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Carbene addition to the 2,3-bond of naphthalene and thermal Wolff rearrangement of bis(methoxycarbonyl)carbene
Temhedron Letters. Vo1.32, No.8, pp 995-998. 1991 Printedin Great Britain
CARBENE
ADDITION
WOLFF
00-20-4039/91 $3.00 + .oo Pergamon Press plc
TO THE 2,3-BOND
REARRANGEMENT
OF NAPHTHALENE
AND THERMAL
OF BIS(METHOXYCARBONYL)CARBENE
Martin Pomerantz* and Moshe Levanont Department of Chemistry, Box 19065, The University of Texas at Arlington, Arlington, Texas, 76019, U.S.A.
Abstract: Reaction of naphthalene with bis(methoxycarbonyl)carbene(2) produced thermally from dimethyl diazomalonate (1) gives 7,7-bis(methoxycarbonyl)-2,3-benzobicyclo[4.1.O]-hepta2,4-diene (4), dimethyl (I-naphthyl)malonate (5), dimethyl 2,3-bis(methoxycarbonyl)fumarate (6), the azine 7, 5,5,8,8-tetrakis(methoxycarbonyl)-2,3-benzotricyclo[5.1.0.04~6]oct-2-ene (S), 7,7-bis(methoxycarbonyl)-3,4-benzotropilidene (9) and the two dimers, 10 and 11. Product 9 represents the first time a carbene has been observed to add to the 2,3bond of naphthalene. The Wolff rearrangement derived products (10 and 11) demonstrate that this rearrangement can occur at temperatures as low as 120 “C and this is the first time product 11 has been observed.
Our interest in diazo compound and carbene chemistry2 and in particular in the reactions of dimethyl diazomalonate
(1) and the corresponding
carbene, bis(methoxycarbonyl)carbene
examine the reaction of 2 with naphthalene.
(2),3 has led us to
Reaction of 1 and 2 has been reported with only a few
aromatic molecules4-7 all of which are mononuclear benzene derivatives.
Also, it should be pointed out
that, as far as we are aware, carbene addition to naphthalene and substituted naphthalenes
have only
resulted in products of addition to the 1,Zbond. 8 In this paper we report on the reaction of carbene 2, formed thermally from 1, with naphthalene (3) and on the unprecedented formation of the product of the carbene addition to the 2,3-bond in 3. In addition we report on a heretofore unobserved dimer, 11, formed from a Wolff rearrangement of the carbene 2 followed by a lJ-dipolar
cycloaddition of a second carbene 2
to the ketene. Mixtures of 1 and 3 (weight ratio = 1:5; mole ratio = 1:6.2) were heated and the nitrogen evolution was followed by Hz0 displacement.
At 120 “C the reaction required about 24 hours while at 160 “C it
required about 2 hours to go to completion. naphthalene
was removed
by vacuum
At the completion
sublimation
of the reaction the majority of the
and the mixture
was analyzed
by GC, NMR
spectroscopy, HPLC, and melting point comparison with literature values, where available. The products obtained
were identified
as 7,7-bis(methoxycarbonyl)-2,3-benzobicyclo[4.1.0]hepta-2,4-diene
dimethyl
(1 -naphthyl)malonate
benzotricyclo[5.1.O.O@]oct-2-ene
(5),lo dimer 6,l 1 azine 7,3 5,5,8,8tetrakis(methoxycarbonyl)-2,3(8),9 7,7-bis(methoxycarbonyl)-3,4_benzotropilidene
dimers 1013 and 11.9 The product yields were approximately 4: 30-40%. 5: 5lo%, 5-lo%,
8: 5-15%, 9: 5-lo%,
(4),9
10: 25% and 11: 5%.
(9>12 and two 6: small amount, 7:
The ratio of products varied a little with the
temperature and the run, except that more of 5 was formed at the expense of the cyclopropanated product 995
996
CH30,C
CO&H3
+
;;;;*qNgCo2CH3 3
CH302C +=%O&H3 6
2
CO&H3
7
CH,O,C 8
m;z:;;:
CH302
+
OCH,
0CH3
9
11
10 4 at the higher rearrangement standard
temperatures. to 5 indicating
Indeed,
heating
200 “C for 15 resulted
in about 90%
that all or most of 5 in the reaction mixture comes from 4. Dimer 6 is the of 1 and we were able to observe
dimer which appears in most reactions
previously
4 at minutes
isolated and identified
it. 3 There is also some of the bis-cyclopropanated
azine 7 since we had product which results
from carbene addition to 4. The most significant
product in the product mixture is the benzotropilidene
an unprecedented
carbene addition to the 2,3-bond
formed thermally
from 4. Indeed the control experiment,
only 5 with absolutely decomposition
no 9 detectable.
in naphthalene
In addition,
(eqn.
9. It either results from
1) or it is a secondary
product
heating of 4 at 200 “C for 15 minutes, produced
heating
8 at 250 “C from 15 minutes showed no
of 8 and, once again, no 9. Thus 9 must be a primary product and, as far as we are aware,
this is thefirst time a carbene has been observed to add to the 2,3-bond of naphthalene. We also wish to point out the formation dimer
10.
followed
These dimeric by 1,3-dipolar
Two points are important
products cycloaddition
of the previously
must arise from a thermal to another
molecule
unknown lactone dimer 11 in addition to Wolff rearrangement
of the carbene
here. First is that the Wolff rearrangement
of the carbene
2 as shown
in Scheme
is occurring at temperatures
2 1.
as low as
997
Scheme
1
n
y-6
/
O=c=C’CO,CH,
0 . . II CH,O&-C-C-OCH, 2
2
f? CH,O-C-&CO&H, 2 /
\
i>CH,
bCH,
11
10 12O’C. Jones has previously
reported that, in the gas phase, the lowest temperature
at which this
rearrangement would occur was 280 ‘Cl4 and so we are observing this reaction some 160’ lower. Second, Maas and Regitz7>13 previously observed dimer 10 in a photochemical decomposition of 1, which they pointed out must involve a photochemical Wolff rearrangement, but they did not observe dimer 11. They pointed out, however, that dimer 11 would be the expected one based on other ketene cycloadditions and were surprised it was not observed. We have thus observed, albeit in low yield, the “expected” dimer and it is also not clear to us, as it was not clear to Maas and Regitz, why 10 is the more abundant cycloadduct. Finally, control experiments have shown that dimer 6 was completely stable when heated at 170 ‘C for two hours.
Azine 7, when heated at 170 “C for two hours, was reasonably
chromatography showed that the majority of it remained unchanged.
stable and gas
There was about l-2% of dimer 6, a
few other very small unidentified G.C. peaks but, as far as we can tell, none of the ketene cycloadducts 10 and 11. In addition, we can also say that 10 and 11 appear not to interconvert conditions based on observations,
under the reaction
to be reported later, that in some thermal reactions only dimer 11 is
formed while in other reactions ratios of up to 7: 1 for 1O:ll have been observed. Acknowledgements.
We thank the U. S. Department of Energy, Pittsburgh Energy Technology Center
and the Robert A. Welch Foundation
for financial support.
Purchase of the Bruker MSL-300 NMR
spectrometer and the Perkin-Elmer 2400 C,H,N analyzer with a grant from the Defense Advanced Research Projects Agency monitored by the Office of Naval Research is also gratefully acknowledged. thank Dr. Larry 0. Harding for some technical help. References 1.
and Notes
On leave from Indigo, Ltd., Rehovot, Israel, 1988-1989.
We also
998
2.
Pomerantz,
M; Rooney,
3.
Pomerantz
M.; Levanon,
4.
Wulfman,
D. S.; Lindstrumelle,
P. J. Org. Chem., 1988,53, M. Tetrahedron
4374.
Lett. 1990,31,4265.
G.; Cooper,
C. F. In The Chemistry
Groups: Patai, S., Ed.; Wiley: Chichester,
1978; Part 2, Chapter 18.
5.
Peace, B. W.; Wulfman,
D. S. Synthesis
1973, 137.
6.
Baron,
M. R.; Hendrick,
W. J.; DeCamp,
M. E.; Jones,
of Diazonium
M., Jr.; Levin,
and Diazo
R. H.; Sohn, M. B. In
Carbenes; Jones, M., Jr.; Moss, R. A., Eds.; Wiley: New York, 1973; Chapter 1. 7.
Maas, G.; Regitz, M. Chem. Ber. 1976, 109, 2039.
8.
Kirmse, W. Carbene Chemistry,
9.
Previously analyses
unknown
2nded.;
compounds
and the following
Academic:
New York, 1971; Chapter 10.
4, 8, and 11 gave satisfactory
carbon
and hydrogen
elemental
NMR spectra (6; CDC13). 4: ‘H: 3.00 (dd, 1H J = 8.7, 5.2 Hz), 3.38 (d,
lH, J = 8.7 Hz), 3.34 (s, 3H), 3.80 (s, 3H), 6.20 (dd, lH, J = 9.7, 5.2 Hz), 6.50 (d, lH, J = 9.7 Hz), 7.0-7.5
(m, 4H).
*3C: 30.8,
129.8, 130.0, 131.1, 164.8, 172.1. 3.77 (s, 6H), 7.15-7.23 169.1.
32.0,
35.0,
52.1,
53.1,
122.9,
127.4,
8: tH: 2.76 and 2.71 (AB q, 2H, J = 9.5 Hz),
(m, 4H). l3C: 26.7, 29.9, 41.9, 52.3, 53.0, 127.8,
11: IH: 3.49 (s, 3H), 3.87 (s, 3H), 3.90 (s, 3H), 4.25 (s, 3H).
99.2, 99.4, 160.8, 163.9, 165.0, 175.1.
D. S.; McGibboney,
W. Tetrahedron 12. Burdett,
14. Richardson,
3.42 (s, 6H),
t3C: 52.7 (2C). 54.0, 62.1,
3440.
B. G.; Steffen,
E. K.; Thinh, N. V.; McDaniel,
R. S., Jr.; Peace, B.
F. L.; Yates, D. H.; Swenton,
J. S. Tetrahedron
1974, 30, 2057.
K.; Hoge, R.; Maas, G.; Regitz, M. Chem. Bet-. 1977, I IO, 3272. D. C.; Hendrick,
(Received in USA 6 November
1990)
128.1,
128.6, 130.5, 165.9,
1976, 32, 1257.
K. A.; Shenton,
13. Eichhorn,
127.9,
4 had mp 76 “C, 8 had mp 175 ‘C and 11 was an oil.
10. Keach, D. T. J. Am. Chem. Sot. 1933,.55, 11. Wulfman,
127.6,
M. E.; Jones, M., Jr. J. Am. Chem. Sot. 1971,93,
3790.
CARBENE
ADDITION
WOLFF
00-20-4039/91 $3.00 + .oo Pergamon Press plc
TO THE 2,3-BOND
REARRANGEMENT
OF NAPHTHALENE
AND THERMAL
OF BIS(METHOXYCARBONYL)CARBENE
Martin Pomerantz* and Moshe Levanont Department of Chemistry, Box 19065, The University of Texas at Arlington, Arlington, Texas, 76019, U.S.A.
Abstract: Reaction of naphthalene with bis(methoxycarbonyl)carbene(2) produced thermally from dimethyl diazomalonate (1) gives 7,7-bis(methoxycarbonyl)-2,3-benzobicyclo[4.1.O]-hepta2,4-diene (4), dimethyl (I-naphthyl)malonate (5), dimethyl 2,3-bis(methoxycarbonyl)fumarate (6), the azine 7, 5,5,8,8-tetrakis(methoxycarbonyl)-2,3-benzotricyclo[5.1.0.04~6]oct-2-ene (S), 7,7-bis(methoxycarbonyl)-3,4-benzotropilidene (9) and the two dimers, 10 and 11. Product 9 represents the first time a carbene has been observed to add to the 2,3bond of naphthalene. The Wolff rearrangement derived products (10 and 11) demonstrate that this rearrangement can occur at temperatures as low as 120 “C and this is the first time product 11 has been observed.
Our interest in diazo compound and carbene chemistry2 and in particular in the reactions of dimethyl diazomalonate
(1) and the corresponding
carbene, bis(methoxycarbonyl)carbene
examine the reaction of 2 with naphthalene.
(2),3 has led us to
Reaction of 1 and 2 has been reported with only a few
aromatic molecules4-7 all of which are mononuclear benzene derivatives.
Also, it should be pointed out
that, as far as we are aware, carbene addition to naphthalene and substituted naphthalenes
have only
resulted in products of addition to the 1,Zbond. 8 In this paper we report on the reaction of carbene 2, formed thermally from 1, with naphthalene (3) and on the unprecedented formation of the product of the carbene addition to the 2,3-bond in 3. In addition we report on a heretofore unobserved dimer, 11, formed from a Wolff rearrangement of the carbene 2 followed by a lJ-dipolar
cycloaddition of a second carbene 2
to the ketene. Mixtures of 1 and 3 (weight ratio = 1:5; mole ratio = 1:6.2) were heated and the nitrogen evolution was followed by Hz0 displacement.
At 120 “C the reaction required about 24 hours while at 160 “C it
required about 2 hours to go to completion. naphthalene
was removed
by vacuum
At the completion
sublimation
of the reaction the majority of the
and the mixture
was analyzed
by GC, NMR
spectroscopy, HPLC, and melting point comparison with literature values, where available. The products obtained
were identified
as 7,7-bis(methoxycarbonyl)-2,3-benzobicyclo[4.1.0]hepta-2,4-diene
dimethyl
(1 -naphthyl)malonate
benzotricyclo[5.1.O.O@]oct-2-ene
(5),lo dimer 6,l 1 azine 7,3 5,5,8,8tetrakis(methoxycarbonyl)-2,3(8),9 7,7-bis(methoxycarbonyl)-3,4_benzotropilidene
dimers 1013 and 11.9 The product yields were approximately 4: 30-40%. 5: 5lo%, 5-lo%,
8: 5-15%, 9: 5-lo%,
(4),9
10: 25% and 11: 5%.
(9>12 and two 6: small amount, 7:
The ratio of products varied a little with the
temperature and the run, except that more of 5 was formed at the expense of the cyclopropanated product 995
996
CH30,C
CO&H3
+
;;;;*qNgCo2CH3 3
CH302C +=%O&H3 6
2
CO&H3
7
CH,O,C 8
m;z:;;:
CH302
+
OCH,
0CH3
9
11
10 4 at the higher rearrangement standard
temperatures. to 5 indicating
Indeed,
heating
200 “C for 15 resulted
in about 90%
that all or most of 5 in the reaction mixture comes from 4. Dimer 6 is the of 1 and we were able to observe
dimer which appears in most reactions
previously
4 at minutes
isolated and identified
it. 3 There is also some of the bis-cyclopropanated
azine 7 since we had product which results
from carbene addition to 4. The most significant
product in the product mixture is the benzotropilidene
an unprecedented
carbene addition to the 2,3-bond
formed thermally
from 4. Indeed the control experiment,
only 5 with absolutely decomposition
no 9 detectable.
in naphthalene
In addition,
(eqn.
9. It either results from
1) or it is a secondary
product
heating of 4 at 200 “C for 15 minutes, produced
heating
8 at 250 “C from 15 minutes showed no
of 8 and, once again, no 9. Thus 9 must be a primary product and, as far as we are aware,
this is thefirst time a carbene has been observed to add to the 2,3-bond of naphthalene. We also wish to point out the formation dimer
10.
followed
These dimeric by 1,3-dipolar
Two points are important
products cycloaddition
of the previously
must arise from a thermal to another
molecule
unknown lactone dimer 11 in addition to Wolff rearrangement
of the carbene
here. First is that the Wolff rearrangement
of the carbene
2 as shown
in Scheme
is occurring at temperatures
2 1.
as low as
997
Scheme
1
n
y-6
/
O=c=C’CO,CH,
0 . . II CH,O&-C-C-OCH, 2
2
f? CH,O-C-&CO&H, 2 /
\
i>CH,
bCH,
11
10 12O’C. Jones has previously
reported that, in the gas phase, the lowest temperature
at which this
rearrangement would occur was 280 ‘Cl4 and so we are observing this reaction some 160’ lower. Second, Maas and Regitz7>13 previously observed dimer 10 in a photochemical decomposition of 1, which they pointed out must involve a photochemical Wolff rearrangement, but they did not observe dimer 11. They pointed out, however, that dimer 11 would be the expected one based on other ketene cycloadditions and were surprised it was not observed. We have thus observed, albeit in low yield, the “expected” dimer and it is also not clear to us, as it was not clear to Maas and Regitz, why 10 is the more abundant cycloadduct. Finally, control experiments have shown that dimer 6 was completely stable when heated at 170 ‘C for two hours.
Azine 7, when heated at 170 “C for two hours, was reasonably
chromatography showed that the majority of it remained unchanged.
stable and gas
There was about l-2% of dimer 6, a
few other very small unidentified G.C. peaks but, as far as we can tell, none of the ketene cycloadducts 10 and 11. In addition, we can also say that 10 and 11 appear not to interconvert conditions based on observations,
under the reaction
to be reported later, that in some thermal reactions only dimer 11 is
formed while in other reactions ratios of up to 7: 1 for 1O:ll have been observed. Acknowledgements.
We thank the U. S. Department of Energy, Pittsburgh Energy Technology Center
and the Robert A. Welch Foundation
for financial support.
Purchase of the Bruker MSL-300 NMR
spectrometer and the Perkin-Elmer 2400 C,H,N analyzer with a grant from the Defense Advanced Research Projects Agency monitored by the Office of Naval Research is also gratefully acknowledged. thank Dr. Larry 0. Harding for some technical help. References 1.
and Notes
On leave from Indigo, Ltd., Rehovot, Israel, 1988-1989.
We also
998
2.
Pomerantz,
M; Rooney,
3.
Pomerantz
M.; Levanon,
4.
Wulfman,
D. S.; Lindstrumelle,
P. J. Org. Chem., 1988,53, M. Tetrahedron
4374.
Lett. 1990,31,4265.
G.; Cooper,
C. F. In The Chemistry
Groups: Patai, S., Ed.; Wiley: Chichester,
1978; Part 2, Chapter 18.
5.
Peace, B. W.; Wulfman,
D. S. Synthesis
1973, 137.
6.
Baron,
M. R.; Hendrick,
W. J.; DeCamp,
M. E.; Jones,
of Diazonium
M., Jr.; Levin,
and Diazo
R. H.; Sohn, M. B. In
Carbenes; Jones, M., Jr.; Moss, R. A., Eds.; Wiley: New York, 1973; Chapter 1. 7.
Maas, G.; Regitz, M. Chem. Ber. 1976, 109, 2039.
8.
Kirmse, W. Carbene Chemistry,
9.
Previously analyses
unknown
2nded.;
compounds
and the following
Academic:
New York, 1971; Chapter 10.
4, 8, and 11 gave satisfactory
carbon
and hydrogen
elemental
NMR spectra (6; CDC13). 4: ‘H: 3.00 (dd, 1H J = 8.7, 5.2 Hz), 3.38 (d,
lH, J = 8.7 Hz), 3.34 (s, 3H), 3.80 (s, 3H), 6.20 (dd, lH, J = 9.7, 5.2 Hz), 6.50 (d, lH, J = 9.7 Hz), 7.0-7.5
(m, 4H).
*3C: 30.8,
129.8, 130.0, 131.1, 164.8, 172.1. 3.77 (s, 6H), 7.15-7.23 169.1.
32.0,
35.0,
52.1,
53.1,
122.9,
127.4,
8: tH: 2.76 and 2.71 (AB q, 2H, J = 9.5 Hz),
(m, 4H). l3C: 26.7, 29.9, 41.9, 52.3, 53.0, 127.8,
11: IH: 3.49 (s, 3H), 3.87 (s, 3H), 3.90 (s, 3H), 4.25 (s, 3H).
99.2, 99.4, 160.8, 163.9, 165.0, 175.1.
D. S.; McGibboney,
W. Tetrahedron 12. Burdett,
14. Richardson,
3.42 (s, 6H),
t3C: 52.7 (2C). 54.0, 62.1,
3440.
B. G.; Steffen,
E. K.; Thinh, N. V.; McDaniel,
R. S., Jr.; Peace, B.
F. L.; Yates, D. H.; Swenton,
J. S. Tetrahedron
1974, 30, 2057.
K.; Hoge, R.; Maas, G.; Regitz, M. Chem. Bet-. 1977, I IO, 3272. D. C.; Hendrick,
(Received in USA 6 November
1990)
128.1,
128.6, 130.5, 165.9,
1976, 32, 1257.
K. A.; Shenton,
13. Eichhorn,
127.9,
4 had mp 76 “C, 8 had mp 175 ‘C and 11 was an oil.
10. Keach, D. T. J. Am. Chem. Sot. 1933,.55, 11. Wulfman,
127.6,
M. E.; Jones, M., Jr. J. Am. Chem. Sot. 1971,93,
3790.