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Investigations of Cyanine Dyes by P.M.R. Spectroscopy

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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
These results supply information on the fine structure of the
cyanines and contribute to the theoretical interpretation of
these dyes. Our investigations are therefore continued on a
broad basis.
Received, February 15th, 1963
NM R-Spectrometer.
Preparation of 1-Hydroxypropane-2-sulfonicAcid
By Dr. Heinz Schmitz, Dr. H. Grosspietsch,
Dr. H. Kaltenhiiuser, and Dr. H.Wendt
Farbwerke Hoechst AG. vormals Meister Lucius & Bruning,
FrankfurtIMain-Hiichst (Germaiiy)
I-Hydroxypropane-2-sulfonicacid is said to have been
prepared by Raschig and Prahl [l] bq treating chloropropylene glycol acetate with K2SO3 (synthesis I) and by Manecke [2]by hydrolysis of an anhydride of the acid made by
treating sulfuryl chloride with n-propanol and dehydrochlorinating the propyl chlorosulfonate obtained (synthesis
11). As rearrangements may possibly occui in these syntheses,
we have prepared 1-hydroxypropane-2-sulfonicacid by
reduction of cr-sulphonylpropionic acid with LiAIFI4 in
dioxan (synthesis 111).
I
LiAIH4
d H3C-CH-CHZOH
dioxan
I
SOsH
SO3H
The infrared spectrum of the barium salt of this acid was
different from those of the barium hydroxypropanesulfonates
made by syntheses I and 11, which corresponded. The
hydroxypropancsulfonic acid made by the othei authors
must therefore be either 2-hydroxypropane-1-sulfonicacid
or 1 -hydroxypropane-3-sulfonic
acid. The latter is obtainable
by hydrolysis of 1,3-propanesultone; the infrared spectrum
of its barium salt differs from the spectra of the barium salts
obtained by syntheses I, 11, and 111. 2-Hydroxypropane-lsulfonic acid was made by reduction of acetonesulfonic acid
(synthesis IV); its barium salt had the same infrared spectrum
as that of the barium salts from syntheses J and 11.
I t can also be shown by comparison of the melting points of
the phenylhydrazonium salts and of the N-methylaminopropanesulfonic acids (obtained by reaction with methylamine) that the hydroxypropanesulfonic acids described both
by Raschig and Piahl and by Manecke are in fact 2-hydioxypropane- 1 -sulfonic acid.
Method of
synthesis
1
Phenylhydrazoniurn salt
rn.p.[ “C];
m.p.
By Dozent Dr. Ulrich Schmidt and
Dip1.-Chem. Asmus Muller
[Z 454/292 IE]
[ l ] G. Scheibe, H . J . Friedrich, and G. Hohlneicher,Angew. Chem.
73, 383 (1961).
[2] The investigations were carried out with a Varian A 60 Mode
H2C-CH-COOH
Detection of the Phenylsulfur Radical [11
N-Methylaminopropanesulfonic acid
m.p. [ T I ; mixed m.p. I “Cl
Chemisches Laboratorium
der Universitit FreiburgIBreisgau (Germany)
P
Ionic radicals of doubly-bonded sulfur (R--S-R) were
detected by us in oxidized solutions in sulfuric acid of di-pmethoxyphenyl sulfide, p-di(arylthio)benzenes, and tetraphenylthiophenes [l]. Free radicals of singly-bonded sulfur
(R-So) have been sought repeatedly, but were not found
hitherto [2]. However, the existence of the phenylsulfur
radical (Ph --SO)has now been demonstrated by us.
On irradiating diphenyl sulfide vapor with short-wave ultraviolet light at 1 mm. Hg pressure and high carrier-gas (N2)
speeds, phenylsulfur radicals were detected as thiophenol by
dehydrogenation of injected cumene 10 cni from the irradiated
zone.
Irradiation of diphenyl sulfide vapor without carrier-gas at
0.1 mm Hg pressure resulted in the formation of a red
coating of Ph -S. a few cm away on a finger cooled with
liquid nitrogen. This was stable for some hours in vcicuo at
-2OO”C, but disappeared within a few minutes at -100°C.
Thiophenol was formed by disproportionation or dehydrogenation of diphenyldisulfide.
Measurement of the electron spin resonance spectrum at
-200 “C showed a strong signal with a typically anisotropic
g factor. The g tensor is almost axisymmetrical with limiting
values g I = 2.006 and gi 1 = 2.012 as far as can be determined
from the powder spectra. This indicates that the unpaired
electron is associated mainly with the sulfur, since such a
large degree of g anisotropy can only be explained by an
electron which is strongly localized.
Received, February 25th, 1963
[Z 453/281 IE]
[ l ] Communication No. 2 on Organosulfur Radicals; Communication No. 1 : Angew. Chem. 72, 708 (1960).
[2] For literature references, see Communication No. 3, Liebigs
Ann. Chem., in the press.
Proton-Resonance Investigations of
“4 (or 5)-Substituted Imidazoles”
By Prof. Dr. H. A. Staab and Dr. A. Mannschreck
Organisch-chemisches Jnstitut
der Universitat Heidelberg (Germany)
Tautomeric forms A and B of 4 (or 5)substituted imidazoles
cannot be isolated [I]. It has also not been possible to determine whether these compounds exist as either structure A or
structure B.
193.5
-
111
IV
I1 f IV
A
194
135
135
Willems [3] also designated a substance he obtained from 2bromopropanol and N a ~ S 0 3 as 1-hydroxypropane-2-sulfonic acid, as it proved to be identical with the acid described
by Manecke. It appears from our work that Willems too
obtained 2-hydroxypropane-1-sulfonicacid.
Received, February 21st, 1963
[Z 451/280 IE]
[ I ] F. Raschig and W. Prahl, Ber. dtsch. chem. Ges. 61, 185
(1928).
[2] G. Manecke, Chem. Ber. 85, 160 (1952).
[3] J. Willerns, Bull. SOC.chim. Belg. 64, 409 (1955).
216
13
193.5
Concepts, such as the hypothesis of a special “mesohydric
tautomerism” [2], or the postulate [3] based on spectroscopic
results that, in both the crystalline state and non-polar solvents, imidazoles exist as ion-pairs made up of imidazole
anions and imidazole cations led to the assumption that it is
impossible to differentiate between 4-and 5-substituted imidazoles [3,4]. Our proton-resonance experiments show that
such postulates do noi apply to the 4(or 5)-substituted
imidazoles investigated in the present work. They demonstrate that these compounds exist predominantly in one
definite form, for which distinction can be made between 4and 5-substitution on the basis of the respective spin-spin
coupling constants.
Angew. Chem. internat. Edit. / Vol. 2 (1963) No. 4
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