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Dimerization of Azaallyl Diazaallyl and Oxaazaallyl Groups by Way of Copper-containing Intermediates.

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with a coupling constant of 16 Hz. The signal of the phenyl
protons ortho to the imino nitrogen atom is a multiplet
centered at 7 = 2.4 (relative intensity 2); and that of the
remaining aromatic protons is a multiplet centered at T 2.8
provide an
(relative intensity 8). Analogous substances
indication of the shift of signals of the CH2 protons on the
four-membered ring to lower field owing to the neighboring
nitrogen atom. Further, we also derive structure ( I ) from the
mass spectrum, specifically from the appearance of the ion
M-42 and of a fragment at m ' e 42 (H~C-N-CHZ). The
compound is found to have molecular weight 234. The UV
spectrum (in alcohol) includes a n absorption band at 244 nm
(E = 12200). In the I R spectrum (KBr) the C = N absorption
is at 6.2 pm and, remarkably, three absorption bands occur
between 9.98 p n and 10.16 pm.
It is tempting t o ascribe the formation of ( I ) to addition of
ketene phenyl imine t o phenylazirine. According t o Smolinsk y 111, phenylazirine and ketene phenylimine coexist after
pyrolysis of c/.-azidostyrene. The characteristic ketene imine
absorption[ll at 5 pm in the IR spectrum of our reaction
mixture after photolysis can be explained by presence of a
small amount of ketene phenyl imine. However, no trace of
( I ) is t o be found in the gas chromatogram after pyrolysis of
a-azidostyrene at 350 "C. N o r is any trace of ( I ) t o be found
in the mixture obtained o n addition of azidostyrene t o
boiling phenylazirine (ca. 180 "C). From o u r results, together
with the observation that ( I ) is also formed on photolysis
of phenylazirine, we conclude that it is formed by photochemical and not by thermal activation. This is thus the first
case of intermolecular photocycloaddition t o a carbonnitrogen double bond.
~
Received: November 23, 1967
[Z 662 LEI
German version: Angew. Chem. 80, 119 (196E')
[*I Dr. F. P. Woerner and Dr. H. Reimlinger
Union Carbide European Research Associates,
95, rue Gatti de Gamond, Bruxelles 18 (Belgium)
Dr. D. R . Arnold
Union Carbide Research Institute
P.O. Box 278, Tarrytown, New York 10592 (U.S.A.)
[l] G. Smolinsky, J. org. Chemistry 27, 3557 (1962).
[2] L. Horner, A. Christmann, and A . Gross, Chem. Ber. 96, 399
(1963); G . R . Harvey and K. W . Ratts, J. org. Chemistry 31, 3907
(1966); A. Hassner and F. W . Fowler, Tetrahedron Letters 1967,
1545.
[3] Mercury high-pressure lamp: Philips HPK 125 W.
141 The NMR spectra were measured with a Varian A-60
apparatus for CC14 solutions with tetramethylsilane as internal
standard.
[51 S. J . Bruis, J. oig. Chemistry 27, 3532 (1962).
161 W . F. Erman, J. Amer. chem. SOC.89, 3828 (1967); J . A .
Moore, F. J . Marascia, R. W . Medeiros, and R . L. Winehoit, J .
org. Chemistry 31, 34 (1966).
X-Ray Structure Analysis of
Tri- p-chlorobis[bis(tri-n-buty1phosphine)ruthenium Chloride]
+
2 333
12326
The X-ray analysis confirms the structure ( I ) and the Ru-CI
and Ru-P distances are shown in the figure. The coordination
round the ruthenium atoms is approximately octahedral (the
largest angular distortion is 12.4 ") and the environments of
these atoms are very similar. The Ru....Ru distance is
3.115 A, and is thus much longer than that found in the
metal (2.650 A) [41. The Ru--CI distances fall into two groups:
those trnns to other Ru--C1 bonds are considerably shorter
(2.340-2.376 A) than those (2.444-2.505 A) trans to Ru-P
bonds.
Received: November 7, 1967
IZ 664 I E I
German version: Angew. Chem. 80, 116 (1968)
[ * ] Dr. G. Chioccola, Dr. J. J. Daly, and Dr. J. K. Nicholson
Monsanto Research S.A.
Binzstr. 39
CH-8045 Zurich (Switzerland)
[I] J . K . Nicholson, Angew. Chem. 79,273 (1967); Angew. Chem.
internat. Edit. 6, 264 (1967).
[2] Determined by Drs. G. and S. OlivP, Zurich.
[3] U.W. Arndf and D. C. Phillips, Acta Crystallogr. 14, 807
(1961).
141 A . Hellaweit and W. Hiime-Rothery, Philos. Mag. 45, 797
(1954).
Dimerization of Azaallyl, Diazaallyl, and
Oxaazaallyl Groups by Way of
Copper-containing Intermediateslll
By Th. Kauffmann, G. Beissrrer, E . Koppelmann,
D. Kidilmann, A . Scliott, and H . Schrecken [*I
We are studying systematically the dimerization of organic
compounds by way of organo copper derivatives, a reaction
whose unusually wide applicability[z] is not yet fully recognized [3,41.
We observed dimerization of the 3-azaallyl group contained
in ( I ) when treating the compound 151 with 1 molar equivalent
of CuCl or CuBr2 in tetrahydrofuran/ether (1:l) under
nitrogen at 60 "C. The product (2) was formed in, respectively
72 and 78 % yield with separation of Cu or CuBr [GI.
By G. Chioccola, J . J . Daly, and J . K. Nicholson[*]
The synthesis of Ru~C15[P(n-C4H9)3]4 has been described
recently and the results of chemical investigations suggest 111
the structure ( I ) . The complex has a magnetic moment of
0.75 B.M. per ruthenium atornI21 corresponding to one
unpaired electron in the molecule.
The dark red crystals are monoclinic, space group P21,'c with
a = 13.866, b = 16.003, c = 30.545 A, p = 110.0". There are
four molecules in the unit cell and the observed density gives
a molecular weight of 1170.7 (theoretical 1188.8). The intensities were measured on a linear diffractometer [31 and the
structure was determined by Patterson and Fourier methods.
A least squares refinement of 3776 planes gives a current
R-factor of 0.083. The standard deviations of the Ru-CI and
Ru-P bond lengths are 0.0052 and 0.0054 8, respectively.
Angew. Chem. internat. Edit. 1 Vol. 7 (1968) 1 No. 2
When CuI in dimethoxyethane at 85'C is treated with 1
molar equivalent of the deep red compound (3) (formed by
the action of NaNH2 o n N-benzylidenebenzylamine), the
2-azaallyl group of ( 3 ) dimerizes analogously, yielding
compound (6) (58 % yield) specifically in the meso-form
(m.p. 163 "C; lit. [71, 164 "C).
The 1,2-diazaallyl group in (4) is also coupled by successive
action of 1 molar equivalent of CuCl and oxygen in dimethoxyethane at 60 "C, to give a known [*I product of m.p.
131
calculated o n the hexanamide taken (49 %, calculated on the
hexanamide consumed).
Received: November 25, 1967
[ Z 666 I€]
German version: Angew. Chem. 80, 117 (1968)
[*I Prof. Dr. Th. Kauffmann, G . Beissner, E. Koppelmann,
191 O C (yield 59 %), t o which structure (7) applies 191. Compound (S), which is obtained on oxidation of benzaldehyde
phenylhydrazone by iodine [lo], is not formed. The CU(I)
compound (5) arising as intermediate is thermally stable but
very sensitive to oxygen; it was isolated[l'l as a colorless
crystalline substance and converted into (7) by way of a
thermally labile green CU(II)compound.
Treating compounds (9) and (10) analogously with CuC12/Oz
led t o ca. 40 % yields of the corresponding azines. The compounds ( 1 1 ) , or the derived copper compounds, that are t o
be assumed as primary dimerization products apparently
undergo secondary changes.
r
7
L
(9), R
= H;
(lo), R = R'
R' = C,H,
= CH,
J
(11)
Here circumstances are thus similar to those in the case of
the dimerization of 1,3-diazaallyl groups of the type (12) by
means of CuC1/02, where substituted s-triazoles result from
secondary reactions[3,121. In this connection it is of interest
that successive action of one molar equivalent each of CuCl
and oxygen o n (13) in dimethoxyethane a t 65-75 "C affords
a product (14) in 75 % yield.
Dipl.-Chem. D. Kuhlmann, Dip].-Chem. A. Schott, and
H. Schrecken
Organisch-Chemisches Institut der Universitat
44 Munster, Hindenburgplatz 55 (Germany)
111 Part 3 of Activation of Organic Compounds by Introduction
of Transition-metal Atoms. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der chemischen
Industrie. - Reference [3] is considered to be Part 2 of this
Series; the less comprehensive series title given there is abandoned.
12) According to isolated observations [ H . Gilman and H. H.
Parker, J. Amer. chem. SOC.46, 2823 (1924); K. Issleib and H.-0.
Frohlich, Chem. Ber. 95, 375 (1962)l S-S and P-S linkages by
way of copper compounds are also possible.
[3] Th. Kauffnrann,J . Albrecht, D . Berger, and J . Legler, Angew.
Chem. 79,620(1967); Angew.Chem. internat. Edit. 6, 633 (1967).
[4] Th. Kaiiffhzann and W. Sahm, Angew. Chem. 79, 101 (1967);
Angew. Chem. internat. Edit. 6, 85 (1967).
[5] P. C . Campbell and P. C . Teague, J. Amer. chem. SOC.76,
1371 (1954).
[6] Solvents used in all the reactions were anhydrous; before
being further worked up, the batches were hydrolyzed by water.
Unless otherwise stated, yields (which in some cases may perhaps
be increased) refer to the amount of organic compound used. In formulation of the metal compounds n o attempt has been
made here to represent the bonding between metal and organic
group realistically.
171 H . Grossmann, Ber. dtsch. chem. Ges. 22, 2298 (1899); cf.
also W. Stiirmer and G. Messwarb, Arch. Pharmaz. 286, 221
(1953).
[8] P. Grammaricakis, C. R. hebd. Seances Acad. Sci. 223, 1139
(1946); 224, 1509 (1947).
[9] We were unable to obtain a usable NMR spectrum owing to
the insolubility and ease of decomposition of this substance. The
IR spectrum is in agreement with structure 17).
[lo] E. Bamberger and J . Grob, Ber. dtsch. chem. Ges. 34, 523
(1901).
1111 The molecular weight was not determined.
[12] J . Albrecht, Diplomarbeit, University of Munster (Germany) 1967.
Preparation of Tungsten Pentafluoride
By J. Schroder and F. J. Grewe[*l
The 1,3-oxaazaallyl group of (15) was not dimerized, to
yield (17), when (15) was treated with CuCl or CuC1/02 in
tetrahydrofuran. However, (17) was obtained when (15) was
treated with one molar equivalent of CuBr2 in tetrahydrofuran, though the yield was only 26 % calculated on the
benzamide taken (43 % calculated on the benzamide consumed). Addition of oxygen barely increased the yield. In
the analogous dimerization of the 1,3-oxaazaallyl groups of
(16) with CuBr2, product (18) was formed in 3 0 % yield
132
Not only tungsten hexafluoride but also lower tungsten
fluorides play an appreciable part in the chemical transport
reactions by means of which fluorine leads to homogenization
of tungsten filaments in incandescent lamps [I]. The fluorides
dissociate to tungsten and fluorine on tungsten filaments
whose temperatures exceed 2000 OC, and tungsten is transported from the colder to the hotter zones of the glowing
body until the temperature of the hot filament is completely
homogeneous. At lower temperatures, lower fluorides of
tungsten are formed and these disproportionate in the gas
space or on the walls of the vessel into tungsten metal and its
hexafluoride. However, if the wall of the vessel is cooled, the
lower fluorides can be trapped out of the gas space and can
be thus isolated.
For the synthesis of tungsten pentafluoride the carefuliy
baked out quartz apparatus (Fig.) was filled with 500 torr of
WF6 and plunged into a cooling bath at -50 to -60 'C. The
WF6 condensed in the quartz ampoule and a WF6 vapor
pressure of ca. 10 torr was set up in the gas space. The four
tungsten wires were heated to 500 to 700°C; WFI, then
separated on the cold quartz wall as a yellow crystalline
substance; after the excess of WF6 had been pumped off, the
Angew. Chem. infernat. Edit.,/ Vol. 7 (3968) / No. 2
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containing, diazaallyl, azaallyl, dimerization, oxaazaallyl, group, intermediate, way, coppel
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