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cis-Triazatris--homobenzene (cis-УBenzene TriimineФ).

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[I521 G. Wilke in: Ullmanns Encyklopadie der Technischen Chemie.
Urban iind Schwarzenberg, Miinchen 1963. 3rd. Edit.. Vol. 14. p. 776.
[I531 G . Wilke, 5. Bogdunorii, ef al., Brennst.-Chem. 4Y, 323 (1968);
Ind. Eng. Chem. 62, 34 (1970).
[I541 G. Lefebtire and I! Chaurin: Aspects of Homogeneous Catalysis.
C. Manfredi, Mailand 1970, Vol. I, p. 108.
[ 1551 K . Zirgler, Angew. Chem. 72,829 (1960); see also R. Sfreck,Dissertation, Technische Hochschule Aachen 1961.
[I561 A . W Langer, Jr., Symposium on New Routes t o Olefins. Division
of Petroleum Chemistry, Inc., Amer. Chem. SOC.,Boston Meeting, April
1972; G. Hmricr-OlitiPand S. OliaP, Angew. Chem. 82,255 (1970); Angew.
Chem. internat. Edit. 9, 243 (1970).
[I571 R . F . Mason, DOS 2234734 (1973), Shell International Research
Maatschappij.
[I%] W E . Billups, J . H . C r o s , and C . I/. Smrrh, J. Amer. Chem. SOC.
95, 3438 (1973).
[I591 W Brenner, P. Heimhach, H . J . H q , K.-J. Plonrr. and R. Schimpf,
Chimia 23, 274 (1969).
[ 1601 P . Heimbach, Angew. Chem. 78,983 (1966); Angew. Chem. internat.
Edit. 5 , 961 (1968).
[ 1611 P. Heimbach and R . SchimpA Angew. Chem. XU. 704 (1968); Angew.
Chem. internat. Edit. 7, 727 (1968).
[I621 R. Schimpfand P Heimbach, Chem. Ber. 103, 2122 (1970).
11631 P. Heimbach and U? Brmner, Angew Chem. 78,983 (1966); Angew.
Chem. internat. Edit. 5 , 961 (1966).
[I641 P. Hrimbach and R . Schimpf, Angew. Chem. 81, 186 (1969); Angew.
Chem. internat. Edit. 8, 206 (1969).
[I651 C. P. Brock, J . P. Collman, G . Dolcetti, P. H . Farnham. J . A . Ibers,
J . E. Lester, and C . A . Reed, Inorg. Chem. 12, 1304 (1973).
C 0M M U N I CAT1 0N S
cis-Triazatris-o-homobenzene (cis-"Benzene
Triimine")[**l
By Reinhard Schwesinger and Horst Prinzbach"'.
Directed nucleophilic substitutions of cis-trioxatris-o-homobenzene(cis-"benzenetrioxide")""' have given accessto a
series of potential precursors for the synthesis of aza-, thiaand phospha-analogous compounds ( I ) and the related
bishetero-bishomobenzene systems (2)[lb1.
osed for (6) and (7) because of the behavior of ( 5 ) with
univalent nucleophiles" b1 and is proved unambiguously
analysis of (7). Here it is noteworthy
by 'H- and 13C-NMR
that once more[' b1 all the cyclohexane-protons and
-carbon atoms can be assigned on the basis of heteronuclear double resonance experiments (Table
Three-fold reduction and elimination to give ( l o ) can be
achieved in one operation by known procedures"] (4.5 mol
of LiA1H4, tetrahydrofuran, 20'C, 10min). We have not
found any indication of formation of isomeric by-products.
The specificity of the reaction makes it probable, for steric
reasons and as required by our working hypothesis, that
the equatorial azide group on C-5 of (7) is reduced first
and that after inversion the monoaziridine (8) is the primary product, although it has not yet been isolated.
New possibilities also open up for construction of carbocyclic[2]and mixed cis-tris- and cis-bis-o-homobenzene derivatives (3jL31and (4)[41. Here we describe the preparation
X,Y,Z =-O-,-NR-,-S-,-PR-,-CR~R~of cis-triazatris-o-homobenzene(cis-"benzene triimine";
3,6,9-triazatetracyclo[6.1.0.0z~4.
05.7]nonane) (10) as the
first example of such syntheses starting from cis-"benzene trioxide" (5)[51.
Reaction of ( 5 ) with six equivalents of NaN3 in MgClz-buffered methanol (65 "C ; 48 h) affqrds crystalline 3,5,6-triazido-1,2,4-cyclohexanetriol(6) in 98 % yield ; tosylation
thereof with 4.5 equivalents of p-toluenesulfonyl chloride
(pyridine, 20"C, 14 days) gives the triester (7) in almost
quantitative yield. The chiro-inositol configuration is prop[*] Prof. Dr. H. Prinzbach and DipLChem. R. Schwesinger
Lehrstuhl fur Organische Chemie der Universitat
78 Freiburg, Albertstrasse 21 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
Anguw.
Chem. internat. Edit. f Vol. 12 (1973) f No. 12
The geometry and symmetry of ( 8 ) allow the sole route
leading to (10) by way of (9)[*l.
989
The triimine ( 1 0 ) separates from CHzCIz as colorless
crystals [45% yield calculated on ( 5 ) : not optimized] ;
it is very readily soluble in water or methanol, Iess readily
in ethanol and sparingly in methylene chloride, chloroform,
acetonitrile, acetone or tetrahydrofuran. (10) is thermally
stable up to ca. 150°C; when heated rapidly to ca. 200°C
it explodes.
For the singly (11) and doubly ( 1 2 ) protonated compounds in aqueous perchloric acid we obtained the pK,
values 6.42 and 2.71 (20"C), respectively. A pK, value
of cu. - 1.0 can then be calculated for the trication (13) by
extrapolation, but the true value is probably lower owing
to steric compression of the three inner hydrogen atoms.
The N ... Hinneidistance (cu. 2.35A) and the good agreement of the measured pK, values for ( 1 1 ) and ( 1 2 ) with
those estimated by means of model compounds make it
improbable that the conjugated acid (1 I ) profits significantly from a delocalization of the inner proton in the
sense of ( I 1 a)' I].
Comparison with aziridine discloses no unusual features
in the UV, 'H- or ' T - N M R or IR data of (10) (Table
k), due to the special relative arrangement of the three
Table 1. Physical properties of compounds (61, (7)and (10) [a].
(6)
142
(dec.)
281
(80)
4.80 ( b r s ; 1 OH)
5.35 ( b r s ; 2 OH)
68.8
5.8-6.5 (m, 6 H)
71.6
[cl
(7'1
154-155
274 (1850)
263 (2300)
227 (35 500)
2.1-2.7 (m. 12 H)
7.51 (s, 2 C H J
7.56 (s, 1 CH,)
5.08 (dd, H-1)
5.69 (dd, H-2)
6.41 (dd, H-3)
5.44 (dd, H-4)
6.07 (dd, H-5)
5 64 fdd. H-6)
[dl
(10)
[el
c Z Z O=400
J , , 2= 3.0
J,,,=10.5
J3,4= 9.5
J 4 , 5 =10.0
.15.6= 3.5
J , , = 4.0
146.3; 145.9; 145.3;
133.9; 132.0; 131.6;
13@4 ; 130.0; 129.8 ;
128.4; 1282; 127.9
(aromat. C); 21.7 (CH,)
75.7 (C-1)
74.5 (C-2)
61.9 (C-3)
78.6 (C-4)
60.9 (C-5)
61.3 (C-6)
[dl
7.55 [U,O]
7.62 (6 C - H); 9 39
( 3 N - H)
[dl
[a] Correct elemental analyses were obtained for (6). (7) and ( I O J .
[b] In ethanol.
[c] In perdeuterioacetone.
[d] InCDCI,.
[el IR (Nujol; C,Cl,): 3310 (NH), 3140, 3080, 1305, 1250, 1175, 1035,
1010, 984, 855, 826, 804, 750, 730 c m - ' ; m / e : 124; 123 ( M + ) ; 122; 107
( M t - N H z ) ; 95 ( M + - H C N H ) ; 81 (M'-C,H,NH,);
80. 68
( M t - H C N ; -HCNH); 67 (100%; M t - 2 H C N H ) ; 61.5 (M2+);
54;
41 (Mf-2C2H,NH); 28 (HCNH).
aziridine rings in the latter; and in this respect trioxa( 5 ) and triaza-o-trishomobenzene (10) behave similarly.
This similarity is emphasized by the mass spectra of ( 5 )
and (10) which show much correspondence in their fragmentation pattern and relative intensities (Table 1)['41.
+ H@
#
-H@
Received: June 25, 1973 [Z 879 IE]
German version: Angew. Chem. 85,1107 (1973)
Publication delayed at authors' request
[I]
a) E. Vogef,
Altenbach, and C -D. Sommerfefd, Angew. Chem.
84,986(1972);Angew.Chem.
internat. Edit. 11,939(1972),R. Schwrsrngrr
and H . Prinzbach, Angew. Chem. 84,990 (1972): Angew. Chem. internat.
Edit. 1 1 , 942 (1972): b) R. Schwra.$ingrr, H . Fritz. and H . Prinzbach,
Angew. Chem. 85,1110(1973);Angew. Chem. internat. Edit. 12,993 (1973).
[2] H . W Whitlock, Jr. and P . F . Schatz, J. Amer. Chem. SOC. Y3,
3857 (I97 I).
[3] H. Prinzbuch and D.Stusche, Angew. Chem. 82, 836 (1970); Angew.
Chem. internat. Edit. 9, 799 (1970).
[4] D. Sftwrhr, M . Brruningrr, and H . Prinzhuch. Helv. Chim. Acta
85, 2359 (1972).
990
Angew. Chem. internat. Edit. 1 Vof. 12 (197'3) No. 12
[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
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