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Monohetero Derivatives of Bis- and Trishomobenzenes.

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=
: I/z ( J x , , y + J y , , x ) = t 0.85 Hz[**J. The magnitude
of Jayand Jaxsuggests a large 5-it overlap and therefore
a large external H-C-Ha
angle.
Jx,y,xyr
Received: July 27, 1970
IZ 257 IEI
German version: Angew. Chem. 82, 810 (1970)
['I Dr. R. Bloch, Dr. P. Le Perchec, and Prof. Dr. J. M. Conia
products are the all-cis-pyrazolines (5a), (6a), and (6b)
respectively.
The monoadduct (5a) crystallizes out when diazomethane
(0.5 g, 12 mmoles) is added t o a solution of (3a) (2.1 g,
10 mmoles) in ether (100 ml) in a yield of 65-70 %. The
bisadduct (6aj was prepared by the same method as was
previously used for ( 6 6 ) 151, i. e. by precipitation with ether
from a mixture of (3a) (1 g, 4.7 mmoles) and diazomethane
(0.42 g, 10 mmoles) in dichloromethane (100 ml) that has
been allowed to stand for 72 h (yield 65-70 %).
O n photolysis (300 ml solvent, -2OoC, Hanau Q 81 high
pressure mercury lamp), (5a) (0.6 g, 2.4 mmoles; methanol;
2 h) affords the oxabishomobenzene (7a) (80-90 %); (6a)
and (6b) (4.0 mmoles; acetone; 2 h) give (8a) and ( 8 b )
(60-65 %), (9a) and (96) (5-10 %), and ( I O U ) and ( l o b )
(20-25 %), respectively, after thin-layer chromatography
(silica gel/benzene).
The product ratio in the photolysis of ( 6 a ) and (6b) varies
with the solvent. In methanol the amount of (9a) and (9b)
is increased considerably a t the expense of (8a) and (8b).
Laboratoire d'Etude des Carbocycles,
Universit6 de Paris-Sud, Biitiment 490
F-91 Orsay (France)
111 N . C . Baird and M . J . S . Dewar, J. Amer. Chem. SOC.89,
3966 (1967); J. Chem. Phys. 50, 1262 (1969); I. J . Miller,
Tetrahedron 25, 1349 (1969).
[2] F. Bleiholder and H . Shechter, J. Amer. Chem. SOC.86,
5032 (1964); J . K . Crandall and D . R . Paufson, ibid. 88, 4302
(1 966).
[3] P . Le Perchec and J . M . Conia, Tetrahedron Lett. 1970,
1587; Ya. M . Slobodin, V. E . Maiorova, and A . P. Khitron, Zh.
Org. Khim. 5, 851 (1969).
[4] R . Bloch, J . M . Dedieu, and J . M . Conia, Bull. SOC.Chim.
Fr. 1970, 1875.
[* * ] Solvent Cc14; external standard Si(CH&.
Monohetero Derivatives of Bis- and
TrishomobenzenesI1l [**I
The bishomobenzene (7a) adds diazomethane [0.5 g, 2.2
mmoles of (7aJ in ether (100ml); 0.13 g, 3.1 mmoles of
CHzNz; 1 week; 10°C] to give a mixture of pyrazolines,
which is photolyzed directly (methanol; 2 h). The crude
product consists of (9a) (12%), (IOa) (25%), and ( I l a )
(27 %) (separated by preparative thinlayer chromatography;
silica gel/benzene).
The structures of the new compounds prepared were confirmed by elemental analysis and spectral data (see Table).
In the case of the pyrazolines (5a), (6a), and ( 6 b ) , the ex-
By Horst Prinzbach and Dieter Stusehe[*]
In this communication we report o n the compounds (IOa),
( l o b ) , and ( I l a ) , which are the first isolable monohetero
derivatives of the trishomobenzene series ( l a ) and ( I b ) ;
we have also prepared (7a), (9a), and (96) as hetero
derivatives of the bishomobenzene series (2) 121.
4,5-Bis(methoxycarbonyl)oxepin (3n) 131 and -N-tosylazepine (3b) 141 add diazomethane, reacting as the bicyclic
structures (4a) and (46)151, respectively; the preferred
(3)
(4)
I
bBl
C
D
B
A
A'
f 71
I
IhV
w:t lhy
pyrazoline mixture
C
B
A
A'
R
=
A'
A
+
(8)
BA
(9)
C02CH3, A=B=C=D=H, M e
i
=
A'
CH3
(a),X = 0
(b), X = N-Tosyl
Angew. Chem. internat. Edit.
Vol. 9 (1970) / No. 10
799
NMR(7)
Cpd.
M.p. ( " C )
7.43(1,M)
JBC - 2.5 Hz
J B D = 8.0 Hz
i5ai
112- 114
(dec.)
6.63 (2, M) [a]
J A A ~= 3.8 Hz
JAB = JA'B' = 4.6 Hz
(64
135-136
(dec.)
2.44(1,M)
4.85 (1,M)
J c ~ = 1 7 . 5Hz
1-
5.31 (1,M)
322 ( 180)
232 (5900)
5.03 (2, M)
7.10 (2, M)
JBB,
0.1 Hz
JAB, = J A B = --0.2 Hz
5.53 (2, M)
JCD = J ~ D =, 17.0 H z
JBC - JB'c, = 8.0 H z
JBD = J B ' D , = 5 . 5 Hz
<
321 ( 360)
~
6.65 (2, M) [a]
JAN = 6.7 Hz
JAB = J A ~ B .= 6.3 Hz
5.25 (2, M)
JBC
8.30(1, M)
3.03 (1, D)
=
JCD
JB'C,
5 85 (2, M)
=
=
Jc D,
7.5 H z
=
8.00 (1, M)
17.0 Hz
JBD = JB'D,
5 5 Hz
=
322(
272(
262(
254(
4001
510)
740)
680)
9.33 (1, M)
J B D = 5.7 Hz
JBC= 9.3 Hz
~
(84
68-69
6.77 (2, M) [b]
7.0 (2, M)
8.2 (2, M)
9.1 (2, M)
239 (4900)
(86)
118.5-119
6.60 (2, M) [a]
6.9 (2, M)
8.15 (2, M)
9.0 (2, M)
273( 950)
267 (1220)
261 (1610)
€245 = 3800
(90)
82-83
ca. 6.3
6.88
(9b)
134
6.53 (1, M)
(100)[el
76.5-77
6.57 (2. M) [c]
J A =~4.1 Hz
JAB = J ~ B=T4.9 H z
1 6.98
6.6--7.0 (2, M) [c]
JAM
[a] I n CDCl3.
=
4.1 H z
Ibl I n
C6H6.
I
HB+HC
Me
8.0-8.2 (2, M) 7.77 (3, S)
I
9.33 (1, M)
HB+HC
Me
7.9-8.3 (2, M) 8.02 (3, S)
9.25 (1, M)
I
8.30 (2, M)
JBB,
0.1 Hz
€229 =
JA'B = -0.2 Hz
8.80 (2, M)
9.65 (2, M)
JCD = J C ~ D=
. 5.2 Hz
JBC = JB'c, = 9.8 Hz
JBD = J B ~ D .= 5.9 Hz
8.25 (2, M)
J B B < 0.01 H z
JAB' = J A . B = -0.2 H z
8.75 (2, M)
9.63 (2, M)
JCD = J c ~ D , = 5.6 H z
Jgc = JB,c, = 9.8 Hz J B D = J B ~ D=~6.3 Hz
273 (1000)
267 (1000)
<
JAB,
=
I
8.0-8.6 (4, M)
JAB = 4.9 Hz JAB, = 0.8 Hz JBC = 9.6 Hz
J A B * =1.4Hz J A B < O . l H z J ~ , c , = 9 . 1 H z
J B B ~ 0.1 Hz
<
ICI
I
In CC14.
Id1 In CH3OH.
[el Molecular ion m/e 238.
9.20 (1, M)
JCD = 3.7 Hz
JBD = 5.7 Hz
If] Molecular ion
8.90 (1, M)
Jc~'=3.8Hz
JB'D, = 6.4Hz
€230 =
200
250
m/e 391.
[3] H. Prinzbach, M. Arguelles, and E. Druckrey, Angew'
pected n + K* bands and the typically large coupling
Chem. 78, 1057 (1966); Angew. Chem. internat. Edit. 5 , 1039
constants of the methylene protons were observed. The
(1966).
spatial relationships of the three-membered rings in (7a),
[4] R . Kitzing, R . Fuchs, M . Joyerix, and H. Prinzbach, Helv.
(IOa), ( l o b ) , and ( I I a ) , and hence those also of the rings
in (5a), (6a), and (6b), follow from JAB and J A , B , [ ~ ~ . Chim. Acta 51, 888 (1968).
[5] H. Prinzbach, D. Stusche, and R . Kitzing, Angew. Chem.
Compound (8a) is identical with the partially hydrogenated
82, 393 (1970); Angew. Chem. internat. Edit. 9, 377 (1970).
adduct of dimethyl acetylenedicarboxylate and oxepin 171.
161 In the NMR spectra of compounds ( 6 a ) , (6b), (IOU), and
Its formation from (6a) affords additional proof of the
( l o b ) , the signals of the protons HA, HA', HB, and H B give
cis arrangement of the three hetero rings in (6a).
AA'XX' systems which were evaluated: a) (IOU) with the
The crystalline trishomobenzenes (IOU), ( l o b ) , and ( I l a ) ,
NMR program NMREN 1, QCPE 34; we thank Dip1.which are stable a t room temperature, differ considerably
Chem. H. H. Limbach for his assistance; b) ( 6 a ) , ( 6 b ) , and
in their thermal behavior. Whereas ( I l a ) remains un( l o b ) with the NMR program LAOCN 3, QCPE 111.
changed a t temperatures up t o about 16OoC, ( I O a ) and
[7] P . Wiirsch, Dissertation, Universite de Lausanne 1970.
(106) isomerize smoothly a t 7OoC t o form hetero-2,5,8[8] H. Prinzbach and D . Stusche, to be published.
cyclononatriene derivatives 181.
Received: August 6, 1970
[Z 256 IE]
German version: Angew. Chem. 82, 836 (1970)
[*I Prof. Dr. H. Prinzbach and Dip1.-Chem. D. Stusche
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.
[l] Photochemical Transformations, Part 40. - Part 39:
G. Kaupp and H. Prinzbach, in press.
[2] W . R . Roth and B. Peltrer, Angew. Chem. 76, 378 (1964);
Angew. Chem. internat. Edit. 3, 440 (1964); J . Zirner and
S . Winstein, Proc. Chem. SOC.(London) 1964, 235.
800
Stable Complexes of Bullvalene [**I
By Rudolf Aumann [*I
Bullvalene[ll ( I ) is a notorious case of a molecule with
degenerate valence isomerization, in which all the H atoms
are magnetically equivalent on the N M R time scale a t
temperatures above 80 "C. This degeneracy disappears with
introduction of a substituent into ( 1 ) . In this connection,
particular interest attaches to the study of metal complexes
Angew. Chem. internat. Edit.
Vol. 9 (1970)
1 No. 10
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