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Decomposition of Diimine.

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Table I . Reaction sequence ( 2 )
t (3)
H@
+ ( 4 ) d( 5 )
OHQ
+
(6).
Acid chloride ( I ) of:
I
I
I
I
I
57
54
43
57
94 [a1
74 [a1
la1 Calculated for the step (5)
[bl Hydrochloride.
--f
~~
acetic acid
hutyric acid
n-caproic acid
oenanthic acid
dihydrocinnamic acid
144 -1 50/0.01
133 -l55/0.007
I50-155/0.03
120-125/0.2
136-137 [h]
168-169
(6).
12-Amino-7-ketododecanoic acid ( 6 ) can be reduced with
hydrazine to give 12-aminododecanoic acid (m.p. 179 to
181 "C.) 75 O/O yield.
Received, February 7th, 1963
New Synthesis of Allenecarboxylic Esters
52/11
70/11
97/11
59
55
66
109/11
Il4/l
80
51
The infrared spectra of all the esters ( 3 ) listed contain a
pronounced allene band at 1950 cni-1. The derivative obtained from dihydrocinnamic acid polymerizes slightly on
distillation. Startins from phenylacetic acid, an allenecarboxylic ester is obtained with R
CsH5 which is stable
only in solution and which polymerizes completely on
evaporation.
y i
Received, February Sth, 1963
[Z 4451275 IE]
[I] Syntheses with Enamines X ; Part IX: S. Hiinig and W.
Eckardt, Chem. Ber. 95, 2493 (1962).
[2] V . Meurer, Ph. D. thesis, Universitlt Wurzburg, 1962.
[3] Cf. M . Coenen, Angew. Chern. 61, 11 (1949); G. Stork, R . TerreN, and J. Szurnszkovicz, J . Amer. chem. SOC. 76, 2029 (1954);
S. Hiinig, E. Benzing, and E. Liicke, Chem. Ber. 96, 2833 (1957)
and subsequent publications.
[4] Tautomeric forms are possible here.
H
CZH5
C4Hp
C5HlI
CsH5-CHz
[ Z 446/276 IE]
Decomposition of Diimine
By Prof. Ilr. S. Hiinig, Dr. H. R. Miiller [l],
and Dipl.-Chem. W. Thier [2]
lnstitut fur Organische Chemie der Universitit Miinchen and
Cliemisches Institut der Universitlt Wurzburg (Germany)
According to Ruschrg [ 3 ] . diimine (2) [4] is formed on
thermolysis of arylsulfonylhydrazides ( I ) in strong alkali but
then breaks down into its constituent elements.
By Priv.-Doz. Dr. H. J. Bestniann
and Dipl.-Chem. H. Hartung
ArSC)zlI
Institut fur Organische Chemie
der Technischen Hochschule, Miinclicn (Germany)
a-Ethoxycarbonylethylidenetriphenylphosphorane (2) reacts
with acid chloridei ( I ) to give allenecarboxylic esters ( 3 ) ,
triphenyl-(a-ethoxycarbony1)ethyl phosphoniuni chloride ( 4 ) ,
and triphenylphosphine oxide:
+
I
-L
1 / 2 N, +
I1 N=N-II
(2)
(
loo%)
I,/z iy21q4
( 1 oo";,)
We have found that the fission of ( I ) in boiling methoxyethanol is dependent on the excess of alkali (Table I). It was
only when the medium was strongly basic that the reaction
Table I. Yields of Nz,H , , and NzH4 o n fission of 5.00 mmoles of
benzenesulfonylhydrazide in 50 ml of methoxyethanol with varying
concenlrations of KOH (temperature p a . 125 "C)
.
98 I 2
91
71
65
2.50
0.63
0.32
0.17
97 -k 2
83
54
29
-
48.5:l
5.2: I
1.3: I
0.4: 1
2 5 2
16
46
73
As a first step, an acylated phosphoniuni salt is formed from
( 1 ) and (2) :
is/
I
KOH [mole/l]
2.00
__ 1 7 2 + 2
I
1.00
180
I
0.25
191
I
0.125
Hydrogenation yield
(ethylbenzene)
Compound (2) then abstracts a proton from the y-position
to the phosphorus atom. The mesomeric carbanion formed
rearranges into ( 3 ) . The yields are quoted in Table 1 .
214
The percentages of N2 arid N2H4 in Table 1 therefore give a
direct indication of the proportion of the rates with which
diimide reacts further along routes A and B, respectively.
This makes it probablc that route A proceeds as follows:
HN=NH
HN=NI'
+ Nz
+ OHO
+
T? H ~ O HN=NIQ
+ H i e ; HI0 + HB
??
Hz
Angew. Chem. internat. Edit. 1 Vol. 2 (1963)
+ ,Be
1 No. 4
whereas the newly discovered disproportionation according
to route B can be regarded as a hydrogenation of an azo
double bond [4]. The structure (3) can be considered as a
transition state, especially since diimide produced from
benzenesulfonylhydrazide hydrogenates added tolane stereospecifically to gibe cis-stilbene in at least 95 "/, yield, according
to infrared analysis.
5
The consequences of this auto-hydio~eii:rtion ore currently
being investigated.
[Z 449/279 IE]
Received, February 13th. 1963
[ I ] S . Hiinig and H. R . Muller, Ph. D. thesis, Universitiit Wurzburg 1962.
121 S. Hiinig and W. Thier, Diplom thesis, Universitat Wurzburg
1963.
[3] S. Hiinig et al., Tetrahedron Letters 11, 353 (1961); E. J.
Corey et al., ibid. 11, 341 (1961); E. E.van Turnelen et al., J.
Amer. chem. SOC.83, 3725 (1961).
[4] F. Raschig, Angew. Chem. 23, 972 (1910).
New Heptafulvene Derivatives
By Prof. Dr. K . Hafner, Dr. H. W. Riedel, and
Dip1.-Chem. M . Danielisz
1,2-Dimethyltropylium fluoroboratc ( 6 ) reacts with ethyl
orthoformate in acetic anhydric!c to give the known
azuienium fluoroborate (7) [51.
i 71
i6J
Received, February 13tI1, 1963
[ Z 448/278 IE]
[11 Cf. H. Meerwein et al., Liebigs Ann. Chem. 641, 1 (1961).
[2] Compound ( 3 ) has also been prepared by another route by
T. Noroe el al., see J . W. Cook, Progr. org. Chemistry 5, 159
(1961).
131 K . Hafner et al., Liebigs Ann. Chern. 624, 37 (1959); 650, 80
(1961); Angew. Chem. 71, 378 (1959).
[4] K. Hufner and H . Pelster, Angew. Chern. 73, 342 (1961).
[ 5 ] K . Hafner et al., Liebigs Ann. Chcm. 650, 62 (1961).
Chemische? Institut der UniversitLt Marburg (Germany)
We have found that the ieactivity of the carbony1 group in
cycloheptatrienone ( I ) can be increased by 0-alkylation.
With triethylosonium fluoroborate [I], ( I ) gives a quantitative 3ield of ethoxytropylium fluoroborate (2) (m.p.
40"C), which reacts smoothly with malonic dinitrile in the
presence of bases t o form thermostable orange P&dicyano-,
heptafulvene (3) (m.p. 200°C; Amax = 252 (log E = 3.98).
368 (4.26), 374 (4.27), and 381 (4.27) m p in n-hexane) [2].
Other reactive methylene compounds also react thus with
compound (2) to yield heptafulvene derivatives.
Investigations of Cyanine Dyes by
P.M.R. Spectroscopy
By Dr. ff. J . Friedrich
Chemisches Jnstitut der Universitiit Wiirzburg (Germany)
Cyanine dyestuffs of type ( I ) can occur i n geometrically
isomeric forms and for steric reasons mostly exist i n one
fixed configuration under normal conditions [I]. Proton
resonance of the 6 0 j)N-CH3 group is particularly suitable
for determining this configuration and for investigating its
geometric isomerism [2].
Symmetrical metliinecyanines with a planar structure and a n
all - trans configuration [ I ] e.g. N,N'- dimethylpseudoisocyanine or N,N'-dimethyl-dibenzoxazolo-monomethinecya'\
nine, give a single 8e ),N-CH3 proton - resonance signal.
:\
Two different 6 0 j,N-CH3 resonance signals are observed
with formally symmetrical, but for steric reasons non-planar
derivatives, e . g . meso-substirutcd N,N'-dimethyldibenzthiazolomonomethinecyanines. Similarly, formally symmetrical
planar cyanines with a mono-cis-configuration [l], e . g . N,N'dimethyldipyridomonomethinecyanine, give two different
'\
8 0 ,i,N-CH3 signals.
The P.M.R. spectra show that all the azacyanines so far
investigated exist (for a n as yet unknown reason) in the
mono-cis-form (2), e.g. the N,N'-dimelhylmono-azacyanines
containing pyridine, quinoline, and benzthiazole rings. This
surprising result is supported even further by ultraviolet and
infrared spectroscopic findings.
-
Heptafulvene derivatives also result from condensation of
methylated tropylium salts with orthoesters of carboxylic
acids or their vinylogs in acetic anhydride [3]. Methyltropylium perchlorate ( 4 ) and triethyl orthoformate yield the
deep blue [3-(cycloheptatrienylidene)allyl]tropylium perchlorate ( 5 ) (decomp. > 200°C; Amax = 604 m p ; log E =
4.1 in acetonitrile), a non-benzenoid isomer of the diarylpolymethine-carbonium salts [4].
Analogous colored salts are formed from.compound ( 4 ) and
azulene- 1 -aldehyde (deep blue crystals, decomp. > I50 "C;
Amax = 632 m p ; log E = 3.7 in acetonitrile) andp-dimethylaminobenzaldehyde (deep blue crystals, decomp. > 150 "C;
Amax = 657 m?; log E = 3.76 in acetonitrile).
Angew. Chem. internut. Edit.
Vol. 2 (1963)
No. 4
215
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