partition
chromatography), and on commercial ion-exchanger papers
(substituted celluloses) they cannot be separated at all with
neutral electrolytes.
Impregnated celluloses are also suitable for column and
thin-layer chromatography, separations being particularly
sharp in the latter case. A mixture of AMP, ADP, and
ATP can be completely resolved in 3-4min. on a polyethybneimine-cellulose layer with 0.8 M sodium chloride
solution.
The mild conditions of these separations seem particularly
noteworthy.
[Z 336/168 IEI
Received, August 30th, 1962
RS'
Suitable solvents include dimethylformamide, N-methylpyrrolidone, and dimethylsulphoxide, while conc. sodium or
potassium hydroxide may be used as base.
The salts I1 may be isolated or converted directly into I11 and
IV. Good yields can be obtained only if MOH and CSp are
added in portions to the solution of I (at first 1 equivalent of
MOH and 1 / p equivalent CSz, then 1/2 MOH and 114 CSp,
and so on). The alkylthio groups in 111 and IV undergo
nucleophilic substitution readily. As coreactants we have so
far used alcohols, ammonia, primary and secondary amines,
diamines, aminoalcohols, ethyleneimine, hydrazine, guanidine, and CH-acid compounds. Replacement of the second
alkylthio group in IV proceeds only under morevigorous conditions (e.g. with NH3 in phenol at l0OOC).
Oxidation of 111 gives N,N'-disulphonylisothiuram disulphides. Heating I11 in an inert solvent eliminates an alkylthiol; perhaps sulphonyl-mustard oils are also formed as
intermediates on heating in alcohol; these then react further
to form N-sulphonylthiocarbamic esters.
Received, August 30th, 1962
We recently reported that on treatment with ammonia 3thiocyano-acrolein is converted into isothiazole [I 1. An analogous cyclization occurs when 3-cyanoseleno-acrolein (I,
R=H) is treated with liquid ammonia. The product is the
hitherto unknown isoselenazole (11, R=H), a colorless liquid
with a pyridine-like odour (b.p. = 68"C/46mm.; n g =
1.603; Amax = 266 mp; E = 4680, in dioxane)
Ammonia and 3-cyanoselenobutenone (I, R=CH3) yield the
analogous 3-methylisoselenazole (11, R=CH3 ; b.p. = 51 to
51.5 OC/13 mrn; n 8 = 1.575; Amax = 268 mp; E = 3630, in
dioxane).
Cyanoseleno-acrolein (I, R = H; m.p. = 73-75 "C)is prepared by the addition of selenocyanic acid to propynal; 3cyanoseleno-butenone (I, R = CH3; m.p. = 50-53OC) is
obtained similarly from butynone.
Received, September 7th. 1962
[Z 337/167 IE]
[Z 335/166 IE]
[l] F. Wiiie, L. CupeZZer, and A . Steiner, Angew. Chem. Internat.
Edit. I, 335 (1962).
A Simple Method for Preparing Cellulose
Anion-exchanger Powders and Papers
New Heterocyclic Ring Systems
By Dr. K. Randerath
By Dr. K. Stach and Dr. F. Bickelhaupt
Institut fur Organische Chemie der Technischen Hochschule,
Darmstadt (Germany)
We have found that cellulose powder and chromatography
paper can be impregnated with polyethyleneimine [l] to produce anion-exchanger materials which give excellent resolution. These exchangers are markedly superior to
Augew. Chem. internat. Edit. 1 Voi. 1 11962)
NO.10
C. F. Boehringer & Siihne G.m.b.H.,
Mannheim-Waldhof (Germany)
7,12-Dihydro-6H-dibenzo[b,e]thiocin-l2-one
(I) (m.p. 149
to 149.5'C, from diethyl ketone) is prepared smoothly in
70 % yield within 30 min by dehydration with polyphosphoric
553
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