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Binorbornadienylidene Biquadricyclanylidene.

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[5] Attempts to obtain derivatives of (10) by a method analogous to
the synthesis of cis-monoazatris-u-homobenzene from azepines and diazomethane [3] have so far failed (H. Prinzbach, G. K a u p p , R. Fuchs, M .
J o y r i i r . P K i l z i n y . and J . Marhcv-t, Chem. Ber. in the press).
[6] We thank Dr. H. f r i t z , Ciba-Geigy AG, Basel, for these measurements.
[7] K . Ponsoid and D. Klemm, Chem. Ber. 99, 1502 (1966).
[8] In syntheses involving triamine intermediates of type ( 1 4 ) [numbered
as ( 7 ) ] corresponding to ( 7 ) . the first cyclization should preferably
involve participation of the trans-diaxial substituents on C-I/C-6, yielding
( 1 5 ) . However, unlike the situation with ( 8 ) . the geometric relations
Binorbornadienylidene, Biquadricyclanylidene['I[**]
By Hubert Sauter, Heinz-Giinther Horster, and
Horst Prinzbach"]
Binorbornadienylidene ( I ), norbornadienylidenequadricyclane ( 2 ) , and biquadricyclanylidene (3) warrant inter-
R-Ne-R
f 20)
A
R-NGN-R
dR
f
(17)
est, inter alia, as potential intermediates for the synthesis
of cyclic cross-conjugated K systems'2.31and of new polycycled4].
OOR
-R-NGo;
RHN
NHR
(15)
RO
OR
OR
(14)
I
J
R-NwN-R
(4)
R-N
p-JN-R
(3)
in ( I 5 ) permit four competing partial eliminations, leading to (16)-( 19)
and finally to a mixture of ( 2 0 ) and ( 2 1 ) in proportions that can
hardly be estimated in advance. We are in the process of testing this
hypothesis experimentally for the case of 3,5,6-tribromo- 1,2,4-cyclohexanetriol[9]. That the preparatively accessible, symmetrical 2,4,6-triamino1,3,5-cyclohexanetriol [I b] [used as tris(hydrogen sulfate)] with the allequatorial configuration shows little tendency for the formation of aziridines is hardly surprising in view of the extremely unfavorable position
of the equilibrium with the all-axial conformer [lo].
[9] L. Km)rhc and H . Prinzhnch. unpublished work.
[lo] See T.Posternak, Les Cyclitols, Herman, Paris 1962, p. 104.
[ I I ] Piperazine is a Food model for the N---N
separation in ( 1 0 ) (estimated as 2.88 A). The inductive influence of the nitrogen atom in the
P-position on theacidity ofthe piperazinium monocation can be estimated
as 0.9 pK, unit by comparing the pK., value (9.83) with the pK, value
(10.73) of the dimethylammonium ion [12]. Starting from pKa=8.0 [I31
for aziridine one thus obtains for (11) a pK, value of 8.0-2 0.90=6.20.
From pK,,=S.56 for the piperazinium dication [12], a value of
pK,=6.20-4.27= 1.93 follows for ( 1 2 ) .
[I21 Handbook of Chemistry and Physics. 50th edit. 1969-1970, S.
D-116.
[I31 C . E . O'Roiirkr. L. B. Clapp. and J . 0. Edwards, J. Amer. Chem.
SOC 78, 2159 (1956).
1141 The structural parameters as determined by X-ray analysis of trisoxa- ( 5 ) and trisazd-o-trishomobenzene (10) are essentially comparable
( W. Lit& and U.Driick, In preparation).
Aiigew. Chem. internat. Edit. 1 Vol. 12 ( 1 9 7 3 )
/ No. 12
Starting from quadricyclanone ( 4 ) [ 5 1we have synthesized
(3) by the thiadiazolidine method16.1' . The reaction of
H,S-saturated DMSO solutions of ( 4 ) with aqueous hydrazine at 0°C leads to about 80% yields of mixtures of
( 5 ) and (6) in a ratio of 6:4. Without separation of
the components ( 5 ) is dehydrogenated to the thiadiazoline
(7) by lead tetraacetate (CHZC1,; 0 "C). After subsequent
treatment with triethyl phosphite (80"C), preparative layer
chromatography (silica gel, pentane) affords about 20 %
of ( 3 ) [based on ( 4 ) ] as colorless readily sublimable
prisms.
In the presence of catalytic amounts of palladium(I1)chloride norbomadiene complex[81,(3) isomerizes in solution
[*] Prof. Dr. H. Prinzbach, DipLChem H. Sauter, and Dip].-Chem.
H:G. Horster
Lehrstuhl fur Organische Chemie der Universitat
78 Freiburg, Albertstrasse 21 (Germany)
[**] This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
991
Table 1. Physical data for compounds ( I ) - ( 3 ) and (8)-(I+)
286 (sh, 120)
276 (160)
269 (sh, 150)
250 (sh, 250)
243 (sh, 330) [h]
3.2
6.2
(8H,m),
(4H, m) [a]
30
5.9
8CG3.5
8.04
387 ( 1 200),
255 (23000)
230 (18000) [d]
2.5 -3.1
3.48
3.71
5 71
(4H,m)
(2H. m)
(6H, m) [a]
(8H,m)
(4H,m)[c]
(10H, m)
(2H, m)
(2H. s)
(2H, m) [el
347 fsh, 3100),
265 ish, 12800),
230 ( 3 1 '001 [dJ
2.76
3.02
5.49
5.69
6 22
(IOH, m)
(2H, m)
(2H, s)
(2H, m)
(12H. s) [a]
330 ( 4 100)
263 1x900)
2.6- 2.8
2.90
5.48
5.67
2.70
2.97
549
5.69
6.21
6.22
(lOH, m)
(2H, m)
(2H, s)
(2H. m) [a]
(iOH, m)
( 2H,m)
( 2H.s)
(2H. m)
( 6 H , s)
( 6 H , s) [a]
210(25000) [b]
810
211l21 W O I [ d J
350 (sh, 26001,
365 (sh, 122iltli
230 t30500) [d]
332(4100)
265 18600)
233 (21 000) [d]
220 (29000) [d]
220 (22000) [d]
248 (sh, :
1R0001
222 1=20000) [d,fl
233 (sh, 12000),
220 (21 000) [d]
340 (sh, = 2700)
283 ish, zl000Oj
240(=31000)[d,fl
( 9 b ) : ( l O b ) z 1 : 1;90%]"01(isomerssepdrated bypreparative layer chromatography).
Direct excitation of ( I O U ) with light of wavelength
?L > 370 nm effects selective [27t + 2~lcycloadditionin the
fourfold substituted norbornadiene partial structure to give
(lla)(100mgin650mlofCH2C12;O"C;
20min; Hanovia
450W Hg high pressure lamp; filter: Pyrex and a 1.4%
solution of phenanthrene in CHzCl2).In the case of (ZOb),
irradiation with light of wavelength h>280nm (150 mg
in 300ml ofether,O"C; 2 h; Hanau Q 81 Hg high pressure
lamp; pyrex filter) preferentially generates ( I 1b ) in addition to a little (12b).
Expectedly, ( I I a ) is thermally reisomerized readily
(60"C)[111,and ( l l b ) less readily (130"C)r'21,to (1Oa)
and ( l o b ) respectively.
R
H5C6
/CsH5
\
/
R
H5c&
(9)
( 8)
R
2.6 -2.85 (10H. m)
2.93
5.49
5.68
2.8
5.42
6.16
6.37
6.98
28
5.43
7.27
27
6.25
6.34
6.19
7.13
2.7
7.03
7.26
2.7
5.23
6 19
6.32
7.32
4.63
7.08
[a] In CDCI,, 60 MHz. [b] In acetonitrile. [c] In CDCI , 220 MHz.
[d] In ethanol. [el In C,D,, 60 MHz. [fl Because of low solubility only
semiquantitative. [g] In nitrobenzene, 60 MHz. [h] In n-hexane.
(CH,Cl,) to crystalline binorbornadienylidene (1 ); 'HNMR measurements show the conversion to proceed via
(2).
( 9 a ) , ( 9 b ) , ( I O U ) , ( l o b ) , stable derivatives of ( I ) , were
' dimethyl acetylenediobtained by reaction of ( 8 ~ 7 ) ' ~with
carboxylate [20"C; ( 9 a ) : ( I O U ) -1 : 3 78x1 and of
(8b)Ig1 with hexafluoro-2-butyne [bomb tube, 20°C;
992
The conversion (11 a)+(12a), necessarily with light of
shorter wavelength (h>280nm; Hanau Q 81 lamp, Pyrex
filter) takes a nonuniform course. ( 1 2 a ) can be isolated
in 5 0 6 0 YOyield alongside several minor products, some
of which are colored. The same result is obtained when
( 1 2 a ) is prepared by direct photolysis of ( 1 0 a ) (Pyrex
filter). Owing to short-wavelength absorption by ( 11 b)direct irradiation (CH3CN, Vycor filter) leads mainly to
polymeric products-( 12b ) is prepared by acetone-sensitized excitation from ( I 1 b ) or directly from ( l o b ) .
The ease with which ( 1 . 2 ~ (60°C)
)
and ( 1 2 b ) (130°C)
undergo2oj2n cleavage to ( 1 3 a ) and (13 b ) , respectively,
again differs. At 140°C (13a) affords ( I O U ) in about 10%
yield.
Anyew Chem. Internat. Edit.
1 Vol 12 (1973) J No. 12
The structures of all new compounds are confirmed by
elemental analysis, by their spectral data (Table l), and
by their mutual interconversions. Assignment of the isomeric pairs (9a)J(IOa) and (96)/(1Ob), and hence the
anti position of the four R groups in the subsequent products, it is not unequivocal.
Received: May 4, 1973,
supplemented: May 24. 1973 [Z X41 IE]
German version: Angew. Chem X 5 , 1106 (1973)
Pubhcation delayed at authors’ request
Reaction of (1) with an excess of anhydrous methylamine
(autoclave, 2 h at 2 0 T , 1 h at 50-C and 120‘C) affords
the 3,5,6-tris(methylamino)-1,2,4-cyclohexanetrio1( 6 0 ) ,
isolated as the trihydrochloride ( 6 b ) in 60% yield and
liberated by means of an anion exchanger. Proof of the
substitution pattern [to be compared with those in ( 7 a ) ]
and in particular the e,e,e,e,a,a-conformationsof (6a) and
(6b) follow from the numbers and coupling patterns of
the ’H-NMR signals obtained f x the six ring protons
and the methyl protons and also from the I3C-NMR data.
Photochemical Conversions, Part 50.-Part 49: H . Prinzbach. W
M. Basbudak, Chem. Ber. 106. 1837 (1973).
121 Cf., e.g., H . Prinzbach and H . J . Herr, Angew. Chem. 84. 117 (1972);
Angew. Chem. internat. Edit. 11, 135 (1972).
[3] H . Prinzbach and H . Saurur, Angew. Chem. 84. I15 (1972); Angew.
Chem. internat. Edit. / I . 133 i1972).
[4] Compare, r. g., the products of bishomodiene additions to quadricyclanes; G. Kaupp and H . Prinzbach, Chem. Ber. 104,182 (1971).
[I]
Airgu. and
NU
1,3-
[S] R . W Hoffmann and R. Hirsch, Liebigs Ann. Chem. 727, 222 (1960).
[6] D . H . R . Barton, E . H . Smith, and B. J . Willis, Chem. Commun.
1970, 1226.
[7] With experimental cooperation from H . Babsch.
[S] E . W A b d , M . A. Bennett, and G . Wilkinson, J. Chem. Soc. 1959,
3 178.
[9] H . - C . Horster, Diplomarbeit, Universitat Freiburg 1972.
[lo] This route is superior to that starting from 2,3-diphenylf~lvalene’~’;
its reaction with the same dienophiles is dominated by dimerization
of the hydrocarbon.
[ I I ] The half-reaction time of the model reaction (see below) is 45
min at 64 ‘C ( H . Sauter, Dissertation, Universitat Freiburg 1973).
kU
’
OH
Nu
Nu
@
Nu
Nu
R = COzCH3
Nu
[12] Compare the stabilizing action of perfluoroalkyl groups on strained
systems, e.y. M. G . Barlow, J . G. Dinywdl. and R . N . Haszeldine, Chem.
Commun. 1970, 15x0: D. M. Lemal and L. H . Dunlap, jr., J. Amer.
Chem. SOC.94, 6562 (1972); R. S . H . Liu Tetrahedron Lett. 1969, 1409.
Nu1 NHCHn
Chemistry of cis-Trioxatris-a-homobenzene.
Substitutions by Univalent Nucleophiled”’
By Reinhard Schwesinger, Hans Fritz, and
Horst Prinzbach“]
Previous studies of the chemistry of cis-trioxatris-o-homobenzene (“cis-benzene trioxide”) ( 1 ) concerned, mainly
the 3o+3n fission to trioxacyclononatriene“] and the
properties as “crown ether”“a1; preparative applications by substitutions with nucleophiles (Nu) could also
be foreseen[‘”]. In this connection our interest became
directed to the cyclitols (6) and/or ( 7 ) to be expected
as a result of three-fold epoxide ring cleavage12? We report
here typical reactions of (1) with univalent N-, S-, 0and C-n~cleophiles[~].
[*] Prof. Dr. H. Prinzbach and DipLChem. R. Schwesinger
Lehrstuhl fur Organische Chemie der Universitat
78 Freiburg, Albertstrasse 21 (Germany)
Dr. H. Fritz
Ciba-Geigy AG. Basel (Switzerland)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
Anyew. Chrm.
internat. Edit. i Vol. 12 (1973) f N o . I 2
%H2CH3C1@ N3 SCH2C6H, OH
Br
The behavior of ( 1 ) with sodium azide is analogous: the
triazide (6c) is obtained in almost quantitative yield and
can be converted into cis-triazatris-o-homobenzene (“cisbenzene triimine”)[2J.
As our first S-nucleophile we used benzyl thiolF4’.With a
ca. 1S-fold excess of the thiol (methanol/sodium methoxide, 12 h, 60°C) we could isolate only 3,5,6-tris(benzylthio)-1,2,4-cyclohexanetriol(6d), which also was proved to
have the e,e,e,e,a,a-conformation by the H,H coupling
constants. The 13C signals could be assigned to the six
cyclohexane carbons atoms by selective heteronuclear decoupling experiments ; the resulting order of the chemical
shifts of the 13C(OH) nuclei corresponded to those of
~hiro-inositol[~].
Our first hydrolysis experiments with ( I ) were carried out
with 2 YOaqueous perchloric acid. After cu. 24 hours’ storage at 20°C and subsequent heating at 70°C (1 h), NMR
control indicated an epoxide-free product, from which crystallization afforded pure inositol in more than 90% yield:
on comparison with data in the literature (m.p. IR)[‘I,
this product proved to be chilo-inositol ( 6 e ) .
The fact that the symmetrical substitution pattern (7) was
not found in any of these substitutions indicates that the
993
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