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Heterocyclic Azidinium Salts in Preparative Chemistry.

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New azides of the type RHgN3, with R = cyclopentadienyl,
cyclopropyl, and cyclopentyl, can be synthesized in this way,
as can also the compound (CH&BiN3. As(CH3)3, on the
other hand, like the tetraalkyl compounds of the elements
of Group IV A, is inert towards CJN3; (CH&AsN3, however,
can be obtained by reaction (2).
(CH&AsI
+ AgN3
+
+ (CH~)~AS-N~
AgI
(2)
All the above mentioned organometal azides are monomeric
and nonexplosive. I R and laser-Raman spectra afford information concerning their structures; thus, it is found that
the N3 group is covalently bound and distorted at the a-N
atom. Cyclopropylmercury azide occurs as a mixture of the
cis- and trans isomers, whereas the cyclopropyl ring in liquid
dicyclopropylmercury rotates freely (pseudosymmetry Dmh).
In many cases, organometal thiocyanates are accessible from
alkyl- or arylmetal compounds and dithiocyanogen in
accordance with eq. (3).
RnM + (SCN)l
+ Rn-lM-SCN
+ RSCN
(3)
to form a layer structure; in the latter case the four Te-0
bond lengths vary from 1.88 to 2.19 A.
That the following coordination occurs rather often in the
oxygen compounds of tetravalent tellurium appears to be important: a fourth oxygen atom coordinates to a T e 0 3 pyramid
having three short Te-0 bonds to form a bond whose length
i s about 20% longer than those in the pyramid. This results
in a coordination very close to that which has been described
for the TeO4 group. These “long” Te-0 bonds, which are
obviously much weaker than the short ones, vary greatly in
length and it is difficult to give an upper limit. Examples are
(Ca,Mn,Zn)[TezO5], Fe(OH)[TezOs], and cliffordite.
Compounds of oxygen and hexavalent tellurium exhibit
predominantly octahedral coordination and can undergo
polymerization to double octahedra (in K4[Te206(OH4)] .
7.3 H20) or to infinite chains (as in KITe030HI). A coupling
via corners to form infinite chains has been detected in
K ITe02(0H)31.
Lecture at Gottingen, October 30, 1969
[VB 217 1E1
German version: Angew. Chem. 82, 49 (1970)
[*I Prof. Dr. J. Zemann
They differ considerably in their physical and chemical properties from the corresponding well-known isothiocyanates. We have prepared the previously unknown compounds
(C6H5)2 BSCN (monomer), (CH&dSCN),, ( ‘ C Z H ~ C ~ S C N ) ~ ,
(CZH~OC~SCN),,and (CH3)zBiSCN (degree of association
unknown) by the method shown in reaction (3). In contrast
to the substitution reaction (3), addition of (SCN)z in
accordance with eq. (4) leads exclusively to organometal isothiocyanates.
R3M
+ (SCN)Z
+ R~M(NCS)Z
(4)
As(CH3)3, As(C6&)3, Sb(CH&, and Sb(C&)3 react with
(SCN)2 in this manner (4). In a few cases organometal azides
can be converted into thiocyanates as shown in eq. (5).
2 CH3Hg-N3
+ (SCN)2
+ 2 CH3Hg-SCN
+ 3 Nz
Institut fur Mineralogie and Kristallographie
der Universitat
A-1010 Wien, Dr.-Karl-Lueger-Ring 1 (Austria)
Heterocyclic Azidinium Salts in Preparative
Chemistry
By H . Balli[*I
Heterocyclic azidinium salts (4) [I] have previously been
prepared via the routes (a), (b), and (c)[l,Zl. The N-heteroaromatic compounds pyridine, thiazole, 1,2,4-triazole,
(5)
Lecture at Aachen, October 28, 1969
[VB 216 IEI
German version: Angew. Chem. 82, 48 (1970)
[*I Prof. Dr. K. Dehnicke
Institut fur Anorganische Chemie der Universitat
355 Marburg, Gutenbergstrasse 18 (Germany)
111 Including work carried out in collaborationwith 7‘.Wizemann,
D. Seybold, H . Miiller, J . Miiller, F. Weller, A . Shihada, and
R . Schmitt.
Stereo- and Polymerization Chemistry of Tellurites
and Tellurates in the Solid State
By J. Zemann [*I
The following common features for the coordination and
polymerization chemistry of tellurium can be inferred from
the previously reported crystal structures of tellurites and
tellurates:
With oxygen, tetravalent tellurium forms either a trigonal
OTeO ~ 9 O 5(e.g,
pyramid with dTe-0 N 1.95 8, and
CuTeO3 . 2 HzO and ZnTe03) or a trigonal bipyramid in
which an equatorial corner is unoccupied; the deformation
can be explained, therefore, as being due to occupation of
this “free” corner by a lone pair of eIectrons having large
spatial demands (e.g. tetragonal Te02). Coupling of T e 0 3
pyramids, to TezO5 units in (Ca,Mn,Zn)[Te~O51 and
Fe(OH)[Tez05], to Te6OI2 rings in the mineral cliffordite
(whose chemical composition corresponds approximately to
Uz04[Te60121), and to a two-dimensional infinite layer in
Te203[S04], is well known. In Znz[Te3081 one TeO4 group
is bonded to two TeO3 groups via oxygen atoms. In tetrabonds
gonal TeOz, Te04 groups are coupled via Te-0-Te
to form a three-dimensional framework and in rhombic TeOz
<
80
R
.1
secondary reactions
Angew. Chem. internat. Edit.
R
1
possible secondary
reactions
1 Vol. 9 (1970) / NO. I
quinoline, isoquinoline, benzimidazole, benzothiazole, benzoxazole, benzoselenazole, and their substitution products
could be used in the syntheses.
The salts ( 4 ) react as electrophiles having ambidentate
reactivity in the routes (d) or (e).
Hard bases, X, react according to route (d) with substitution
of the azido group o n the hard carbonium ion of ( 4 b ) .
1. Hydrolysis of azidinium salts.
+ HOQ
(-&-N3
I
R
BF,@
+ H C R’
~O
Q=N-N=NB
\.k2
A
R
R1
-q
R
C=O + HN3
+
5. Addition of heteroaromatic amines such as (15) with
formation of condensed triazoles (16).
BF,@
(51.
I
R
~.
4
N
I
R
r
1
L
-I
+
BF,Q
H3C
(15)
(44
cC-N=CQ
NO
i
I
R BF40 R
(6)
(5)
(4b)
+ s=g=C:,,
iY
R
BF,@
I
(13)
O C = N H
2. Synthesis of azamonomethinecyanines (6) with the bases Q=N-N=N@
I
q = N - N = N H\
- c ,/R’
R2
BF,Q
(4c)
f4b)
R
-
Soft bases., X.. react according
- to route (e)
. , with addition at
the terminal nitrogen atom of the azido group of ( 4 c ) ,
secondary reactions often occurring at the same time.
1. Addition of azide ions.
Cc=..
Y
+
R
(16)
Lecture at Freiburg, November 13, 1969 [VB 218 IEI
German version: Angew. Chem. 82, 86 (1970)
[*I Prof. Dr. H. Balli
2. Addition of heterocyclic ylides such as (8) o r ( 9 ) ; synthesis of triazatrimethinecyanines (10)[31.
Institut fur Farbenchemie der Universitat
CH-4056 Basel, S t . Johannsvorstadt 10/12 (Switzerland)
[I] H. Balli and F. Kersting, Liebigs Ann. Chem. 647, 1 (1961).
[ 2 ] G. Henseke and G Hanisch, Liebigs Ann. Chem. 643, 184
(1961); H. Quast, Dissertation, Universitat Marburg 1963.
[3] H. Balli and F. Kersting, Liebigs Ann. Chem. 663, 96 (1963).
141 S. Hiinig, H. Balli, and H . Quast, Angew. Chem. 74, 28
(1962); Angew. Chem. internat. Edit. I, 47 (1962).
[5] H. Balii and V . Miiller, Angew. Chem. 76, 573 (1964); Angew. Chem. internat. Edit. 3, 644 (1964); H . Bolli and R . Gipp,
Liebigs Ann. Chem. 699, 133 (1966).
Dissolution of Bituminous Coals at Temperatures
below 200°C
By G . Kolling[*I
3. Addition of heterocyclic hydrazines (11) with subsequent
oxidation to pentaazapentamethinecyanines (12) 141.
Q=N-.;N
I
R
-N-N=
I
H
N
I
NO
R
R
I
BF,Q
I
R
(12)
4. Addition of anions of reactive methylene compounds (13)
o r hydroxyaromatic compounds involving diazo group or
azo group transfer (synthesis of diazo compounds and azo
dyes) [51. ExampIes for (14) are diazomeldrum acid (yield
46 %), 4-diazo-3-methyl-l-phenyl-5-pyrazolone
(96 %), 2,4,6tris(diazo)-l,3,5-~yclohexanetrione(95 %).
Angew. Chem. internat. Edit.
1 Vol. 9
(1970)
No. I
Bituminous coals are scarcely soluble in most solvents at
temperatures below 200 O C ; however, in “specific” solvents
such as phenols, pyridine bases, and a few arnines, their
solubility can be as high as 40 %.
After alkylation with alkyl chlorides and AICl3 at 50 O C , o r
with olefins, HF, and BF3 at 80°C the solubility increases
still further. Even more efficient is acylation with higher fatty
acids and AlC13 at 50 O C , a treatment which makes mediumrank coals soluble but for their inert constituents.
The carbon matter pretreated in this way can easily be
further investigated. The average molecular weight is found
to be about 3000 after deduction of the alkyl groups introduced. Similar values have been reported by van Krevelen
and his co-workers as a result of a n extrapolation of the
average molecular weights which they had found by studies
o n partial extracts.
Lecture at Mulheim/Ruhr, November 27, 1969
[VB 219 IE]
German version: Angew. Chem. 82, 87 (1970)
I*] Prof. Dr. G. Kolling
Bergbau-Forschung G.m.b.H.
43 Essen-Kray, Frillendorfer Strasse 351 (Germany)
[l] H . N . M . Dormans and D.W. van Krevelen, Fuel 39,213 (1960).
81
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