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Diethylphosphidoaluminum Hydride and Lithium Diethylphosphidoaluminum Hydride.

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During research on the state of cyclooctatetraene in basic
medium [2], two dimeric cyclooctatetraenes were isolated,
which had been previously described by W. 0. Jones [3].
These C16H16 hydrocarbons have m.p. 53 "C and 76 "C and
structures (2) and (3), respectively.
On hydrogenation, (3) absorbs 5 moles of hydrogen to give
C16H26 [4], m.p. 52-54 'C. The ultraviolet spectrum of (3)
exhibits a maximum at 282 my (E = 2300) and a shoulder at
232 m p (E = 4600). Its Diels-Alder adducts with maleic anhydride, diethyl fumarate, and acetylenedicarboxylic ester
absorb in the ultraviolet at h = 232 my (shoulder, E = 3000
to 6000). The acetylenedicarboxylic ester adduct decomposes
at about 160 "C into dimethyl phthalate and C12H12 (4) [4],
m.p. 22'C. The ultravioiet spectrum of ( 4 ) also shows absorption at 232 my (shoulder, E = 2300). Hydrogenation over
palladium yields C12H20 [4].
Ultraviolet irradiation of ( 3 ) in ether affords CloHlo (1) [4]
(75 %; m.p. 96 "C) and benzene.
Hydrogenation of ( I ) over palladium gives C10H18 [4], m.p.
180°C. Treatment of ( I ) with sodium in liquid ammonia
at -75 "C and subsequent decomposition with methanol
yields C10H12 [4], m.p. 45 "C, whose NMR-spectrum indicates a bicycIo[3,3,2]deca-3,7,9-trienestructure. Compound
(1) absorbs in the ultraviolet at 238 m y (shoulder, E = 1700).
Its infrared spectrum has relatively few absorption bands.
Oxidative degradation with ozone at -75 "C in methanol/
ether, subsequent reduction with NaBH4, and esterification
with acetic anhydride 151 lead to C12H1806 [4], m.p. 58 OC,
whose infrared and NMR-spectra are in accordance with a
cis-1,2,3-tri's(acetoxymethyl)cyclopropane structure. The
NMR-spectra of ( I ) , ( 3 ) , (4), and (5) are temperaturedependent [6]. At 100°C the NMR-spectrum of (1) exhibits
a most remarkable property, viz. only one sharp proton
resonance signal at T := 5,8. On cooling, this band broadens.
At -25 "C, two bands are apparent, one centered at T = 4.3
with a relative area of 6, the other centered at T = 7.9 with a
relative area of 4. Further cooling to -85 "C does not alter
the spectrum. Compound ( I ) reacts with dichlorcarbene
(CHCI3/(CH3)3COK) to form a mono-adduct CllHlOCl2
(5) [4], m.p. 101 "C.
( I ) decomposes only above 400 OC to give naphthalene, via
a n as yet unidentified intermediate.
Diethylphosphidoaluminum Hydride and Lithium
Diethylphosphidoaluminum Hydride
By Prof. Dr. G . FrilL and Dipl.-Chem. G. Trenczek
lnstitut fur Anorganisdie und Analytische Chemie der
Universitlt GieRen (Germany)
H2AICI reacts with LiP(C2MS)Z ( I ) in ether to give the trimeric compound [HzAI I'(CzH&]3 (2), which is liquid at
room temperature, crystallires at 1 2OC, and is not pyrophoric in air; molecular weight by cryoscopy in benzene:
350, calc. 356.
Compound (2) correspond\ to [CIzAI - P(C2H5)2]3, which is
obtained from AIC13 and one mole of LiP(CzH5)2 [I]. It
reacts with ( I ) according to:
+
[HzAI-P(CZHS)ZI~ 3 LiP(CzHd2
+
3 Li [AIHz
{ P ( C 2 H h } ZI
(3)
Compound (3) is also obtained as follows:
HzAlCl
+ 2 LiP(CzHsh
==
LiCl
+ Li [AIHz { P(CzH&
} 21
It crystallises well, is colorlcss and inflammable in air, dissolves readily in T H F but more sparingly in ether, and is very
similar to Li[Al{P(C2H&}4] [2].
Received, June 18th, 1963
[Z 526/358 IE]
German version: Angew. Chem. 75,723 (1963).
[l] C . Fritz and G. TrenczeX. Z. anorg. allg. Chem. 313, 236
(1961).
[2] G. Fritz and G. Trrnczeli, Angew. Chem. 74, 942 (1962);
Angew. Chem. internat. Edit. 1, 663 (1962).
The Preparation of a Stable, Non-aromatic
Diazonium Salt
By Dr. H. Reimlinger
Union Carbide European Research Associates S.A.,
Brussels (Belgium)
t
h v 75%
Aliphatic diazonium salts arc hypothetical intermediates of
deamination. The cyclization of a-pyridylphenyldiazomethane
to a triazole derivative [l] suggests that a stable, non-aromatic diazonium salt might be obtained by adding a strong
acid to y-pyridylphenyldiazomethane.
Compound ( I ) is bullvalene, (3), ( 4 ) , and (5) are derivatives
of homotropylidene [l].
Preliminary results indicate that (2) rearranges at 100 "C to
form (3) with simultaneous formation of cyclooctatetraene.
Received, June 18th, 1963
[Z 537/367 IEI
German version: Angew. Chem. 75, 722 (1963).
[l] W. Y. E. Doering and W. R . Rorh, Angew. Chem. 75,27 (1963);
Angew. Chem. internat. Edit. 2, 122 (1963); Tetrahedron 19, 715
(1963).
[2] G . Schroder, Angew. Chem. 75, 91 (1963); Angew. Chern.
internat. Edit. 2, 45 (1963).
[3] W . 0.Jones. Chem. and Ind. 1955, 16.
[4] All the new substances gave correct elemental analyses.
[ 5 ] Method: A. J. Hubert, J. chem. SOC.(London), in the press.
[6] The temperature-dependent NMR-spectra will be reported
in a separate publication.
482
I
I
NO
NO
Ill
Ill
N
N
I
NCB
Ill xo
N
I
NO
Ill
N
xo
x = c13c-co,o
The red solution of the diazo compound obtained by oxidation of a-hydrazono-4-benzylpyridinewith silver oxide in
pentane was evaporated to dryness in V ~ C U Oand the residue
Angew. Chem. internat. Edit. Vol. 2 (1963) / No. 8
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