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New Synthetic Methods for 6a4-Thiapentalenes.

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a six-membered ring; a 36-line spectrum would be expected
for (6). The FD mass spectrum[51also provides important
evidence in favor of the four-membered ring. The peak at
mje=459 corresponds to the dication of ( 4 ) , but could also
be assigned to the trebly charged cation (6). The latter possibility is discounted by the appearance of the highest mass peak
at m/e=917, i. e. for [K2+ -H+]+ and by the absence of ions
in the range m/e= 1000-1 500. Another line at m/e = 841 arises
from a cation containing one less phenyl group [Kz+- Ph+]+.
Procedure
(2): To an ice-cooled, stirred solution of
(17.4g,
41.8 mmol) in a minimal amount of CHZCIZis slowly added
dropwise PhzPCl (18.4 g, 83.6mmol) diluted with the same
amount of CH2C12. After 2 h the precipitated trichlorodiphenylphosphorane is filtered off (10g = 34 mmol = 82 %) and
that remaining in solution decomposed with 1,2-epoxybutane.
The solvent is distilled off in uucuoand the dry residue dissolved
in CH3CN. Ether is added to the gently stirred solution until
it becomes slightly turbid; precipitation is complete within
30min. The product is filtered off, washed with ether, and
dried in uucuo at 40°C. Yield: 16.8g (71 %) of (2), m.p. 192°C
(dec.). 'H-NMR: multiplet at 6=7.4 to 8.0ppm. 31P-NMR:
two doublets at 6 = - 23.63 and + 62.63 ppm; J(P,P)=42.5 Hz.
( 4 ) : To a solution of (2) (8.5g, 15mmol) in CH2C12
is added solid trimorpholinophosphane (4.3 g, 15mmol) in
a single batch and the mixture is stirred at room temperature
for 10 to 20min. After evaporation to dryness at 40°C the
residue is taken up in benzene and the mixture filtered. The
filter cake is stirred with CH2C12, whereupon (OC4HsN)3PC12
dissolves. The white residual solid is recrystallized
from methanol. After washing with CHzClz it is dried at
80°C. Yield: 5.8g (79%) of (4), m.p. 385"C.-The action
of bromine on the solution of ( 4 ) in CHzClz gives ( 5 ) , dec.
365"C, in quantitative yield. 31P-NMR: two triplets at
6 = 14.44 and 33.64ppm; J(P,P)=7.35Hz.
Received: March 14, 1977 [Z 696 IE]
German version: Angew. Chem. 89,415 (1977)
CAS Registry numbers:
( I ), 57557-88-7; (2), ionic form, 62414-93-1 ; ( 2 ) , bonded form, 62337-52-4;
(3), 62337-54-6: (4), 62337-53-5: (S), 62414-92-0; PhZPCI, 1079-66-9; "C,
14762-74-4
[l] Part 7 of Phosphorus-Carbon-Halogen Compounds.-Part 6: R . Appel,
W Morbach, Angew. Chem. 89, 203 (1977); Angew. Chem. Int. Ed.
Engl. 16, 180 (1977).
[2] R. Appel, F . Knoll, W Michel, W Morbach, €2.-D. Wihler, H . Veltmann,
Chem. Ber. 109, 58 (1976).
[3] R . Appel, H . Veltmann, Tetrahedron Lett. 1976, 399; R . Appel, F . Knoll,
H . Veltmann, Angew. Chem. 88, 340 (1976); Angew. Chem. Int. Ed.
Engl. 15, 315 (1976); R . Appel, G . Erbelding, to be published.
[4] A. P . Mironenko, S . B. Stepina, K E. Plyushchev, L. A. Zotova, Zh.
Neorg. Khim. 1968,2838; A . P . Mironenko, L. H . Kulikova, J . J . Alekseeva,
S . B. Stepina, !I E. Plyushcheu, L. 3. Pokroskaya, ibid. 1974, 3272.
[5] We are indebted to Prof. Dr. H . D. Beckey and Dr. H . R . Schulten,
Bonn, for recording the spectrum.
by reaction with alkali metal, we were able to remove all
the phenyl groups with the aid of AlCI3/HCl and to isolate
Si6C112[3].
AlC13 had already been used on former occasions
for cleaving Si-phenyl bonds in simple ~ilanes[~].
The cleavage
reaction, shown by our investigations to be electrophilic, also
proceeds without ring cleavage with phenylcyclosilanes,
whereas hydrogen chloride under pressure in the absence
of AlC13 effects only partial removal of the phenyl groupsr51.
Use of A1C13 has the considerable practical advantage that
the reaction occurs with gaseous HC1 and use of liquified
HCl (bomb tube) can be avoided.
Si6Cl12 can be smoothly hydrogenated to unsubstituted
cyclohexasilane with pure LiA1H4 in benzenejether. Si6H12
is a colorless liquid which ignites spontaneously on exposure
to air. Owing to its low vapor pressure the new compound
is easier to handle than Si5H10. Its 'H-NMR, IR, Raman,
and mass spectra were recorded for purposes of characterization.
'H-NMR (60 MHz; in benzene TMS int.): singlet at r=6.50, 3sl"=195Hz
IR [cm-'1: 330w, 384m (hr), 519w, 625vs, 720vs (hr), 865111, 892vs, 904vs,
2120vs
Raman [cm-'1: 114s (p), 350vs @), 379w (p), 455111, 476vs (sh), 517vw
(p), 625w, 655111, 736vw (?), 893m, 2128vs (br, p)
MS: Molecular ion at m/e 180, usual isotopic distribution due to "Si;
fragmentation pattern results from successive loss of H and SiH4
Assuming a chair conformation similar to that of cyclohexane, the Raman spectrum should display 14 lines (6Alg+8E,),
which are indeed observed (vSiH must be counted fourfold).
In the IR spectrum 13 vibrations are expected (5A2,+8E,)
of which 9 are observable, the SiH stretching vibration being
multiply degenerate; the ring deformation vibrations lie outside the range of measurement. These results and the polarization measurements strongly suggest the assumed conformation
of cyclohexasilane.
Procedure
Benzene (200ml) and AlC13 (1 g, 7.5mmol) are added to
Si6Ph12(4g, 3.6mmol). HCl is passed into this stirred suspension until a clear solution is obtained. A1C13 is filtered off,
and a freshly prepared 0 . 5 ~ethereal solution of LiAIH4
(100ml)is added to the vigorously stirred filtrate with ice-cooling (1 h). Stirring is continued at room temperature, the ether
removed, and the precipitate filtered off; residual benzene
is drawn off at 1 torr. At 0.01 torr and 80°C Si6HI2 condenses over as a colorless liquid, yield 0.39g (60%).
Received: March 17, 1977 [Z 698 IE]
German version: Angew. Chem. 89,417 (1977)
CAS Registry numbers:
SibHI Z r 29 1-59-8; Si6PhL2,1591-06-6
[I] E. Hengge, G. Bauer, Angew. Chem. 85, 304 (1973); Angew. Chem.
Int. Ed. Engl. 12, 316 (1973).
[2] F . S. Kipping, J . E. Sands, J. Chem. SOC.Trans. 119, 830 (1921).
[3] E. Hengge, D. Kouar, J. Organomet. Chem. 125, C29 (1977).
[4] J . D. Austin, C. Eaborn, J . D . Smith, J. Chem. SOC.1963, 4744.
[S] E. Hengge, F. Lunzer, Monatsh. Chem. 107, 371 (1976).
Preparation of Cyclohexasilane, Si6H1
By Edwin Hengge and Dieter KovarC*l
Following the discovery of the first cyclic hydrosilicon
Si5Hl& l l ,we have now succeeded in preparing and characterizing the next homolog Si6Hl2.Starting from dodecaphenylcyclohexasilane,first obtained by Kipping et ~ 1 . [from
~ ] PhzSiC12
p]
Prof. Dr. E. Hengge, Dipl.-Ing. D. Kovar
Institut f i r Anorganische Chemie der Technischen Universitat
Stremayrgasse 16, A-8010 Graz (Austria)
Angew. Chem. l n t . E d . Engl. 16 (1977) No. 6
New Synthetic Methods for 6ah4-Thiapentalenes
By Gerrit L'abbe!, Gabriel Verhelst, and Guido VermeulenC']
1,6,6ah4-Thiapentalenes and analogous compounds have
recently acquired considerable interest owing to their ability
[*I Prof. Dr. G. L'abbe, G. Verhelst, G. Vermeulen
Department of Chemistry, University of Leuven
Celestijnenlaan 200 F, B-3030 Heverlee (Belgium)
403
to engage in no-bond resonance1']. We have now found that
a series of 6ah4-thia-l ,Qheteropentalenes of general structure
( 1 ) can be prepared from the readily available 5-amino-I ,2,3,4thiatriazole (2)[*]. Thus, when (2) is reacted with two equivalents of benzoyl chloride and triethylamine, a thermostable
compound ( l a ) is obtained which exhibits spectral data
(strong M", no v(C=O) above 1600cm-', symmetrical
according to I3C-NMR) consistent with its formulation as
2,5-diphenyl-3,4-dioxa-3ah4-thia-1,6-diazapentalene (compounds (1) have to be designated as 3ah4-thia-1,6-diaza-3,4diheteropentalenes owing to the two nitrogen atoms). Furthermore, compound (I a) was converted by P4S10 into a mixture
of oxadithiadiazapentalene (1 e ) and the known[31orange trithiadiazapentalene (lf). Substituted benzoyl chlorides furnished compounds (1 b ) to (1 d).
Table 1. Compounds oftype ( 1 ) prepared.
Cpd.
X
Y
R'
R2
M.p.["C]
Yield
I%I[a1
0
0
0
0
0
0
Ph
p-MeO-C6H4
p-Me-CsHa
p-N02-C6H4
Ph
Ph
Ph
Ph
NHMe
NHPh
H
Me0
Me
NO2
H
H
H
H
H
H
195-197
241 -242
242-244
270-275
152-153
208-209
278-282
204-205
284-285
244-245
36
23
43
80
11 Cbl
55 Cbl
86
84
66
68
0
0
s
0
s
s
NPh NPh
0
NPh
S
NPh
S
NPh
[a] Yield based on (2).
[h] Yield based on ( 1 a ) ; mixture of (1 e) and (Zf)
Compound (2) was similarly treated with two equivalents
of N-phenylbenzimidoyl chloride in the presence of triethylamine, but the unknown salt ( 3 ) (m.p. 221-221.5 "C) and ( 4 )
(m.p. 231-233°C) were obtained instead of the anticipated
Procedures
Synthesis of (1 a): To an ice-cooled solution of benzoyl
chloride (0.02mol) and triethylamine (0.02mol) in dry tetrahydrofuran (10 ml) is added dropwise with stirring a tetrahydrofuran solution of (2) (0.01 mol in 15 ml). The reaction mixture is allowed to warm to room temperature and stirred for
another two hours until nitrogen evolution has ceased. The
solvent is removed and the residue is washed with water, dried,
and crystallized from chloroform.
Synthesis of (I 9 ) : Equimolar amounts (0.01mol) of (2)
and N-phenylbenzimidoyl chloride are allowed to react in
dry acetonitrile (20ml) until nitrogen evolution has ceased
(2 hours). The precipitate (3) is collected, dried, and crystallized from methanol (yield 87 %).-To an ice-cooled mixture
of ( 3 ) and N-phenylbenzimidoyl chloride (2.5 mmol of each)
is added dropwise with stirring pyridine (10ml). The reaction
mixture is stirred for one hour at O T , and then heated at
reflux temperature for another hour. The mixture is poured
onto ice and ( I g) is filtered off, dried, and crystallized from
CC14/hexane. Compounds ( 1 h ) to ( 1 j ) are prepared in a similar manner.
Received: March 4,1977 [ Z 700 IE]
German version: Angew. Chem. 89,420 (1977)
CAS Registry numbers:
( 1 u), 62302-08-3; ( 1 b ) , 62302-094; ( 1 c ) , 62302-10-7; ( I d ) , 62302-11-8;
( 1 e). 62337-60-4; ( I f ) , 17280-68-1; ( 1 g), 62302-12-9; ( 1 h), 62302-13-0;
( I i), 62302-14-1; ( I j ) , 62302-15-2; (Z), 6630-99-5; ( 3 ) , 62302-16-3; (41,
55434-77-0; benzoyl chloride, 98-88-4; N-phenylbenzimidoyl chloride,
4903-36-0; methyl isothiocyanate, 556-61-6; phenyl isothiocyanate, 103-72-0
[l] Reviews: N . Lozac'h, Adv. Heterocycl. Chem. 13, 161 (1971); E. Klingsberg, Lect. Heterocycl. Chem. 1, 19 (1972); L . K . Hansen, A . Horduik,
L. J . Suethre in C. J . M . Stirling: Organic Sulphur Chemistry. Butterworths, London 1975, pp. 1-17; R . Gleiter and R . Gygax, Fortschr.
Chem. Forsch. 63,49 (1976).
[2] Review: K . A . Jensen, C . Pedersen, Adv. Heterocycl. Chem. 3,263 (1964).
[3] J-L. Derocque, J . Vralle, Bull. SOC.Chim. Fr. 1967, 3079; J-L. Derocque,
M . Perrier, J . Vialle, ibid. 1968, 2062.
Preparation of a fl-PhosphatrimethinecyanineDye[**]
( 1 9). Compound ( 3 ) was the sole product formed when equimolar quantities of (2) and the imidoyl chloride were reacted
in the absence of base. The salt (3) decomposes quantitatively
to ( 4 ) and sulfur in the presence of bases. In order to avoid
this base-induced decomposition in our attempted synthesis
of thiatetraazapentalenes, pyridine was added to a mixture
of ( 3 ) and N-phenylbenzimidoyl chloride: ( 1 g) was obtained
in 86 % yield. Similar treatment of (3) with benzoyl chloride
furnished (I h ) (84 %), and methyl and phenyl isothiocyanate
yielded ( 1 i) and ( l j ) , respectively, in addition to ( 4 ) .
Ph
We believe, the inner salts of type (5) to be the key intermediates in our reactions.
404
By Norbert Gamon and Christian Reichardty]
We wish to report the first synthesis of a P-phosphatrimethinecyanine dye. Hitherto, only phosphamonomethinecyanines['*31but no phosphapolymethinecyanines containing
the structural unit -P- were known (cf. -41).
Reaction of the enamine ( 1 ) with phosphorus tribromide
in boiling dichloromethane affords bromobis(l,3,3-trimethylindolin-2-ylidenemethy1)phosphane (2) as a yellow powder,
which is extremely sensitive to
The preparation
of ( 4 ) from (2), whose UV/Vis spectrum in chloroform shows
it to be slightly dissociated, can be accomplished by alkylation
of the bromide ion with trimethyloxonium tetrafluoroborate.
P-Phosphabis(1,3,3-trimethylindolin-2-yl)trimethiniumtetrafluoroborate ( 4 ) forms dark blue, very fine crystals with a
[*] Prof. Dr. C. Reichardt, Dipl.-Chem. N. Gamon
Fachhereich Chemie der Universitat
Lahnberge, D-3550 Marburg (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie. The results are taken from the
Diplomarbeit of N . Gumon, Universitat Marburg 1977.-Presented at the
6th International Color Symposium in Freudenstadt on September 30. 1976.
Angew. Chem. I n t . E d . Engl. 16 (1977) No. 6
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