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An Expeditious Synthesis of Heptalene from Naphthalene via a Bis(bicyclo[1.1.0]butane) Intermediate

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vacuum afforded the previously unknown 33-dihydroheptalene (b.p. 44--45"C/ca. 10 torr) having a purity of 95%
(yield 35-40%). At this stage (8) is sufficiently pure for use
in further reactions. but if necessary it can be purified by
crystallization from pentane at low temperature, albeit at the
expense of loss in yieldl'l. Conversion of (8) into ( I )could be
accomplished, as already described for the isomeric dihydroheptalenesl"'), by dehydrogenation-hydride abstraction with
triphenylmethyl hexafluoroantimonate in dichloromethane
and deprotonation with trimethylamine (yield 88-93% and
55 -60'4, respectively). The hitherto unknown intermediary
heptalenium salt was isolated, m. p. 155 "C (decomp).
Another practical heptalene synthesis, also starting from isotetralin, has been developed independently by Paquette and
co-workersfhl.
An Expeditious Synthesis of Heptalene from Naphthalene uiu a Bis(bicyclo[l.l.O]butane) Intermediate'**'
By Leo A . Paquette, Alan R. Browne, and Ernest Charnot"'
T o the present time, two syntheses of heptalene ( I ) have
been
and access has been gained to a few derivatives. While both routes to (1) are elegant in their conception,
they are lengthy, and the hydrocarbon has therefore remained difficultly accessible. As a result, theoretical predictions often have preceded the execution of experimental
work in this field.
Br. .Br
Table I . Physical data of compounds (2). (3). 14). (7). and (8)
/I).m. p. 1x5 C (decomp.). U V (cyclohexane): A,,,.,, = 2 X h nm ( b = 17200). 329
(21 100).443 (XX00): 1K (CCI,): 2058. 2040. 1988. 1975 cni ' ( C 0). 'H-NMK
(C<D,,):6 = 2 . 4 4 It. H-4, 9). 2.9X (d. H - I . 6 ) . 4.60 (in.H-2. 7). 4 79 (m. H-3. 8).
5.46 (d. H-5. 10) [a]
/ 3 j . m . p 105'C. U V (ethanol): A,,,.,,=290nm ( t = 15x00). 362 (5100).4X5 (XhO):
I K (Cslt- I670 cm ' (C 0): 'H-NMR [CDCI,: room temperature (region of
rapid exchange)]. 6= 6.1 I (d. H-5. 10). 6.65 (m. H-3.4. X. 9). 7.0X (d. H-2. 7). 9.X0
(5.
2 CHO)
(41. m p. 90- 91 C: U V (ethanol): A,,,,,=271 nm ( > = 1700). 334 (4300). 420
(790. jh). I K ( G I ) . 1720 cm ' I C 0): ' H- NM R r[D,]-tetrachloroethane:
-t 110°C (region of rapid exchange)): S = 3 70 ( 5 . 2 CH,). 6.13 (m. H-5. 10). 6.50
(m. H-3.4. X. 9). 7.15 (d. H-2. 7)
(7). h p 52 -53 C /O 4 torr: 'H- NM R (CDCI,). 6=0.22 (m. H-4. 4. 10. 10). 0.95
( i n . H-3. 5. 9 1 1 ) . 2.1 (m.H-2. 2.6.6. 8. 8. 12. 12)
(8). m.p. 3 3 - 34 C: U V (cyclohexane). A ,,,,,. = 2 3 0 nm ( t = 4 0 9 0 0 . sh). 234
(43 100). 299 (7700). 'H -N M K (CCI,). 8 = 2 . l h (1. J z 6 . X H7. H-3. 3. X. X). 5.50
6.X H r . H-2. 4. 7. 9).h.25 (d. J = 10.2 H r . H-I. 5. 6 . 10)
[a] A closer study of the ' H - and "C-NMR spectra of this complex has shown
that the douhle honds which are localized at room temperature. iis in structure
(I). migrate at higher temperature with siniultaneotis 1.2-shift of the Fe(CO),
groups. the reactant and product being in the relationship ofenantiomers: cf. the
dynamic hehabior of cyclooctatetraene(tricarhony1iron):F. A . ('orron. D L.
Hinwr, J Am Chem. Soc. YX 1413 (197h).
[Z 237h It;]
I'iihlication delayed at authors' requeht
German ver\ion' Angew. Chem. 01. 579 (1979)
Keceived. February 22. 1979
CAS Registry nunihrrr( l ) . 257-24-9, 1-71. 70629-73-1. ( 3 ) . 70576-00-0. ( 4 ) . 70576-01-1. (7). 70576-02-2:
((57, 70576-03-3: hen7~lideneacet~ine(triciirbon~lir~in).
61216-69-1: IF). 493-04-9:
(6).
70576-04-4:
rt-un\.rruns-I 3-oxapenti1cyclolS.5. I 0' '.I)'' 0" "Itridecane.
70592-72-2
[I]a ) H J Dunhen. Jr.. D.J . Berrelli. _I.
Am Chem. Soc. 83. 4659 (1961): E. Vop e / . H. Kunigsho/en. J. Wu.%.wn.K . Mullen. J F. M. Orh. Angew. Chem. 8 6 .
777 (1974): Angrw. Chem. Int. Ed Engl. li. 732 (1974): h ) I f . J. Lindner, 8.
K i r ~ h k ehid.
.
A??. 123 (1976) arid IF, I06 ( I976): J Srcgwnunn. H. J. Lindner.
Tetrahedron Lett. lY77. 25 15.
121 E. V&.
J Ippen. Angew. Chcm. 86. 77X (1974): Angew. Chem. Int. Ed.
I!ngl /I. 734 (1974): L' V o g d . F. Hogrefe. !hid. 86, 779 (1974) and 13. 735
(1974). K. Hujuer. f/. Diehl. H . U . S i r r . ihid XX. I21 (1976) and /.i104
.
(1976)
(31 J Srqemunw. H. J. Luidner. J . Organomet. Chem 166, 223 (1979).
141 Review: A. J Birch. 1. 11. Jenkins in H . Alpcr. Transition Metal Organometallic\ in Organic Synthe\is. Academic Pre\s. New York 1976. V o l . 1. p. I
[ 51 E. J . ( ' w e ) . . N W. Gi/mun. B. E. Gunmi. J . Am. Chem. Soc. UO1. 5616
(IYOX)
[ b ]J lppm. Dissertation. Univerbitat K o l n 1915. It has meanwhile been found
that the tetrachloro analog of / 6 j , obtained hy reaction of- the 4a.Xa-epoxide
ol.irotetraliii IS/ with chloroform and \odium hydroxide under phase-transfer
conditions In1.p. 125 "C (decomp.): yield 75- XO%l. can he advantageously
he w e d instead of ( 6 ) .
171 T h e conbersion of (7) into (8) is similar to the final step i n the synthesi? ofoctalene. \ee E. Vogc/. H: V. Runzheimer. F. Ifogreffr. B. Rnower. J . Lei. Angew. Chem. 89.909 (1977): Angew. Chem. In1 Ed. Fngl. 16. 871 (1977).
[XI I-. A. Pugue/re. A. R. Bruicnr. E C'bomor. Angrw Chem. 91. 5x1 (1979): Angew. Chem Int. Ed. tngl. l X 546 (1979)
546
0 Verlrrg Chemie. CmbH. 6940 Weinheim. /Y7Y
In this communication we describe an efficient six-step
conversion of naphthalene to (f). The new methodology capitalizes on the regiospecificity of two-fold intramolecular carbene insertion to give (4)13)and the ability of silver([) ions to
promote the isomerization of bicyclo[ 1.1.O]butanes to ringopened conjugated dienes141.
Addition of dibromocarbene to tetrahydronaphthalene
(isotetralin) (Z)lsl using a modification1"I of Vogers procedure''] afforded bisadduct (3) (38%) admixed with the corresponding mono- (12%) and tris-adducts (0.8%). These products could be efficiently separated by recrystallization: resubmission of the monoadduct to the same reaction conditions
returned additional (3) in 72% yield. When the tetrabromide
(3) was treated with 2 M ethereal methyllithium at 0-25 "C
for 3 h, the colorless bis(bicyclo[ 1.1.O]bu tane) (4) was obr
tained in 59% yield ufrer molecular distillation (80-100 "C/
0.3 torr). The 'H-NMR spectrum of (4) (C,D,) contains two
series of multiplets at 6=6.03-5.06 (2H) and 2.46--1.11
(10H) while its I3C-NMR exhibits 12 lines, thus demonstrating the isomeric homogeneity of the hydrocarbon. The definitive structural assignment follows from the Ag +-catalyzed
isomerization of (4) exclusively to 1,6-dihydroheptalene (S)
and catalytic hydrogenation of this pentaene to cis-bicycl0[5.5.0]dodecane~~~.
Whereas (5) belongs to the CZhpoint
group, the 1.10 isomer (6) has C2- symmetry; a clear distinction between them becomes apparent upon "C-NMR analysis (in CDCI,) which reveals the six lines ( F = 132.8, 131.0,
125.6, 123.6. 123.0, and 33.6) demanded uniquely by (5).
[*I
Prof. Dr. L A Paquette. D r A K . Browne. L)r E Charnot
Evanr Chemical Laboratories. 7 he Ohio State University
Columhus. Ohio 43210 ( U S A )
[**I
We acknowledge the financial support of the donors to the Petroleum Kcsearch Fund. administered hy the American Chemical Society. the National
Cancer Institute. and an Ohio Stale University tiraduate School postdocturiil
fellow\hip award tu A R H.
(15 70- OX</ 7Y /(I 70 7-0546 $ 0_7,50/0
A n g e u Chem. I n [ . Ed. €fig/. 18 l l Y 7 Y j No. 7
The regiospecificity observed in the carbene insertion step
to give ( 4 ) would appear to have its origins in the geometric
constraints generated by one bicyclobutane unit upon formation of the second. Molecular models reveal that closure of
either the central or peripheral carbene produces conformationally rigid intermediates in which the second insertion is
forcibly directed away from the first-formed bicyclobutane
ring. To establish that the double bond in (3) did not contribute additionally to the regiospecificity, the tetrabromide
(7)'"' was reacted with methyllithium. Separation of (8) (46%)
from an ether insertion product was achieved by distillation
(b. p. 52-58 "C/0.2 torr). The homogeneity of hydrocarbon
(8)was established spectroscopically and by VPC methods.
As a check on the directionality of the ring closure, (4) was
transformed into (8)by diimide reduction.
Although the pair of bicyclo[l.l.O]butane rings within (4)
and (8) are formally conjugated, these molecules show only
customary end absorption in the ultraviolet. Thus, electronic
interaction between bicyclobutane orbitals becomes observable only when the connective bond is linked to the bridgehead carbon atomsIx'. A remarkable feature of these molecules is their stable nature. despite a strain energy which
must be in excess of 120 kcal/moll"1.
I
I
C6H5
C6H5
The ultimate conversion of (5) into ( I ) was carried out according to Dauben's original procedure['I. The brownish red
heptalene (1) entered readily into reaction with 4-phenyl1,2.4-triazolinedione to give in good yield a 10: 1 mixture of
an amorphous solid and a microcrystalline substance (m. p.
>31O"C). The monomeric nature of these cycloadducts was
deduced by mass spectrometry ( M 329) and their inherent
symmetry by "C-NMR spectroscopy (seven signals arising
from the carbocyclic ring C atom of which two are quaternary). The closely similar ' H - N M R spectra are characterized,
infer alia, by an eight-proton olefinic multiplet and a multiplet (2 H ) for the allylic protons vicinal to nitrogen. Their al250 sh nm
most superimposable ultraviolet spectra [Ak&'.""
( F = 1 1 500-12000)]
compare closely to that exhibited by
(X)['I. On this basis. the adducts are formulated as (9) and
(10). although no distinction between the C Land C, forms
has been made.
Tellurium-Catalyzed Reaction of Amines with Carbon
Monoxide
By Nobitaki Kornhc. Kiiwvhi Koriclo. I l i c l i ~ iI d i i i . Shitrli
rai, and Noboric Sotio&i"l
.\!it-
The simplest way of making urea derivatives from aniine
and carbon monoxide may be reprcsented by eq. ( a ) . I n this
communication. we wish to report that the reaction ( a ) can
be catalyzed by elemental tellurium. This i s the lint example
of activation of carbon nionoxide by tellurium and lilthe lormation of equimolar amounts of ureas and hydrogen:
N o typical element was previously known to cataly.c this
reaction. Among group 6 B elements. selenium catalyzes the
formation of ureas from amines and carbon monoxide. but
only in the presence of oxygen: moreover. water is thcn produced instead of hydrogen'''. Sulfur is uneffective in catalyzing reaction (a)"'. Various transition metal complexes have
been reported to catalyze formation of ureas from aminch
and carbon monoxide: little is known about hydrogen formation or the exact stoichiometry of the reactionl".
The tellurium-catalyzed carbonylation reaction ( a ) furnishes equimolar amounts of ureas and hydrogen: timiamides appear as by-products (Table 1 ). The monoanlines
(l a )-(l d ) are suitable starting materials. Ammonia. dialkylamines, and aniline failed to react under the reaction conditions reported.
+
Received January 30. lY79 [Z 237c 11.1
German vcrsioii. Angcw. Chrin. 91. 5 x 1 (1Y79)
Publication drlayed at authors' rcqueht
CAS Kegi\ir) nunibrr,
f I J .257-24-Y. (21. 493-04-9: f71-mt~noaddwx457X-Yh-5: l2)-lris;idduct. 70528.2701.. 70528-30.2: I<Y), 7 0 5 2 ~ 7: (3I. 7 0 5 x z x - x ; (41. 70262-07-1: ( 5 ) . ~ I I ~ ~ x - T - Y
3 1-3 f(J1. 70528-32-4. f/(JI.
70528-33-5: 4-phenyl- 1.2.4-tria7t~linedi1,ne.4233.334. dihroniocarhsne. 4371-77.1
[ I ] L . VoKcl. J . W ~ t \ w nH
. KonrKrho/et?. K Mirllerr. J. I? M . Orh, A n g c w Chcni
86. 777 11974): A n g r w . Cheni Inl. Ld h g l . 1.t. 732 (1974)
[ 21 11. .I. Ilrmhen. Jr.. D J Reriellr. .I.Am. Chem. Soc. 83, 4657. 4659 (I961 ).
[ 31 R. Vfrrdionurho,numi.. D. Derwprohhrrkuru. Chem. Ind. (London) I'J6X. 5 15.
W R . Moorc. .T S Hull. C. i,urgmun. Tetrahedron Lett 106Y. 4353: 1.. A . Payirrrre. (; L o n . R. T Tui,lor. J Org. Chem. i Y . 2677 11974). L. A Poyrrerrc~.R.
7: T ~ i I o r J. Am Chem. Soc. VY. 570X (1977)
[ 4 ] 1. A . Poyrirrr<,. S i n t h e w IV75. 347: h <.. R r h ~ p111. Chem. Rev. 76. 461
( 1976)
51 I:. V O , ~ P /W.
. KIirg. A Rrerrcr. Org. Synlh .M, I I ( I Y74).
[ h J (; 1. lhonipwn. W E Held. L. A. Puqirerl<2. .I Am. Chem Soc Y h . 3177
(1974)
[ 7) E. VoKP/. W. (irrnrml~.S . Koric. Telrdhedron Lrtt. IY6.5. 3625.
[ X I W. R. M m i w . <' R. C'o\rin, J Am. Chem. Soc 0.1, 4910 (1971)
[ Y ] N. C. Hfrrrd. M . .I S. Dcwur. 1 Am. Chem. Soc ,YO. 3966 (1967)
Angrit: Chenr I n i . 1d
.
Engl I 8 1 l Y 7 Y ) No. 7
0 Verlug C'hemie. GmhH.
u
h
c
d
PhCH,NH,
ti-C,H.,NH,
rr-C,H,,NH,
~i.r.Io-C,,H,,Ntj,
41
7.3
2.3
4 I
50
7.4
I.Y
33
I1
ti 7
I IJ
7 2
Experimental
Freshly distilled benzylamine (100 mmol. 10.7 g) and powdered tellurium ( I mmol. 128 mg) are placed with a magnetic
stirring bar in a 50-ml stainless steel autoclave. The apparatus is then flushed several times with CO and charged with
CO at 29 bar. The reaction is conducted at 140°C for 10 h
with vigorous stirring. On completion of reaction, the resulting gas (5.0 mmol H,) is collected in gas sampler at room
temperature and analyzed by gas chromatography (molecular sieve 5 A, 3.3 m; 150 "C: carrier gas, N,, ca. 1 bar). Air is
introduced into the reaction mixture to precipitate tellurium.
Filtration followed by evaporation gives a mixture of products: G L C analyses and comparison with authentic samples
showed dibcnzylurea /2a) (4.7 mmol) and N-benzylformamide /-fa/ ( I , 1 mmol) to be present.
6Y40 Wemherm. I Y 7 Y
lJ~7IJ-/IH.?~/7Y/~I707-O.~47
$ 02 .W/lI
547
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expeditions, synthesis, bicycle, naphthalene, heptalene, intermediate, bis, butant, via
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