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Cycloadditions to Derivatives of Oxaquadricyclanes (Bishomofuran).

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I
(9al
187
108
1
232
230
1
24800 [a]
I9 100 [a1
(96)
1
[4] C. D. Smith, J. Amer. chem. SOC. 88, 4273 (1966); H. Prinzbach, M . Argiielles, P. Vogel, and W. Eberbach, Angew. Chem.
79, 1103 (1967); Angew. Chem. internat. Edit. 6, 1070 (1967);
H . Prinzbach, P. Vogel, and W. Auge, Chimia, 21, 469 (1967);
H . Prinzbach, W. Eberbach, M . Thges, and W. Auge, unpublished.
[ S ] D . Hunkler, Diploma Thesis, Universitat Freiburg/Brsg.,
2.62 (4,s) [ h ]
6.24 (12,s)
1965.
2.66 (3,s) [h]
3.66 (2,s)
6.18 (3,s)
6.20 (3,s)
6.27 (3,s)
[6] S. Sure1 and E. Breuer, J. Amer. chem. SOC.81, 6522 (1959).
chem. SOC. (London)
17) D . Bryce-Smith and J . E. Lodge, .I.
1963, 695; A. C. Cope and .I. E. Medi, J . Amer. chem. SOC.89,
1883 (I 967).
[8] J . Sauer, Angew. Chem. 78, 233 (1966); Angew. Chern.
internat. Edit. 5, 211 (1966).
I t is doubtful whether the bishomocyclopentadienone system
(-5) has the same importance for the synthesis of derivatives
of cyclooctatetraene as cyclopentadienones have for the
preparation of substituted benzene derivatives [81. Experiments with cycloctatetraene, methyl 1,2-dimethylcyclopropene-1-carboxylate, and dimethyl 1 -cyclobutene-1,2-dicarboxylate as dienophilic reagents for (5a) did not give decisive
results, even under drastic conditions.
Received: August 18th. 1967
[Z 601b IEI
German version: Angew. Chem 79, 1102 (1967)
[*I Prof. H. Prinzbach and Ing. chirn. dipl. J. Rivier
Universite de Lausanne, Laboratoire de Chimie orkanique
3, Place du Chiteau
CH-1000 Lausarine (Switzerland)
Cycloadditions to Derivatives of Oxaquadricyclanes
(Bishomof wan) 1
By H . Prinzbach, M . Argiielles, P. Vogel, and W . Eberbach [*I
The tetracyclic ethers (2) are readily accessible from oxanorbornadiene derivatives ( I ) by photochemical valence isomerization and can be pyrolysed to oxepins (3) under very
mild conditions[*]. We have used the strain energy indicated
by this pyrolysis of system (2) to advantage for a series of
cycloadditions. In the temperature region where the change
(2) + (3) plays only a subordinate role [small proportions
of (6) can be separated by crystallization], the tetracycles
(2) afford 1 : 1 adducts with reactive dienophiles.
I
1
(8)
(a), R = K' = H,
(b), R = R'= H,
R2 = C02CH3
H2 = H
(C), R = R
' = CH3, R2 = COZCH3
(d), R = E l = CH3, R2 = H
(11 Part XI1 of the series "Photochemistry of Cyclohexadienes".
Part XI. - H . Prinzbnch and J . Rivier, Angew. Chem. 79,1101.
(1967); Angew. Chem. internat. Edit. 6, 1068 (1967).
[2] H . Prinzbnch and J. Rivier, Tetrahedron Letters 1967,3713
I31 F. D. Marlgo and J . H . Schachtschneider, J. Amer. them.
SOC.89, 2484 (1967); H . Hogeveeit and H . C. Volger, ibid. 89,
2486 (1967).
.
.
1070
For this purpose, the bishomodiene (2) is heated with a fiveto ten-fold excess of dimethy lacetylenedicarboxylate (DMA),
methyl Propiolate (MP), or maleic anhydride (MA). Depending upon the substituents in (2) and the reactivity of
the dienophile, temperatures between 80 and 110°C and
reaction times between 30 min and 9 h are necessary. The
Angew. Chem. internat. Edit. 1 Vol. 6 (1967)
No. 12
adducts (7) and (9),’(10) are obtained in good t o very good
yield. The physical data relevant t o proof of structure are
given in the Table (31.
That addition to (2) occurs at positions 214 [giving (7) or ____
(9)/(IO)],and not, as with the isocyclic analogues[11 and
their 3-methylene
and %OX0 derivatives 111, at positions
6/7 [to give (8) or ( I l ) / ( l 2 ) ] ,is shown, at least for (7b) and
1 Molecular
uv
Amax
239--240
234
240
234
199.5
234 (S)
f 100)
215-219
230
5100
[Dzl--ilOai
2 16-2 19
230
5100
ilob)
177.5
234 ( S )
lD,I--I9n)
NMR
(i,TMS
10) Ibl
M.P. ( “ C )
4.9s ( 2 . 9
6.1 I (6,s)
6.72 (3,s)
6.81 (2,s)
3200
310
4.95 (2,s)
6.11 (6,s)
6.81 (2,s)
4800
336
6.07 (6,s)
6.78 (2,s)
6.81 (2,s)
8.37 (6,s)
~~
157-158
(70)
230(br.s)
80
(761
11400
fa1
352
2100
7 400
Ial
265 (s)
218
294
4.95 (2, S ) [a1
6.13(12,S)
6.91 (2, S )
2.78 (1,D). J = 2.0 Hz
5.05 (1,s)
5.17 (l,D), J - 2.0 H z
6.10 (3,s)
6.15 (3,s)
6.20 (3,s)
7.20 (2,s)
~
_
1
_
_
5 . 0 0 (2,M)
6.08 (6,s)
6 IO(2,M)
6.65 (2,s)
310
5.00 (2,s)
6.08 (6,s)
6.65 (2,s)
______
iidi
226 ( s )
106
(7r)
1
I
380
9900
[bl
I
1
6.18 (6,s) [c. d l
6.19 (6 S)
6.96 (2,s)
8.42 ( 6 3 )
I 2.93 (1,s)
6.12 ( 6 3 )
6.19 (3,s)
7.12 (2,s)
8.36 (3,s)
8.47 (3,s)
Ial I n CHIOH. - [bl I n isooctane. - [c] I n CDCI3. - [d] In CCI4
( I O a ) , as follows: The alternative formula (86) is excluded
by the vicinal coupling, shown in the N M R spectrum of the
M P adduct (7b), between the olefinic proton (T = 2.78) and
the proton R in the a-position t o the bridging oxygen
atom (T = 5.17). Similarly, formulae (11)ifZZ) are excluded
by the coupling existing in the MA adduct (IOa) between
the protons introduced by MA (7 = 6.10) (assigned with the
aid of [Dzl-MA) and the bridgehead protons R/R’ (7 = 5.00).
Evidence in favor of the structure (9a) (which then becomes
probable for the second M A adduct) and against ( I l a ) /
(120) (61 is provided by the singlet character of the signal of
the MA protons (7 = 6.72), which also proves the excarrangement of the anhydride ring in (
9.). A second indication of the correctness of this assignment is the finding
that the signals of the M A protons cis to the 0 atom in ( I O U )
are shifted paramagnetically by 0.62 ppm in relation t o those
of ( 9 4 171.
5300
_
308
336
6.08 (6,s)
6.38 (2,s)
6.64 (2,s)
8.32 ( 6 . 9
[a1 In C H K N . - [bl In CDCli
Received: August 18th. 1967
[Z 601c I€]
German version: Angew. Chem. 79, 1103 (1967)
[*I Prof. H. Prinzbach, Ing. chim. dipl. M. Arguelles,
Ing. chim. dipl. P. Vogel, and Dr. W. Eberbach
Universite de Lausanne, Laboratoire d e Chimie organique
3. Place du ChBteau
CH-1000 Lausanne (Switzerland)
[ I ] Part XI11 of “Photochemistry of Cyclohexadienes”. - Part
XII: H . Piinzbach and J. Rivier, Angew. Chem. 79,1102 (1967);
Angew. Chem. internat. Edit. 6, 1069 (1967).
121 H . Prinzbach, M . Arguelles, and E. Druckrey, Angew. Chem.
78, 1057 (1966); Angew. Chem. internat. Edit. 5, 1039 (1966);
H . Prinzbach, Chimia 21, 194 (1967); H. Prinzbach, P. Vogel,
and W . Auge, Chimia 21,469 (1967); E . Payo, L. CortPs, J . Mantecon, C . Rivas, and C . de Pinto, Tetrahedron Letters 1967, 2415.
131 Elemental analyses are available for all the new products.
Experiments are being carried out on photochemical isomerizalion of (7u) and on deowygenation [4] of the adducts (6) and (7).
[4] W. Grimme and B. Hoas, unpublished work, cited by E. Vogel and H . Gunther, Angew. Chem. 79, 429 (1967); Angew.
Chem. internat. Edit. 6, 385 (1967).
151 We thank Dr. B. WiNhalm, Firmenich Co., Geneva, and
Dr. H. Achenbach, Universita t Freiburt/Brsg., for the mass
spectra.
(61 H. Weitlcamp and F. Korte, Tetrahedron Suppl. No. 7, 75
(1966); I . Fleming and D . H. Williams, Tetrahedron 23, 2747
(1 967).
171 M. A . Battiste and M . E. Brenrmn, Tetrahedron Letters 1966,
5857; S . Winstein, P. Carter, F. A . L . Anet, and A . J . R . BGurn,
J . Amer. chern. SOC.87, 5247 (1965).
Formation of Selenanthrene from Diphenyl Selenide
and of Dipotassium Triimidotellurite from
Diphenyl Telluride
By 0. Schmitz-DuMont and B. Ross[*]
Whereas diphenyl sulfide S(C6H& in liquid ammonia
containing KNHz undergoes partial ammonolysis with
formation of C ~ H S S Kand aniline [I], reaction of diphenyl
selenide Se(CsH& (I) under the same conditions leads t o
selenanthrene(2),the yield thereof depending o n theamount of
KNHz present; byproducts are K2Sex(x>2) and CsHsSeK.
Angew. Chem. internat. Edit.
/ Vol. 6 (1967) / No. 12
1071
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cycloadditions, bishomofuran, oxaquadricyclanes, derivatives
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