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Oxidative Addition of Nitroalkanes to Tetrakis(triphenylphosphane)platinum(0) a Simple Route to Complex Metal Fulminates.

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low even only the most important of these investigations
in broad outline (cf. e.g.IzsoI). Neither a biochemical
cause nor a biochemical correlate of endogenous psychoses has so far been found[251],though the relation
between disease and amine metabolism appears to be
obvious in the case of the endogenous depressions. Thus
the symptoms of the depression are modified by measures that affect the amine metabolism in the brain. Monoamine oxidase inhibitors and substances of the imipramine type have an antidepressant action, while treatment
with lithium chloride leads to an improvement of the
symptoms[2821and causes an increase in the turnover of
norepinephrine in the brains of experimental animals as
well as increased metabolic transformation of this amine
by the monoamine o ~ i d a s e [ ~ Depressions
~ ~ - ~ ~ ~ ! that are
frequently indistinguishable from endogenous depressions can be produced again. by treatment with reserThere are also numerous observations that
point to differences in the amine metabolism of diseased
persons as compared with healthy subjects, but no conclusions can be drawn as yet from these observations
on critical
There are many reasons why our knowledge about the
biochemistry of mental diseases is still very limited despite great efforts, quite apart from whether the approach
via the amine metabolism, which is only one of the many
possible approaches to the understanding of these diseases, does in fact lead to the desired result. One of the
[250] H. E. Hirnwich, S. S. Kety, and J. R. Smytbies: Amines in Schizophrenia. Pergamon Press, London 1967.
[251] C. P. Rosenbaurn, J. Nervous Mental Diseases 146, 103 (1968).
[252] M. Schou, J. Psychiat. Res. 6, 67 (1968).
(2531 J. 1. Schildkraut, M. A. Logue, and G. A. Dodge, Psychopharmacologia 14, 135 (1969).
[254] H. Corrodi, K. Fuxe, T. Hokfelt, and M. Schou, Psychopharmacologia 11, 345 (1967).
[255] D. M. Stern, R. Fieve, N . Neff, and E. Costa, Pharmacologist 9,
210 (1967).
most important reasons seems to us to be as follows. To
be able to recognize pathological modes of reaction, it
is necessary to know the physiological processes for
comparison. However, the biochemistry of the central
nervous system is still largely unknown, even in a field
that has been studied as intensively as that of the biogenic
amines.
6. CIosing Remarks
The function of some biogenic amines as transmitter substances at certain synapses can now be regarded as certain, though their precise mode of action is not yet known
and very many questions remain to be answered in connection with the functioning of the synapses. The undeniably significant expansion of our knowledge concerning the biogenic amines during the past few years
is an excellent example of the fact that progress in biology
can only be achieved by the combined efforts of workers
in a wide range of disciplines, ie. biologists, morphologists, physiologists, pharmacologists, and chemists.
Received: May 28, 1970 [A 798 IE]
German version: Angew. Chem. 83.53 (1971)
Translated by Express Translation Service, London.
12561 W. E. Bunney and J. M. D a ~ s ,Arch. Gen. Psychiat. 13, 483
(1965).
(2571 W G. Dewhurst, Proc. Roy. SOC.Med. 62, 32 (1969)
1258) 1.M. Robson and R. Stacey: Recent Advances in Pharmacology.
Churchill, London 1962, 2. Edit. p. 2.
[259] H. M. Adarnand H. K.A. Hye, Brit. J. Pharmacol. 28,137 (1966).
12601 L. M. Zieher and E. D e Robertis, Biochem. Pharmacol. 12, 596
(1963).
[261] L. M. Zieher and E. D e Robertis, 6. Congr. Assoc. Latinoam.
Cienc. Fisiol. Vina del Mar, 1964.
[262] E. De Robertis, A. Pellegnno de Iraldi, G. Rodriguez de Lores
Arnaiz, and L. Salganicof~J. Neurochem. 9,23 (1962).
[263] S. Fahn, J. S. Rodrnan, and L. J. Cbtk, J . Neurochem. 16, 1293
(1969).
[264] D. G. Grahame-Smifh, Biochem. J. 105, 351 (1967).
COMMUNICATIONS
Oxidative Addition of Nitroalkanes to
Tetrakis(triphenylphosphane)platinum(O):
a Simple Route to Complex Metal Fulminates
Pt(PPh3)d
Pt(PPh3)z
+
2 PPh,
By Wolfgang Beck, Karl Schorpp, and Franz Kern"]
Dedicated to Professor Walter Hieber on the occasion of his
75th birthday
Complex metal fulminates have hitherto been synthesized
by treatment of alkali-metal fulminates [accessible from
Hg(CN0)' and the alkali-metal amalgam] with metal salts[',*].
Although fulminatometalate anions with bulky cations, and
complexes containing phosphanes, are not explosive and are
relatively stable['], work with the starting materials [NaCNO
and Hg(CN0)2] requires particular care.
We have now found that reaction of tetrakis(tripheny1phosphane)platinum(O) with nitromethane provides a convenient
and completely safe method of preparing difulminatobis(triphenylphosphane)platinum(
66
I. + CH~NOI
2.
- 2 H20;
- Hz *
PPh,
I
0-N-C-Pt-C-N-0
I
PPh3
W e assume that nitromethane reacts as a compound containing
an acidic CH group in this process, primarily by oxidative addition, analogously to the reaction of Pt(PPh,), with other protonic acids[,]. Accordingly, the reaction medium is decisive for
formation of fulminate: whereas no fulminate can be detected
Angew. Chern. internat. Edit. / Vol. 10 (1971) / N o . I
after 70 hours' heating under reflux in benzene/nitromethane,
the fulminato complex is formed in 80% yield in ethanol/wateribenzenelnitromethane (1 : 1:1: 3 L7) [cf. the acidity of
nitromethane: pK (in H,O) = 10.2i)51; pK (in an aprotic
medium) = 15.96[6]].
of diphenylanthracene used is less than that given above, the
chemiluminescence ceases prematurely, but it can be restarted
by addition of further diphenylanthracene. Investigation of the
obviously complex mixture of products is in pro ress (for thermolysis of phthaloyl peroxide in benzene see[2).
If a large excess of triphenylphosphane is used, the cyano
complex is the main product, fulminate being reduced to
cyanide by the phosphane as in the reaction of organic nitrile
oxides[8).
We did not find any chemiluminescence from these two components in other organic solvents. The luminescence is appreciably catalyzed by addition of a little water to the phthalic
esters: it then begins already at 25" C, although it reaches only
about 1/3 of the intensity, but the same quantum yield is obtained in 20 min as in the reaction without water. Glacial acetic
acid has a strong quenching action. Oxygen['] was not found
to be inhibitory, but it does not appreciably increase the light
emission.
Reactions of Pt(PPh,), with nitroethane or 2-nitropropane
do not lead to fulminates with loss of methanol or dimethyl
ether, respectively, but instead the dinitro complexes
(PPh,),Pt(NO,), can be isolated.
Difulmina tobis(tripheny1phosphane)platinum(xr)
7
Dibenzoyl peroxide affords no chemiluminescence under the
above conditions.
Pt(PPh3), (1.25 g, 1 mmole) is heated under reflux in benzenelethanollwaterinitromethane (1 : 1 : 1 : 3) (60 ml) under
N, and with exclusion of light. Above 60°C the solvent mixture
forms one phase in which the platinum(0) complex dissolves
completely within a few hours. After 50 hours the fulminato
complex is partly precipitated even in the hot; it is filtered from
the cooled reaction mixture and recrystallized from chloroformllight petroleum, forming colorless crystals that contain 1
mole of chloroform per formula unit of the complex (yield0.75 g,
80%). IR: 2v,(CNO) = 2325 ern-', vas(CNO) = 2190 cm-l,
v,(CNO) = 1153 cm-lu3l.
Hercules e t af.r31 recently studied the role of energy transfer
processes in the chemiluminescence of compounds such as 3,6diphenyl-1,2,4,5-tetroxane(dibenzylidene diperoxide), also in
the presence of diphenylanthracene. The sensitized chemiluminescence occurring in that reaction is ascribed to triplet
benzaldehyde and/or singlet oxygen as primary excited particles
(species which do not come into consideration for phthaloyl
peroxide) and is weaker by several orders of magnitude than
that now reported for the first time.
Received. October 19, 1970 [2 302 IE]
German version: Angew. Chem 83,43 (1971)
Received: November 2, 1970 [ Z 303 IE]
German version: Angew. Chem. 83, 43 (1971)
[*I
Prof. Dr. W. Beck, DipLChem. K. Schorpp, and F. Kern
Institut fur Anorganische Chemie der Universitat
8 Mhnchen, Meiserstr. 1 (Germany)
[ 11 L. Wohlerand A. Berthmann, Ber. dtsch. chern. Ges. 62,2742,2748
(1929).
[2] W. Beck, P.Swoboda, K . Feldl, and E. Schuierer, Chem. Ber. 103,
3591 (1970).
[3] W. Beck and E. Schuierer, Chem. Ber. 98, 298 (1965).
[4] F. Cariati, R. Ugo, and F. Bonati, Inorg. Chem. 5, 1128 (1966);
J. McAvoy and D. W. A . Sharp, J. Chem. SOC. 1965, 1376; H. Singer
and G. Wilkinson, J . Chem. SOC.A 1968, 2516.
[5] D. Turnbulland S. H. Maron, J. Amer. Chem. SOC.65,212 (1943).
[6] C. D. Rizchie and R. E. Uschold, J. Amer. Chern. Sac. 90, 2821
(1968).
[7] The fulminates Hg(CNO), and PhHgCNO are obtained also by the
"acid-base'' reaction of, respectively, HgO or PhHgOH with
CH2NO2Na or CH3NOZ; I. U. Nef, Liebigs An;. Chem. 280, 276
(1894); M. V. Kashutina and 0.Okhlobystin, J. Organometal. Chem.
9, 5 (1967).
[8] Ch. Grundmann, J. Org. Chem. 30, 2077 (1965).
Sensitized Chemiluminescence on Thermolysis
of Phthaloyl Peroxide in the Presence of
9,lO-Diphenylanthracene
['I Prof. Dr. K.-D. Gunderrnann, M. Steinfatt, and Dr. H. Fiege
Organisch-Chemisches Institut der Technischen Universitat Clausthal
3392 Clausthal-Zellerfeld, Leibnizstr. 6 (Germany)
[ l ] K.-D. Gundermann, H. Fiege, and G. Klockenbring, Liebigs Ann.
Chem. 738, 140 (1970).
[2] F. D. Greene, J. Amer. Chem. SOC. 78, 2246 (1956).
[3] S. R. Abbott, S. Ness, and D. M. Hercules, J. Amer. Chem. SOC.92,
1128 (1970).
Addition of Electrophiles to Diethyl
2,4-Bis(diethylamino)cyclobutadiene-1,3-dicarboxylate'"]
By Rudolf Gompper and Gijnter Seybold[']
Owing to the known stability of cyclobutenecyanine salts, the
should be a strong
"push-pull" substituted cyclobutadiene (l)[']
nucleophile and thus make possible a study of the hitherto unknown reactions of electrophiles with cyclobutadienes.
O n reaction with strong acids such as HBF, in ether, compound
(1) is converted quantitatively into protonated products, e.g.
(Za), from which it may be regenerated by treatment with
sodium hydridel'l.
By Karl-Dietrich Gundermann, Manfred Steinfatt, and Helmut
Fiegef 'I
As was recently described"], weak chemiluminescence occurs
when potassium tert-butoxide reacts with phthaloyl peroxide
in dimethyl sulfoxide in the presence of fluorescein. We have
now found that warmingphthaloyl peroxide (1.5 X lO-%ole/l)
- 10-3mole/l) in diwith 9,lO-diphenylanthracene
methyl or diethyl phthalate for ca. 10 min at 50-70°C causes
a relatively strong blue chemiluminescence (Ama, = 435 nm)
which reaches ca. 5 % of the maximal intensity and 6-7% of the
quantum yield of luminol emitting in the same spectral region.
The emission spectrum is identical with the fluorescence spectrum of 9,lO-diphenylanthracene;
this is thus a case of sensitized
chemiluminescence due to transfer to the diphenylanthracene
of the excitation energy liberated on decomposition of the
phthaloyl peroxide. The latter is partly converted by the reaction
into yellow, non-fluorescing products. When the concentration
Angew. Chem. internat. Edit. / Vol. 10 (1971) / N o . 1
ROOC
NR2
( ~ a jx, = B F ~
(26), X = C H 3 0 @
ROOC
COOR
NR2 NR2
141, R'
= CH,O
(S), R' = H
67
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simple, triphenylphosphate, platinum, complex, nitroalkanes, metali, oxidative, additional, fulminates, tetrakis, route
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