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Diethyl Cycl[4.3

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Retention of the silicon-silicon bonds in all the carbene
reactions described above was demonstrated, not only by
analytical and spectral data of the isolated products, but
also by spontaneous evolution of hydrogen on alkaline
hydrolysis and reduction of Ag' ions to metallic silver.
Pentachloro( trich1oromethyl)disiiane (2):
Phenyl(trichloromethyl)mercury (1 5 g, 38 mmol) was
heated with hexachlorodisilane ( I ) (21 g, 77 mmol) and
NaI (0.5 g) under argon for 6 h at 120"C (bath temperature).
The solid that separated was filtered off after addition
of light petroleum. Fractional distillation of the filtrate
gave pure (2), b. p. 68 "CIO.6 torr (32 YOyield, 4.2 g), along
with ( I ), b. p. 25"C/3 torr. The product (2) (4.0g) was
also obtained analogously from (bromodichloromethy1)phenylmercury ( I 5 g) and ( I ) (21 g).
IR (capillary; cm-I): 860s, 790m, 732vs, 702s, 610vs,
590vs, 580vs, 525s, 498s, 458s, 448m, 420s, 360s, and
342 m.
Received: April 5, 1973 [Z 824 IE]
German version: Angew. Chem. 85, 507 (1973)
[ I ] D.Sryfrrrh and J . M. Burlirch, J. Organometal. Chem. 4, 127 (1965).
[2] D. Seykrrh, M . E. Gordon, J . Y. P . Mui, and J . M. Burlirch, J.
Amer. Chem. SOC.89, 959 (1967).
[3] D. Seyfrrrh, Pure Appl. Chem. 23, 391 (1970).
[4] D . Seyfrrth and R . L . Lambrrcht .jr., J . Organometal. Chem. 16,
21 (1969).
[5] W M . Wagner, H . Kloostrrzirl, and S . can drr Vrn, Rec. Trav. Chim.
Pays-Bas 80. 740 (1961).
[6] Measured as pure liquid at 60 MHz, with benzene as internal standard.
171 M . Kumada and M. Ishikawu, J. Organometal. Chem. 1 , 41 1 (1964).
in contrast to earlier expectations. A comparison of tricyclic
arenes and hetarenes having a 1271 periphery requires cycl[4.3.2]azine ( 4 a ) , corresponding to the anion of (2), the
first derivative of which will now be described.
The synthesis of the ester was accomplished starting from
3a-azaazulen-4-one ( 5 ) which we obtained by Wittig olefination of 2-pyrrolecarbaldehyde with 3-methoxycarbonyl-2-propenylidenetriphenylphosphoraneand subsequent base-catalyzed cy~lization[~!A Vilsmeier reaction
of ( 5 ) afforded (6) [yellow needles, m. p. 112°C from
benzene,70% yield, IR:vco= l665,1650cm-'] from which
we obtained (7) [yellow oil, 50% yield, IR: vco= 1735,
1710, 167Ocm-'] by heating for 24h with 1,2bis(ethoxycarbonyl)ethylidenetriphenylphosph~rane~~~
in
benzene. Two hours' heating in pyridine/piperidine (10: 1)
resulted in ring closure to give diethyl cycI[4.3.2]azine-4,5dicarboxylate (diethyl 9b-azabenz[cd]azulene-4,5-dicarboxylate) ( 4 b ) [violet needles, m. p. 87 "C from light petroleum, 50% yield, IR: vco= 1726, 1709cmThe ring proton signals appear at very high field in the
NMR spectrum of ( 4 b ) , in spite of the two ester groups.
The influence of the ester groups on the chemical shifts
becomes apparent on comparison of the compounds ( 3 a )
and ( 3 b ) (Table 1).
Diethyl Cycl[4.3.2]azine-4,5-dicarboxylate[**]
By Wilhelm Flitsch and Bernhard Muter"]
The potential formation of a 1271 electron periphery in
the tricyclic arenes ( I ) and (2) and in the corresponding
cyclazines (3) and ( 4 ) , respectively, confers a certain
degree of similarity to antiaromatic systems on these compounds.
Both phenalene ( I ) and the isoelectronic compound 2 H benz[cd]azulene (2) possess a nonbonding molecular orbithe
tal[l-'bl so that, in spite of differing
two compounds can form cations, anions, and radical^^^].
Symmetry-based differences between the two resonance
systems appear mainly in the chemical properties of the
compounds''].
Leauer et aI.[41described the cycl[3.3.3]azine ( 3 a ) , corresponding to the anion of (I), and found it to be paratropic,
Table I . 'H-NMR spectra (T values) of compounds 1 3 0 ) [4] in
[(CH,),Si],O, ( 3 6 ) [4] in CDCI,, and ( 4 h ) in CS2.
Cpd.
I-H
(30)
f3b)
f4b)
-
2-H
3-U
4-H
5-H
6-H
7-H
8-H
9-U
1.93 6.35 7.93 7.93 6.35 7.93 7.93 6.35 1.93
2.84 3.23 3.86 4.71 4.11 3.86 3.23
from 5.52 .to
6.52
4.82 4.94 4.00 -
Like the isomeric cyc1[3.3.3]azines, the cyc1[4.3.2]azines
are strongly paratropic. Symmetry-based differences
between the two systems will only be clearly apparent
when the NMR spectrum of ( 4 a ) becomes available.
Nevertheless the nonuniform peripheral charge distribution expected for the nonalternant system ( 4 ) can already
be seen from the properties of the two ester groups: two
vco bands are observed in the IR spectrum, and only
one ester group undergoes transesterification on treatment
with 5% methanolic sodium methoxide solution at the
boiling temperature.
We were able to prepare a further cycl[4.3.2]azine derivative ( 9 ) in 10% yield by reaction of 4-cyanomethylen-3aazaazulene ( 8 ) ,obtainable from ( 5 ) and cyanomethylenetriphenylphosph~rane[~J,
with oxalyl chloride in benzene
(12h, 25°C). Compound ( 9 ) decomposes without melting
p]
Prof. Dr. W. Flitsch and DipLChem. B. Muter
Organisch-Chemisches Institut der Universitat
44 Munster, OrlCans-Ring 23 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen lndustrie.
Angew. Chem. internat. Edit. Vof. 12 ( 1 9 7 3 J / No. 6
NC
0
501
above 300°C. NMR signals at r=1.7-2.5 correspond
to the ring protons. The position of the vco bands (1645,
1610cm- l ) accordingly indicates strong interaction
between the CO groups and the n electrons of the ring
system.
Received: March 22, I973
supplemented- April 25, 1973 [Z 829 IE]
German version: Angew. Chem. 85, 543 (1973)
[I] R. Zahradnt, Angew. Chem. 77, 1097 (1965);Angew. Chem. internat.
Edit. 4, 1039 (1965); R. Zahradnik and J . Mich/, Collect. Czech. Chem.
Commun. 30, 3529 (1965).
[2] a) For a review of pentalenes see: D. H. Reid, Quart. Rev. Chem.
SOC.19, 274 (1965); b) V. Boekelheide and C . D. Smith, J. Amer. Chem.
SOC.88, 3950 (1966); c) Derivatives of ( 2 ) have been described by K .
Hufnerand H. Schaum, Angew. Chem. 75,90, 1041 (1963); Angew. Chem.
internat. Edit. 2, 95 (1963); 3, 165 (1964); K . Hafner and W Rieper,
Angew. Chem. 82,218 (1970); Angew. Chem. internat. Edit. 9,248 (1970);
E. Galantary, H. Agahigian, and N . Paoletfa, 1. Amer. Chem. SOC.88,
3875 (1966); W K . Gibson, D. Leaver, J . E. Roff, and C . W Cumming,
Chem. Commun. 1967,214.
[3] E.g. ( I ) forms an alternant L system, whiie ( 2 ) forms a nonalternant
one.
[4] D. Farquhar and D. Leaver, Chem. Commun. 1969, 24.
[5] W Flifsch, B. Muter, and U . WOK to be published.
[6] All compounds were characterized by their mass spectra and analytical data.
[7] H. Hoffmann, Chem. Ber. 94, 1331 (1961).
A Simple Synthesis
of Hexafluoroacetone Azinep*I
By Klaus Burger, Josef Fehn, and Willy Thenn"]
The syntheses previously reported for perfluorinated
azines". 21, in particular for hexafluoroacetone azine
(2)[3-51, are complicated and proceed in several steps.
On direct treatment of hydrazine or hydrazine hydrate
with an excess of hexafluoroacetone we obtained the diadduct (I), which afforded hexafluoroacetone azine ( 2 ) by
loss of water on treatment with phosphorus oxide trichloride and a tertiary amine (e.g. quinoline) at 0-15°C.
All the properties of the product agree with those previously
recordedr31.
HZN-NH,
+ - - +
2 CF3COCF3
H
H
O H H O
F3c\1 I I 1,CF3
C-N-N-C,
F3C'
CF3
4-6 h and the product (2) is removed by condensation
in a high vacuum. Purification is accomplished by fractional
condensation or distillation through a short column. Yield
21.4g (65%) of ( 2 ) .
Received: April 2, 1973 [Z 822a IE]
German version: Angew. Chem. 115,541 (1973)
[I] W J . Chambers, C. W Tullock, and D. D. C o f f a n , J. Amer. Chem.
SOC.84, 2337 (1962).
[2] W J . Chambers, US-Pat. 3117996 (1964); Chem. Abstr. 60, 6745e
( 1964).
131 W J . Middlefon and C . G. Krespan, J . Org. Chem. 30, 1398 (1965).
[4] D. M . Gale, W J . Middleton, and C. G. Krespan, J. Amer. Chem.
SOC.88, 3617 (1966).
[5] F . J . Weigerf,J. Fluorine Chem. I , 445 (1972).
Synthesis of l,2k5 -Azaphosphoridines["[**I
By Klaus Burger, Josef Fekn, and Willy Thenn"]
Addition of criss-cross type is characteristic of azinesr21
derived from aromatic aldehydes, cyclohexanone, cyclop e n t a n ~ n e ~ or
~ . ~hexafluoroa~etone~~l,
],
but examples of
1,2-t61and 1,4-addition['] are also known. A five-membered
ring structure has been ascribed to an adduct of an azine
and phosphorochloridic esterl81.
In anhydrous hexane at 0 "C hexafluoroacetoneazine ( I ) I 9 ]
reacts with phosphorous esters or tris(dimethy1amino)phosphane to yield 1 : 1 adducts (2) (Table 1). These compounds have considerable thermal stability.
The 'H-NMR spectra of ( 2 a ) and ( 2 b ) show signals
for three equivalent P-alkoxy groups [(CCI,, internal TMS)
(Za): 8=3.75ppm (d), J,,= 11.7Hzl. The 19F-NMR
spectra [(CF,COOH external) ( 2 ~ ) 6: = -0.32 (m),
-12.45 ppm (broad); ( 2 b ) : -0.78 (m), -12.65 ppm
(broad)] also lie in the expected region['']. These data
con traindicate formation of the products by 1,4-addition
(3) and suggest 1,2-addition to afford ( 2 ) .
The formation of the hitherto unrecorded 1,2h5-azaphosphoridine system[''] is further indicated by the l3C-NMR
spectra"
An unambiguous molecular peak, absence of
the fragment m/e=[M - N 2 ] + , and occurrence of the fragment m/e=[M-(CF,),CN]+ of intensity 100%, for
( 2 b), m* = 220.4 (494+330), are further arguments in favor
of structure (2).
Hexafluoroacetone azine (2)
Hydrazine (3.2 g, 100mmol) or its hydrate (5.0g, 100mmol)
in methylene dichloride (100ml) is treated with an excess
of hexafluoroacetone with vigorous stirring in a closed
apparatus and under a C0,-cooled reflux condenser. The
reaction is exothermic; cooling is necessary if the hexafluoroacetone is introduced very rapidly. Then the volatile
products are removed at water-pump vacuum. The residue
is added to ice-cooled quinoline (131 g, 1 mol) and thereafter
treated with POCI, (38.1 g, 250mmol) with vigorous stirring. The mixture is finally left at room temperature for
[*] Priv.-Doz. Dr. K. Burger, Dr. J. Fehn, and DipLChem. W. Thenn
Organisch-chemisches Institut der Technischen Universitat
8 Miinchen 2, Arcisstrasse 21 (Germany)
[**I This work was supported by the Fonds der Chemischen Industrie.
502
(3)
1-(Hexafluoroisopropylimino)-2,2,2-trimethoxy-3,3bis(trijluoromethy1)-1,2h5-azaphosphoridine( 2 a )
Trimethyl phosphite (2.48g, 20 mmol) is slowly added d r o p
wise to a stirred solution of hexafluoroacetone azine ( 1 )
[*] Priv.-Doz. Dr. K. Burger, Dr. J. Fehn, and DipLChem. W. Thenn
Organisch-chemisches Institut der Technischen Universitat
8 Miinchen 2, Arcisstrasse 21 (Germany)
[**I This work was supported by the Fonds der Chemischen Industrie.
Angew. Chem. internat. Edit.
Vol. I2 (1973)
1 No. 6
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