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Inversion of the Triphenylamine Molecule.

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We have found that compounds of type ( I ) can also be dehydrogenated to (2) simply by heating to 125 ' C . In addition
to (21,ammonia and a high molecular-weight nitrogenous
residue are formed.
On addition of Cu(1) or Cu(l1) salts to solvent-free ( I ) ,
strongly exothermic dehydrogenation starts, according to
the type of the groups R, either spontaneously at room
temperature or o n warming to 60 "C. In the presence of water
and copper or copper salts, 1 mole of (1) is converted in
96.5 % yield into 0.5 mole of (2), 1 mole of NH3, and 0.5
mole of a ketone with the same carbon skeleton as ( I ) .
The products were separated by distillation and identified by
infrared spectroscopy, gas chromatography, and refractive
We assume that in this reaction 1 molecule of ( 1 ) is dehydrogenated by a second molecule of ( I ) , giving rise to
(2) and the C,C-dianiino compound ( 3 ) . The latter condenses to high molecular-weight compounds with loss of
Table I. Examples o f the reaction 12) + ( 5 j
Yield of
f 5 i [ %I
M. p.
[ 'Cl
24 I
1 no
Starting with. aminoanthracene or aromatic diamines, we
obtained more highly condensed ring systems.
Received, January Znd, 1964
[ Z 6481475 IE]
German version: Angew. Chem. 76, 188 (1964)
[ I ] U.S. Pat. 2768 174 (Oct. 23rd, 1956) Societe des usines chimiques Rhbne-Poulenc, inventors : R . E. Poul and S. Tchelitehef;
Chem. Abstr. 51, 5818 (1957).
Inversion of the Triphenylamine Molecule
ammonia or, in the presence of water, is hydrolysed to the
ketone and ammonia.
[ Z 655/480 IE]
Received, January 3rd and 29th, 1964
German version: Angew. Chem. 76, 229 (1964)
[I] S. R. Poi//sen, Angew. Chem. 72, 781 (1960).
[2] E. Schrnitz and R. Ohme, Chem. Ber. 94, 2166 (1961).
Syntheses with (3-Alkoxyacrylyl Chlorides
By Dr. F. Effenberger and Dipl.-Chem. W. Hartmann
Institut fur Organische Chemie und Organisch-Chemische
Technologie der Technischen Hochschule Stuttgart (Germany)
The interaction of P-alkoxyacrylyl chlorides ( I ) [I] with
alcohols, phenols, thiophenols, hydrazines, and amines has
afforded new derivatives of P-alkoxyacrylic acids, some of
which are suitable for the synthesis of otherwise difficultly
accessible heterocyclic compounds.
By Dip1.-Phys. P. Knobloch and Dipl.-Phys. M. Stockhausen
Physikalisches Institut der Uiiiversitat Mainz (Germany)
Conclusions can be drawn from the relaxation time of
dipole orientation in dilute solution about the mechanism by
which the electrical moment of a polar molecule orientates
in the applied electrical field. Moments that are rigidly incorporated into the molecule can only orientate by rotation
of the whole molecule, resulting in a relatively long relaxation
time. However, if intramolecular adjustment can occur
making more rapid dipole orientation possible, without the
whole molecule having to move, the relaxation time is less.
Table I. Relaxation times 7 of the dipole orientation and dipole
moments $ of triaryl derivatives of Group V elements in benzene.
77,IO '2
60' 10-'2
0.7 I l0-12 (approx.)
70 1 0 - 1 2
I I* [Debye]
R' - o - c H=y - C,
When the anilides (2) are ground with concentrated mineral
acids, carbostyrils ( 5 ) are obtained smoothly within a few
minutes in good yields. Table I gives a list of examples.
The action of concentrated acids on the naphthalides ( 3 )
gave benzoquinolones ( 6 ) [R2 = H, m.p. 257'C, 100%
yield; Rz = CH3, m. p. 240"C, 95 "/, yield] and o n the
phenylhydrazides ( 4 ) gave 1-phenylpyrazol-3-ones ( 7 )
[R2 = H , m.p. 153 " C , 98 ?< yield].
Our relaxation measurements [ 13 yielded direct information
about the different modes of behavior of triphenylamine and
the triaryl derivatives of the higher elements of Group V.
Results obtained for solutions in benzene are shown in
Table 1 .
Relaxation times of the magnitude shown for the first two
substances in Table 1 were to be expected, in view of the
rotatory orientation of the entire molecule. This could be
Angew. Chem. infernot. Edit. / Vol. 3 (1964)
/ No. 3
estimated from the molecular volumes and data derived from
a large amount of experimental material 121. In contrast, the
considerably shorter relaxation time for triphenylamine can
only be explained by internal mobility. Evidently inversion
takes place, facilitated by the arrangement of the N-Ph bonds
in a pyramid that is flatter than those of the other two molecules. The low dipole moment of triphenylamine also implies
very close approximation to a flat structure, with valence
angles greater than the tetrahedral angle. These determinations assure that any inversion in triphenylarsine and
triphenylphosphine should be at least 100 times less probable
than in the amine. Moreover, the values for tribenzylamine
show that inversion evidently occurs only when the nitrogen
is linked to an aromatic ring [*I.
The relaxation times were determined by microwave absorption. For this purpose, dilute soldtions (about 1 mole- %)
in benzene were examined at 20°C at frequencies varying
between 500 Mc (A = 60 cm) and 115 Gc (A = 2.6 mni).
[Z 651j482 IE]
Received, January Sth, 1964
German version: Angew. Chem. 76, 186 (1964)
[l] For apparatus and methods of measurement, see H. Kramer,
Z.Physik 157, 134 (1959); F. Hufnagel and G. Klages, Z . angew.
Physik 12, 202 (1960).
[2] F. Hufnagel, Z. Naturforsch. 150, 123 (1960); F. Hufnagel,
G. Klages, and P. Knobloch, ibid. 17a, 96 (1962), where further
references are given.
[ * ] This may be explained as follows: The bonding state of the
nitrogen atom may contain sp2-hybridization which is energetically favored because of mesomeric interaction between the
phenyl groups and the lone electron pair at the nitrogen atom.
Since the gain in energy due to mesomerism is greatest in the
planar form of the molecule, inversion will be facilitated.
A New Approach to Tetraarylphosphonium Salts
By Prof. Dr. G. Wittig and Dipl.-Chem. H. Matzura
Institut fur Organische Chemie der Universitat Heidelberg
A recent note dealing with the interaction of dehydrobenzene
with diphenylmethylphosphine [l] prompts us to report
results we obtained some time ago. o-Fluorophenyl-lithium
prepared according to Gilman and Gorsich [2] does not react
with triarylphosphine at -75 "C. On being allowed to thaw
in the presence of fluorene, the reaction mixture affords the
tetraarylphosphonium salt at -4OOC in 67 % yield. Analogous reactions with methyl iodide in place of the fluorene
produce the o-methyl derivatives, also in good yield.
preparation of pentaarylphosphoranes with five nonidentical substituents for the purpose of studying their stereochemistry.
Received, January 17th. 1964
[Z 645/473 IE]
German version: Angew. Chem. 76, 187 (1964)
- .-
[ I ] D. Seyferlh and J. M . Burlitch, J. org. Chemistry 28, 2463
[2] H . Gilmnn and R. D . Gorsich, J. Amer. chem. SOC.78, 2217
[3] For an analogous synthesis of ammonium salts, see G. Witrig
and E. Ben;, Chem. Ber. 92, 1999 (1959).
The Crystal Structure of Titanium Phosphide TiSP,
By Prof. Dr. G. Brauer, Dr. K. Gingerich, and
Dipl.-Chem. M. Knausenberger [ I ]
Chemisches Laboratorium der Universitiit FreiburgIBreisgau
and The Pennsylvania State University, Dept. of Chemistry,
University Park, Penns. (U.S.A.)
We have found a hitherto unknown Ti/P phase with about
68.5 % (by weight) T i and 30.3 % P. The X-ray powder diagrams of samples of this and similar composition display a
consistently characteristic diffraction pattern, which is easily
distinguishable from those of neighboring phases. A single
crystal was isolated from one of the samples. X-ray examination of this crystal and of the powdered material indicated
a hexagonal unit cell with dimensions a = 7.234 A; c =
5.090 A; cia = 0.704 A. The phase appears to have a range
of homogeneity. From the density of the substance (d =
4.85 g/cm3) we calculated that the unit cell contains 10 Ti and
6 P atoms. This leads to the formula TisP3 and a crystal structure of the D88 type (MnsSil); space group P63/mcrn. This
structure was confirmed by intensity measurements on integrated Weissenberg photographs. The free parameters X T ~=
0.251 and xp = 0.610 of the six-fold point of symmetry (g)
in the space group P63/mcm were obtained from the electron density distribution along the line parallel to the x-axis
and passing through the point O,O,'j4 (unidimensional Fourier analysis using three-dimensional data).
Received, January 21st, 1964
[Z 6501472 IE]
German version: Angew. Chem. 76, 187 (1964)
[ l ] We wish to thank Dr. H. Barnighnusen for assistance with the
X-ray investigations.
By Dr. Ingeborg Ruidisch and Prof. Dr. Max Schmidt
Institut fur Anorganische Chemie
der Universitat Marburg (Germany)
We have obtained lj1,1,3,3,3-hexamethyldigermazane
( I ) in
dry ether as a colorless liquid, b.p. 47 'C/17 mm, which reacts
readily with the slightest trace of moisture to yield the isosteric germoxane and ammonia.
2 (CH3)3GeCI
+ 3 NH3 + (CH3hGe-NH-Ge(CH3)>
-1- 2 NH&I
a) Ar' = A? = A r 3 = phenyl
b) A r '
= phenyl, A r Z =
p-tolyl, A r 3
= p-biphenylyl
The NMR spectrum of ( I ) has ~ ( c H , - G ~ )as a sharp singlet
c 126.5 cps [1,2]; its infrared spectrum
at -13 cps, J I H . ~ ~=
has peaks at 3390, 2960, 2861, 1405, 1234, 1183, 819, and
780 cm-1 [3]. Trisdimethylchlorogermylamine (2) is obtained from (CH&GeCI2 under analogous conditions
according to the equation
3 (CH3)2GeClz
Compound ( l a ) was characterized as its bromide, m.p.
288-290 OC, and iodide, m.p. 330-332 "C. The structures of
the iodides (Za), m.p.294-296 "C, and(Zb), m.p. 271-273°C.
were confirmed by elemental analyses and infrared spectra.
l h e new method [3] is being applied principally for the
Angew. Cliem. infernnt. Edit.
Val. 3 (1964) No. 3
4 NH? + [ ( C H ~ ) I G ~ C I ] ~
r N3 NH4CI
(together with polymeric dimethylgermazanes and amines) as
colorless crystals, m.p. 62 "C, subl. p. M 75 "C/2 mm, which
are quantitatively hydrolysed by water, albeit more slowly
than ( I ) .
23 I
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triphenylamine, molecules, inversion
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