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Dicyanoketene.

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Synthesisof 1,2-Diazepin-3-oneDerivatives by Reaction
of Alkynes with the N=N Group Coordinated to
Fe2(C0)6[
By Barbel Ulbrich and H o s t Kischi*]
Complexes of type (2) contain a reactive diazene group
which can undergo thermal and photochemical reactions with
alkynes to form tricyclic organoiron compounds (3)[']. We
now wish to report the transformation of these "double addition products" into the hitherto unknownr3] 1,2-dihydro-1,2diazepin-3-one derivatives ( 4 ) .
Procedure
A solution of Brz (0.44g, 2.76mmol) in glacial acetic acid/
methylene chloride (1 :1,50ml) is added dropwise to a solution
of (3 b ) (1 g, 1.38mmol) in the same solvent system (50ml).
Excess Br2 is removed by Na2S03 and the organic product
is washed with benzene (3 x l00ml). After drying and evaporation, column chromatography on Florisil(60-100 mesh) gives
some tetracyclone on elution with toluene/ether (2: I), and
pure ( 4 b ) with CH2C12.Crystallization from CHZClZ/MeOH
at room temperature gives colorless crystals of ( 4 b ) (0.48 g,
57 %), m.p. 110-116°C (dec.). Compound ( 4 a ) is accessible
in like manner: 60 %, m. p. 207-215°C (dec., lilac coloration).
Received: March 8. 1978 [Z 952 IE]
German version: Angew. Chem. 90, 388 (1978)
CAS Registry numbers:
(3 a ) , 66255-77-4; ( 3 h ) , 66255-76-3; ( 4 a ) , 66255-63-8; (4 b), 66255-62-7
( a ) : R=Ph
( b ) : R = iPr
X =COOMe
IOO'C
I
[l]
2PhCeCF'h
[2]
[3]
[4]
[5]
[6]
Starting from the I-pyrazolines ( I a ) or ( I b ) , the corresponding complexes (3) can be prepared in 40-50% yield[21.
Oxidative decomposition of, e. g., (3 a ) with bromine in glacial
acetic acid/methylene chloride gives 2mol of CO per mol
of ( 3 a ) and, after column chromatography, a 60% yieldC4]
of colorless crystals of ( 4 a ) . Elemental analysis and the mass
specirum ( M +at m/e=646) confirm the composition; the
IR spectrum (CC14) contains not only the v(C0) band of
the methoxycarbonyl groups at 1730cm-' but also an intense
absorption at 1640 crn-', which agrees well with the v(C0)
value of 1650cm
for a comparable benz~diazepinone[~].
The 'H-NMR spectrum (CDZCl2,100 MHz) shows the singlets
of the ester methyl groups at 6 = 3.25 and 3.95, the multiplets
of the pyrazoline ring protons at 6=3.3-4.1, and those of
the aromatic protons at 6 = 6.75-7.4. Chemical proof of the
two C=C double bonds was obtained for the isopropyl derivative ( 4 b ) synthesized in the same way: uptake of 2mol of
Br2 per mol of ( 4 b ) at 0°C in CHCl3 gives a tetrabromo
compound which can be dehalogenated by Znldimethyl sulfoxide at room temperature to regenerate ( 4 b ) . The presence
of an N-N bond is evidenced by the nuclear magnetic
resonance data, and above all by the result of thermolysis
of ( 4 a ) at 180°C: tetracyclone is accompanied by 1,l-dimethoxycarbonyl-2-phenylcyclopropane and 1,l-dimethoxycarbonyl-2-phenyl-1-propene, which are also formed on thermolysis of the free 1 -pyrazoline ( I
The reaction sequence (1)- ( 4 ) provides the first demonstration that diazenes activated by transition metals can react
with alkynes by C-N and C-C bond formation to give
organic heterocycles. This should also be possible with other
reactants such as alkenes or 1,3-dienes;use of other transition
metal complexes could lead to the discovery of a catalytic
variant of this new synthetic approach.
[*] Priv.-Doz. Dr. H. Kisch, B Ulbrich
Institut fur Srrahlenchemie im Max-Planck-lnstitut fur Kohlenforschung
Stiftstrasse 34-36, D-4330 Miilheim-Ruhr (Germany)
Angew. Chem. Inr. Ed. Engl. 17 (1978) N o . 5
Transition Metal Complexes of Diazenes, Part 11. This work was supported by the Deutsche Forschungsgemeinschaft.-Part 10: C . C . Frazier
I l l , H. Kisch, Inorg. Chem., in press.
A . Albini, H. Kisch, J. Organomet. Chem. 101, 231 (1975).
1,2-Diazepines are reviewed by M . Nastasi, Heterocycles 4 , 1509 (1976).
Use of cerium(1V) ammonium nitrate instead of bromine gives 3 mol
of CO and a mixture of products which was not further exdmiiird.
N . Dennis, A . R . Katritzky, E. Lunt, M . Ramaiah, R . L. Harlow, S .
H . Simonsen, Tetrahedron Lett. 1976, 1569.
K. Tortschanoff, H . Kisch, 0.E. Polansky, Justus Liebigs Ann. Chem.
1975. 445.
Dicyanoketenep*l
By Richard Neidlein and Ernst Bernhard"]
Dedicated t o Professor Adolf Butenandt on the occasion of
his 75th birthday
We have synthesized dicyanoketene (3)-previously
unknown !-from
2,5-diazido-3,6-dicyano-l,4-benzoquinone
( 2 ) which in turn is formed under special conditions from
2,5-dichloro-3,6-dicyano-l,4-benzoquinone
( I )[ 'I and sodium
azide in tetrahydrofuran (yield 75%). AlkoxycarbonylcyanoketenesC2]
are not accessible by an analogous route. The highly
reactive ketene (3) could not be trapped by alcohols, amines,
etc., for these compounds react with (2) itself by substitution
of the azide group, and only trapping reactions with polarized
ketones were initially considered. Among other compounds,
we used thiapseudophenalenones ( 4 ) and ( 6 a ) - ( 6 c ) .
(5)
[*] Prof. Dr. R. Neidlein, Dipl.-Chem. E. Bernhard
Pharmazeutisch-Chemisches Institut der Universitat
Im Neuenheimer Feld 364, D-6900 Heidelberg (Germany)
[**I This work was supported by the Fonds der Chemischen Industrie
and by the Deutsche Forschungsgemeinschaft.
369
If (2) is subjected to thermal decomp~sition[~l
in the
presence of the thiapseudophenalenones (4)L41 and ( 6 a j(6c)['], then dicyanoketene ( 3 ) reacts to form the otherwise
inaccessible thiapseudophenafulvenes ( 5 ) and (7a)-( 7 c ) ;
R3
(6)
tor with exclusion of moisture, yield: 780mg (74 %) of (2);
IR (KBr): 2240, 2210 ( S N ) , 2155, 2100 {N3),1660 (C+O),
1560 cm-' (C=C); UV (CH,CN): im,,=334nm (~=25300),
260 (17 300), 226 (15 OOO).
Synthesis of ( 5 ) , (7aj-(7c),
(8)-(10):
A 0.25mmol
sample of ( 4 ) , (6 a)-(6c), diphenylcyclopropenone, tropone,
or phenalenone and (2) (90.0mg, 0.375mmol) are refluxed
in anhydrous benzene (25 ml) under Nz for 4 h. The evaporated
solution is applied to a silica gel PLC plate (PSC Kieselgel,
"Merck) and developed with dichloromethane. The reddish
fractions (yellowin thecase of ( 9 ) ) are extracted with dichloromethane (Soxhlet)and the solutions carefully evaporated. The
physical data of ( 5 ) and (7a)-(7c)
are listed in Table 1.
Received: February 3, 1978;
revised: March 3, 1978 [Z 953 IE]
German version: Angew. Chem. 90, 395 (1978)
[l]
121
[3]
the paramagnetic shift of the 'H-NMR signals suggests polarization of these products.
[4]
[5]
[6]
[7]
[XI
The dicyanofulvenes(8)'6J(yield: 26 %), (9)"' (yield: 20 %),
and (lo)[*] (yield: 37%) which we obtained from dicyanoketene ( 3 j and diphenylcyclopropenone, tropone, and phenah o n e were identical with authentic material in their physicochemical and spectroscopic properties.
Table 1. Physical properties of compounds ( 5 ) and ( 7 a j - - ( 7 c )
(5):m.p.253-254"C;
yield: 54 %; M + =234.0247(calc.: 234.0251); 'H-NMR
(CDClj): 6=8.06 (s, H2), 7.49 (d, H3, J=9.7Hz), 7.45 (d, H4, J=9.7Hz),
9.13 (d of d, H6, J,,,h0=7.9Hz, Jm,,.=0.17H~), 7.71 (t, H', Jorf,,o=7.9H~,
Jortho=7.9HZ),8.81 (d of d, Ha, J0,,h,=7.9Hz, Jmet0=0.7Hz);UV (CH3CN):
i,,,=456nm (&=24760),305 (4430). 273 (5760), 242 (10000)
(7a): m.p. 222-223°C; yield: 48 %; M+=234.0247 (calc.: 234.0251); 'HNMR ([D6]-acetone): 6=9.64 (s, H'), 7.42 (d, H4, J=9.4Hz), 7.87 (d, H5,
5=9.4Hz), 7.93 (d of d, H6, Jarlho=7.5Hz,Jm,,,=l.2Hz), 7.77 (t, H', J O r t h o
=7.5HZ, Jortha=7.5Hz), 8.31 (d ofd, Ha, Jur,ho=7.5Hz,Jm,,,=1.2Hz); UV
(CH3CN): E.,.,=458nm
(~=16050),323 (3105), 264 (18220), 239 (10490)
( 7 b ) : m.p. 188-189°C; yield: 3.2 %; M+=248.0404 (calc.: 248.0408); 'HNMR ([D,]-acetone): 5=3.01 (s, CH3), 7.55 (d, H4, J=9.5Hz), 7.86 (d,
H5,5=9.5Hz), 7.91 (d o f d , H6, J,,,h,=7.6Hz, Jm,,,=1.2Hz), 7.70 (t. H',
Jorrho=7.6HZ, Jorth.=7.6HZ), 8.23 (d of d, Ha, Jortho=7.6Hz, Jmet,=1.2Hz);
UV (CH3CN): /.,.,=457nm
(&=19160),324 (5350), 267 (20760), 248 (18650)
(7c): m.p. 270°C (dec.); yield: 27 %; M + =301.9468 (calc.: 301.9472); 'HNMR ([DsI-DMSO): 5 ~ 9 . 6 0(s, H'), 7.32 (d, H4, J=9.5Hz). 7.85 (d, H5,
J =9.5 Hz), 7.98 (s, H'); UV ( CHKN): i
,
,
=480nm
,
(&= 18 170), 459 (19340),
325 (2120), 272 (21610), 246 (12830)
Experimental
Synthesis of (2): A 25 % aqueous solution of sodium azide
(2.6m1, 10mmol) is added to a stirred solution of (I) (1.00g,
4.40mmol) in THF (20ml) at -5°C. The product is precipitated from the red solution by addition of ice-water ( W m l ) .
The orange crystals are filtered off after a few minutes, the filter
crucible being cooled with ice. The crystals are washed several
times with cold ether, dried in vucuo,and stored in a refrigera370
K . Walienfels, G. Bachmann, D. Hofmann, R. Kern, Tetrahedron 21, 2254
(1965).
R. Neidlein, G. Humburg, Chem. Ber., in press.
W Weyler, W G. Duncan, H . W Moore, J. Am. Chem. SOC. 97, 6187
(1975), and references cited therein.
E. Campaigne, D. R. Knapp, J. Heterocycl. Chem. 7, 107 (1970).
R. Neidlein, K . F . Cepera,, Justus Liebigs Ann. Chem., in press; R.
Neidlein, G . Humbug, ibid. 1977, 904.
E. D. Eergmann, I . Agranat, J. Am. Chem. SOC.86, 3587 (1964).
?: Nozoe, T Mukai, K . Osaka, Bull. Chem. Soc. Jpn. 34, 1384 (1961);
K . Hafner, H . W Riedel, M . Danielisz, Angew. Chem. 75, 344 (1963);
Angew. Chem. Int. Ed. Engl. 2, 215 (1963).
H. Prinzbach, V Freudenberger, Angew. Chem. 77, 346 (1965); Angew.
Chem. Int. Ed. Engl. 4,243 (1965).
Azoalkanes by Anodic Oxidation of Anions of N,"Dialkylsulfamides [**I
By Reinhold Bauer and Hartmut Wendt ['I
Hypochlorite oxidation of ammonia, alkylsulfamides or
geminal diamines is the usual reaction path to hydrazine, substituted hydrazines or azoalkanes, respectively"]. The anodic
oxidation of anions of primary and secondary amines in aprotic
solvents opens another route to N-N-coupling products"].
This electrochemical method can also be used for the anions
of N,N'-dialkylsulfamides (I) and thus offers the possibility
of carrying out anodic N-N-coupling in protic solvents, in
a reaction which is easy to perform and which affords azoalkanes in about 90 % yield with attractive current efficiencies.
Table 1 lists the anodic half-wave potentials of some sulfamides
(1 ) and their monoanions (2 j . The anions are generally oxidized in a one-electron step at potentials which are 600 to
800mV more negative than the half-wave potentials of the
corresponding sulfamides. Oxidation products are the azoalkanes ( 4 ) . Table 2 lists mass yields and current efficiencies
for the potentiostatic oxidation of (2).
Table 1. Anodic half-wave potentials of N,N'-dialkylsulfamides and their
anions in methanol at a carbon electrode with 0.1 M n-Bu4BF4 as supporting
electrolyte (E,/' [mV] measured us. aqueous SCE).
R
RHN-SOZ-NHR
n-Butyl
t-Butyl
Cyclohexyl
Adamantyl
1655
1650
I520
1510
(1 j
RHN--SO,-NReLie
(2)
850
loo0
880
910
[*] Dip].-Ing. R. Bauer, Prof. Dr. H. Wendt
Institut fur Chemische Technologie der Technischen Hochschule
Petersenstr. 20, 6100 Darmstadt (Germany)
[**] This work was supported by the Deutsche Forschungsgemeinschaft.
Angew. Chem. Int. Ed. Engl. 17 ( 1 9 7 8 ) N o . 5
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