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Formation and Trapping of 4 5-Didehydrotropone.

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CH(OR),, CHO, COOR) in position 4 can however be accomplished by Sn/As exchange reactions of suitably substituted
1,4-dihydrostannabenzenes"!
We now report the first preparation of 4-hydroxyarsabenzene (6) from 4-acetoxy-1 ,l -di-n-butyl- 1,4-dihydrostannabenzene (3). 1,4-Pentadiyn-3-01 ( I )r21, accessible from ethynylmagnesium bromide and ethyl formate, is cleanly acetylated
to 1-ethynyl-2-propynyl acetate (3-acetoxy-I ,4-pentadiyne) (2)
by acetic anhydride in ether over powdered potassium hydroxidd3'.
0
(I), H =
(2), R =
11
C-CII3
H
'H-NMR (6) (CDCI,); OH: 7.23 ppm (s); ring H : A2X2
spectrum, H, 7.56 ppm (d having fine structure) J(H,IH,)
11 Hz; HA9.61 ppm (d having fine structure) [ 'H-NMR phenol
(for comparison); O H : 6.11 pprn (s); ring H : 6.65-7.32ppm
(m)];massspectrum:Mt,rn/e 156(rel.int. 100%);[M- As]:,
81 (18
the degradation pattern displays the fragments
[M-CO] and [M-CHO] characteristic of phenols. The
IR spectrum [(KBr); v(0H) 3180 c m - ' ; v(=CH) 3020.
3070 c m - ' ; v(C=C) 1500, 1560 c m - ' ; v(C=O) 1220 c m - ' ;
6'(OH) 1320, 1380 (?) ern-'] is also largely comparable with
that of phenol. The UV spectrum [(ethanol), h,,,=229
( E = 17000); 290nm (30300)l resembles that of 4-ethoxyarsabenzene""] very closely; relative to phenol [h,,,=21 I
(E =6200); 273 nm (2400)], (6) exhibits the bathochromic effect
observed for all arsa- and phosphabenzenes. In ethanol/l N
NaOH an additional pronounced longwave shift of 43nm,
h,,,=233 (13600); 332nm (34200) is observed for (6) owing
to phenoxide formation; this shift is considerably more
pronounced than for sodium phenoxide [h,,,= 238
( E = 11 300); 291 (3200)l.
I%);
(2), b.p. 57"C/14 torr, yield 82%, undergoes a vigorous
cycloaddition reaction with di-n-butyltin dihydride in boiling
anhydrous methylcyclohexane in the presence of azoisobutyronitrile to give the 1,4-dihydrostannabenzenederivative (3).
ComDound ( 3 ) is a Dale yellow oil of b.p. 140"C/0.01 torr
(in bilb tube);'yield 40-jO %.
i
C1
14al
e
0 13
171
4
U
!8J
Thus the spectroscopic findings clearly show that 4-hydroxyarsabenzene ( 6 ) is indeed an arsaphenol. The phenoxide
ion ( 7 ) is formed already on treatment with dilute aqueous
alkali ; in contrast to 4-pyridino1, which exists almost exclusively as y-pyridone in neutral solution[41,no tautomeric equilibrium with 1-arsa-2,5-cyclohexadien-4-one(8) is to be
observed.
0-c- CH3
H
161
0
Received: July 14. 1975 [Z 290 IE]
German version: Angew. Chem. 87. 713 (1975)
i
CAS RegiFtry numbers
( I ) . 5659x-s3-9: i i . s659x-s4-n: ( 3 ) . 5~59x-55-1
: 1 4 a i . 56629-72-2:
f 4 h ) . 56598-59-5: i . 5 ) . 56598-56-2: ( 6 ) . 56598-57-3: ( 7 ) . 5659X-58-4;
The Sn/As exchange reaction of (3) with AsC1, can be
carried out in boiling tetrahydrofuran (3 h). Examination of
the reaction mixture by 'H-NMR spectroscopy shows that
the 1-chloro-l,4-dihydroarsabenzene
derivative ( 4 ) undergoes
partial dehydrohalogenation to give 4-acetoxyarsabenzene ( 5 )
under the reaction conditions. Since the product distribution
( 4 ) / ( 5 ) does not change on work up of the reaction mixture
either by column chromatography over silica gel[**] or by
distillative separation it may be assumed that one of the
possible cis/truns isomers ( 4 ) [probably ( 4 a)] spontaneously
eliminates HCI; the other isomer is only converted into ( 5 )
by reaction with triethylamine in benzene. Compound ( 5 )
can be purified by bulb tube distillation at 80"C/0.01 torr;
the yield [based on (3)] is 20-25%. 'H-NMR (CDCI,);
COCH,: 2.16 ppm (s); ring H: A2X, spectrum H,: 7.50 ppm
(d) J(HJH,) 12Hz; HA: 9.62ppm (d).
Saponification of ( 5 ) in methanolic sodium hydroxide
(room temperature, 36 h) leads to 4-hydroxyarsabenzene (6).
Compound (6) is obtained as the Na salt after evaporation
to dryness and is purified by digestion with benzene. After
acidification with dilute hydrochloric acid the free arsaphenol
( 6 ) is taken up in benzene and, after removal of solvent,
sublimed at 6O0C/0.1 torr. (6), m. p. 102-IO5"C (dec.), forms
strongly refractive compact prisms (after sublimation) displaying an intense phenolic odor; no distinct FeCl, reaction is
observed. On exposure to air, (6) proves to be more stable
than the hitherto known arsabenzenes monosubstituted in
position 4; however, it decomposes after some time to give
brown compounds of unknown composition.
Angew. Chem. inrernur. Edii. lI Vol. 1 4 ( 1 9 7 5 ) 1 N o . 1 0
di-n-butyltin dihydride. 1002-53-5
~
__
a) G. M u r k / and f . Kneidl. Angew. Chem. 86, 745, 746 (1974); Angew.
Chem. internat. Edit. 13, 667, 668 (1974); b) G. Miirkl, H . Kellerer.
and F. Kneidl. Tetrahedron Lett. 1975, 241 I .
E . R. H . .lone$, L. Skarrebul, and M. C. Whirbig. J. Chem. SOC. IY56,
4765; E . R. H . Jones, H . H . Lee, and M . C. Whiting, ibid. 1960, 3483.
R . D. Dillurd and D. E . Puce!., J. Org. Chem. 36, 749 (1971); see also
K . G. Migliorese, Y TrmoLa, and S . 1. Miller, ibid. 39, 739 (1974).
S. F. Mason, J. Chem. SOC. 1958, 1253 (UV spectrum): A . R . Karrirzhy
and R. A . Jones, ibid. 1960. 2947 (IR spectra); R. A . Y Jones, A . R .
Karrrrzkr, and J . M . Lagon..ski, Chem. Ind. (London) 1960, 870.
Formation and Trapping of 4,5-Didehydrotropone
By Tornoo Nokazawu and Ichiro Murata"]
Arynes such as dehydrobenzene possess considerable interest as important synthetic intermediates[". Among the didehydrotropone derivatives, didehydrotropolone['I and didehydrodibenz~tropone'~'
have been described. We now report the
intermediate formation and trapping of 4,5-didehydrotropone
(4).
Reaction of 1 H-cycloheptatriazol-6-one ( I )[41%accessible
in several steps from tropolone, with 0-(2,4-dinitrophenyl)hy[*] Doz Dr. T . Nakazawa and Prof. Dr. 1. Murata
Department of Chemistry, Faculty of Science
Osaka University, Toyonaka, Osaka 560 (Japan)
711
droxylaminefS1 affords 1-amino-I H-cycloheptatriazol-6-one
(3)Ihl,pale yellow needles of m. p. 220°C, and the 2-amino-2H
isomer (2)f6], pale yellow needles of m. p. 198-200°C (dec.),
in the ratio of 1.7: 1 in 75'%, yield.
7: Nozor. S. Ito. and K . .Mofsui, Proc. Jap. Acad. 30. 3 13 (1954)
Y Tumurri, J . Minamrkuwu, K . Sumoto. S. F q i i . and 1M. Ikedu. J. Org.
Chem. 38. 1239 (1973). We are grateful to Prof. Dr. Y 7Umurii. Dr.
M . Ikedu, and Dr. J . M i n a m i k a w for information concerning the amination of ( I ).
All substances described gave correct analytical data.
C. D. Campbell and C. W Rees. Proc. Chem. Soc. 1964. 296: J. Chem.
Soc. C 1969. 742, 748.
( 5 0 ) . 100 MHz 'H-NMR (CF,COOtI): 6=8.17 (d, H-7, H-9:
.I,,=J,
, , - ~ 1 1 . 3 H7); 8.76 (d. H-6. H-10): 7 5 7 (m, H-I. -4. -14. -17J:
7.17 (m, 11-2. -3. -15. -16): 5 9 2 (5. t1-5. H - I I J ; lJV. J.,,,
iCF,COOH)= 103nm (logs=3.95). 343 (3.95).
C. D. Crimphrll and C . W RPW, Chem. Commun. lY6.5, 192.
Transition Metal Catalyzed Acetylene Cyclizations.
A General Synthesis of Indans and Tetralins[**l
By R. L. Hillurd I11 and K . P. C. Vol/hurtlt[*]
The preparation of polycycles containing functionalized
benzene rings with control of substitution is a formidable task.
We now present a general synthesis of indans ( 3 ) and tetralins
( 4 ) that offersa solution to this problem and could in principle
be extended to the synthesis of larger and more complex
polycycles. Our synthetic scheme involves the cooligomerization of 1,6-heptadiyne (1 ), n= 3, or 1,7-octadiyne (1 ), n=4.
with substituted monoacetylenes (2) catalyzed by dicarbonylcyclopentadienylcobaltf 'I (see Table 1 ). The cyclotrimerization
of terminal diynes by this catalyst is a known reaction'Ia1.
$11
In analogy to the formation of dehydrobenzene from benzotriazolel'] compound (3) was oxidized with lead tetraacetate.
Since the poor solubility of (2) and (3) precludes their quantitative separation themixture was treated with lead tetraacetate
in anhydrous dichloromethane at room temperature in the
presence of excess anthracene as trapping reagent ; evolution
of nitrogen was observed during the reaction. The mixture
of products remaining on crystallization of the anthracene
is chromatographed over basic alumina, previously deactivated with 7.5'7(: of water, with dichloromethane as eluant.
The trapping product 5,11-dihydro-5,11-o-benzenocyclohepta[h]naphthalen-8-one (5)I6I can be isolated in cu. 12';/0 yield
as pale yellow needles (from benzene) of m.p. 260°C idec.).
The structure is proved by the 100 MHz 'H-NMR spectrum:
6=5.34 (s, H-5, H-11);
AX system at 6=6.90 (d, H-7, H-9;
J,,,=J,,,,=11.6Hz)and7.39(d,H-6,H-lO);AA'XX'systems
at 6=7.39 (m, H-1, -4, -14, -17) and 7.03 (m, H-2, -3, -15,
-16). The IR spectrum (KBr) contains the characteristic VC=T
and VC-0 bands of the tropone series at 1614 and I563 crn '.
Typical absorptions of tropone derivatives are likewise
observed in the UV spectrum; h,,
(cyclohexane)= 230 nm
(sh, log&=4.32), 243 (4.26), 280 (3.61), 314 (3.96), and 327
(3.93). The adduct ( 5 ) is present as the hydroxytropylium
form ( S u ) in trifluoroacetic acid[']; the protonation is reversible. Under the reaction conditions employed the conceivable
product arising from ( 2 ) cannot be obtained", ' I .
~
Received: July 14, 1975 [ Z 292 IE]
German version: Angew. Chem. 87. 7-12 11975)
CAS Registry numbers:
( 1 1 . 5659X-7X-X: ( 2 ) . 56598-79-9: 131, 5659X-XI-?: ( 5 ) . 5659X-X2-4:
i - j r r i . 56598-80-2: 0-(2,4-dini~rophenyl)hydroxylamine.17508-1 7-7
[I] R. W H o j f k m n : Dehydrobenrene and Cycloalkynes. Academic Press.
New YorkIVcrlag Chemie. Weinheim 1967.
[2] 7: Xim[itai~i.M . ~ I . ~ L I I ~ oand
I ? ~ K
, . Tukosr, Tetrahedron Lett. 1970. 1725.
and references cited therein.
131 W 7or.hlrrmum~.K . Oppenliinrlrr. and .'7, Wnlro., Chem. Ber. Y7, 1318
( 1964).
712
(I).
II =
(2)
3,4
(31, n
= :3
(4),
= 4
II
Table 1. lndans ( - 3 ) and tetralins ( 4 ) prepared [2]
Compound R '
R'
M. p. ["C]
b. p. [ C/turi.]
Yield
Ref.
['XI
11.
67 -68
74 7 5
119-120
41 0 2
68
69
I15'00i
97 0 5
112
81 002
1105
45 46
90 0 I S
20
[i]
26
24
14
~41
50
26
18
21
14
49
14
[51
[i]
[61
[a] Oil bath tenipcratiire.
[b] We thank C. P. Baskin for the preparation of this compound
The major side products accompanying ( 3 ) and ( 4 ) arise
by CyclotrimeriLation and complex ~ooligomerization~~'.
The
desired compounds ( 3 ) and ( 4 ) are, however, easily separated
by column chromatography. The method described here extends the pioneering studies on the "diyne reaction" by
E . Miiller er ~ l . ' ~ ] .
[*] R. L. Hillard 111 and Prof Dr. ti. P. C \'ollhni-dt
Department of Chemistry. University of California
Berkeley. California 94720 ( U S A )
We thdnk the donors of the Petroleum Reqearch Fund. administered hy the
.knerican Chemical Society. the Rcscarch Corporation, and the National
Institute of Health (Biomedical Sciences Supports Grant RR-7006) for generous financial support.
[**I First reported at the American Chemical Society 30th Annual Northwest
Regional Mectinp, Honolulu. Hawaii, June 12 --13, 1975.
h y e i i . Chrm. iiitcwlui. Edit.
1 Nil. 14 ( I Y 7 5 ) .I_ NIJ. 1 0
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