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Cyclohepta[cd]phenalen-6-one.

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rable I . Starting materials. yields, and physical data of compounds of types ( 3 ) - ~( X ) .
and ( 1 0 0 )
. . _ ~ ~. ~
~ . .. . ~
-.~ - NMR
characterization
(6 [ppm] in CCI,. .I [ H I ] )
Yield
['',,I
Prepared
from
Cpd.
. ~ --.
.
~~_.-_
----.-see [4b]
( l ) , R=SeCoH5. R ' = H , + C H , J
95 [a]
( 3 ) . R=CH,i. R ' = H
x-Se-CH: 4.40 (I. 6.0)
( 1 ) . R=SeC,,Hi, R'=H. + n - C I I , H z I B r
76 [bl
(31. R=n-Cli,H3i, R ' = H
see [4b]
acetone + 2 C , , H S e H
80 [c]
(31, R=R'=CH>
cyclohexanone + 2 CoH5SeH
95 [dl
(3), R--R'=-(CH>)sC H 2 : 1.67 (d, 7.0):C H : 4.48 (I. 7.0)
( I ) , R=CH,,, R'=H. + (ChHsS)>
60 [el
(4). R=CH,, R ' = H
CH.3: 1.57 (s)
( I ) . R = R ' = C H % , + (COHSSII
70
(4). R=R'=CH,
CH ,. 1.35(broadencd by Ll-coupling d. 7.0):
> 9x
( I ) . R=CH.<. R ' = H . + D2O
(5). R=CHj. R'=H, E = D
x-Se-CHD: 2.72 (broadened by D-coupling q, 7.0)
CHI: 1.45 (d. 7.5). x-Se---CH: 3.24 (q. 7.5)
( I ). R = C H > , R ' = H. + cyclohexanonc
(71,R = C H > . R'=H, R"--R'"=-(CH>),CH.,: 1.50 Id. 7.0): x-Se--CH. 3 40 (q. 7.0)
( I ) . R = C H I , R ' = H . + cyclooctanone
( 7 ) . R = C H \ , R ' = H . R"-R"'=-(CH2)-x-Se-CH?. 2 83 ( I . 6.X)
( I ) . R = n - C , , , H i l . R'=H. + H z 0
( 5 ) . R=n-CiiiHii, R ' = H , E = H
x-Se-CHD: 2.84 (broadened by D-coupling 1. 6.X)
( I ) . R=n-CloHzi, R'=H. + D 2 0
( 5 ) . R=n-CII,H2iR
. '=H, E = D
C D ( C H J I I . I 3 7 (broadened by D-coupling s)
( I ) . R=R'=CH.i, + D 2 0
( 5 ) . R=R'=CH.i, E = D
C H . , 1.35 (s)
( I 1, R = R ' = C H ,. + cyclohexanone
( 7 ) . R = R'=CH,. R"--R"'=-(CHI)5-2.0- -CH: 3.15 (m).
terminal CH / . 0.XX (deg I )
+ hexanal
( 7 ) . R-R'=-(CHz)s--.
R"=n-CsH I 1 , R'"= H ( I ) . R-R'=-tCHz).-.
x-S--CHD: 1.26 (hroadcned by D-coupling d. 7 0 )
(2). R=CH,I. R'=H. + D:O
(61, R = C H I . R'=H. E = D
CHA: 1.17 (d. 7.0): 2-S- CH: 4.27 (q. 7.01
( 2 ) . R = C H , , R ' = H , + benzophcnone
( X ) , R=CH.i, R ' = H . R"=R"'=C(3H<
C(CH i ) i . 1.58 IS)
( 2 ) . R=R'=CH.i. + CHII
(61, R = R ' = E = C H ,
C H j : 1 . l X (s)
( Z ) , R = R ' = CH %.
+ cyclohexanone
( 8 1, R = R ' = CH.1. R"-R'"=
-lCH zls-vinylic H: 5 6 ( m )
( 7 ) . R - R ' = --(CHI)+- ,
(Yu)
R " = n - C I H I , , R"'=H. + H 2 0 2 in
CH +: 1 75 (broadened by allyl-coupling 51.
( 7 ) . R = R'=CHi. R"-R"'=
---(CH3)5(IOU)
vinylic H C I S t o CH ,: 4.70 (m):
+ H z 0 3in T H F
vinylic H (ran\ lo CH ,: 4.92 ( m )
_-_
--.
..
--
~ _ -
.~ --
~-~ - -
f Yo).
~-
~
~
~
~
I([
[a]
[d]
[g]
[h]
B.p. 140- 146"C/0 I torr. [b] B.p. 130°C/0.02 torr [c] B.p. 141 144"C!0.08 torr.
M.p.76.5--77S0C. [el B.p 109"C/O.O2torr. [f] B.p. 1 3 0 T 0 . 3 torr.
The alcohols were separated from ChHsSeC4Hvby chromatographlc filtration over silica gel or by preparativc TLC and isolated piire as 011s
Separated by gas chromatography. [i] nb"= 1.4822 "71: i7?= 1.4X00).
The modes of preparation, yields, and physical and NMR
data of the compounds of types [ 3 ) - ( 8 ) , ( Y a ) , and ( I O U )
obtained are listed in Table 1.
Received: J u l y 31, 1974 [ Z 9 0 b IE]
German version: Angew. Chem. 86. 859 (1974)
( I ) , R=CH,.
CAS Registry numbers: [ I ) , R=SeC,H,,R'=H,53198-49-5,
R ' = H , 53198-50-8; ( l ) . R = R ' = C H , , 53230-01-6; ( l j . R = n - C , , H , , . R ' = H .
53198-52-0; [ 2 ) , R = C H , , R ' = H ,
53198-51-9; ( I ) . R-R'=(CH,),,
53198-53-1 ; ( 2 / , R = R ' = C H , , 53198-54-2; ( 3 ) . R = C H , . R ' = H ,
26822-85-5; (31, R=n-C,,H,,, R ' = H , 53198-55-3; ( 3 ) . R = R ' = C H , .
35446-87-8; ( 3 ) , R-R'=(CH2),, 53198-56-4; ( 4 ) . R =CH,. R ' = H ,
53198-57-5; [ 4 ) > R = R ' = C H , , 53198-58-6: (S)%R = C H , , R ' = H , E = 2 H ,
53198-59-7: [S), R =n-C,,H,,R'=
H , E = H,53198-60-0; (S). R = R'=CH,.
E = ' H , 53198-63-3; (S),R=n-C,,H,,. R ' = H , E='H. 53198-61-1 : (6~.
R = C H , , R ' = H , E='H. 53198-62-2; (6). R = R ' = E = C H , 3019-19-0.
(71, R=CH,, R ' = H , R"-R"'=(CH,),,
53198-64-4; (7). R = C H , . R ' = H .
R"=n-C,H, I . R"'= H.
R"-R"'=(CHz),, 53198-65-5; ( 7 ) . R-R'=(CH,),,
53198-66-6; ('7). R = R ' = C H 3 . R"-R"'=(CH2),. 53188-73-1; ( 8 ) .
R=CH,,R'=H,R"=R"'=C,H,,
53198-67-7; [ X ) , R = R ' = C H , ,
R"-R"'=(CH2)5, 53198-68-8; ( 9 u / , 53198-69-9, ( l o o ) , 3908-31-4:
CH,I, 74-88-4; n-C,,H,,Br, 112-29-8: C,H,SeH, 645-96-5; (C,H,S),.
882-33-7; 'H,O, 7789-20-0; H,O,. 7722-84-2 ; Acetone, 67-64-1. Cyclohexanone, 108-94-1 : Cyclooctanone. 502-49-8; Hexanal. 66-25-1 ; Benzophenone, 119-61-9
-- .-
.~~
-.
E. J . Corevand D. Serhuch, J. Org. Chem. 31, 4097 (1966).
[ I ] a ) R. L Sowerhj and R. M . Coutrs, J. Amer. Chem. Soc. Y4 4758
11972): I . Kuwujimu. S Suro, and !I Kurura, Tetrahedron Lett. 1972. 737:
b) J . R Shanklin, C . R. Johnson, J . OIlinger. and R. M . Coarrs, J. Amer
Chem. SOC. 95. 3429 (1973): c) E. J . Core). and M . Juurriar, Tetrahedron
[I]
Lett. 1968. 5787.
[3] D. A. Shirk!, and B. J . Reeves. J. Organometal. Chem 16. I (1969).
[I] a ) H.. Cilmun and R. L. Behh, J. Amer. Chem. Soc. O f . 109 (1939).
H. Cilmun and F . J Webb, ibrd. 71. 4062 (1949): b ) D. Serhuch and N.
Pelrlies, Angew. Chem. 81. 465 (1969). AngeR. Chem. internat. Edit. 8. 450
(1969). Chern Ber. 1 0 5 , 511 (1972).
[ 5 ] D. N. Junes, D. Munil?., and R. D. Whirrhouse. Chem Commun. 1Y70.
86: K . B Shurp1u.s.s and R F. Lauer, J Amer Chem. Soc YS. 2697 (1973).
[6] W Dumoni, P. Barer, and A KrieL Angcw. Chem. 86, 308 (1974): Angew.
Chem. internat. Edit. 13, 274 ( I974).
171 C. R.
.Johnson. C . J . Chew, and D.
J . Goldsmirh. J Org. Chem. 24,
3320 (1964).
Anguw. Chem. internat. Edit.
J Vol. 13 ( 1 9 7 4 ) J N o . I 2
Cyclohepta[ cdlphenalen-6-oneI l ]
By Ichiro Muruta, Kagutoshi Ycmamoro, and Yutuku K c p n d * 1
In connection with current interest in the peripheral conjugation in prri-condensed polyarenes, we have recently reported
thesynthesisand properties ofthephenalenones (/)-(3)[2-41.
We have proposed that compounds ( 1 ) and ( 2 ) can be
regarded as perturbed [13]-annulenones and compound ( 3 1
as a perturbed [I 51-annulenone. In this communication we
report the synthesis and properties of a further example of
this type of compound, a novel tropone derivative, cyclohepta[cd]phenalen-6-one ( 9 ) .
Reformatsky reaction of dihydrophenalenone (4)[51 with
methyl 4-bromocrotonate afforded the hydroxy ester, which,
on hydrogenation with palladium hydroxide on charcoal followed by hydrolysis with potassium hydroxide in ethanol
gave the carboxylic acid (5)[61, m.p. = 9OoC, in 48% yield
[referred to ( 4 ) ] . Cyclization of ( 5 ) with polyphosphoric
acid (PPA) at 90°C for 1 h afforded the tetracyclic ketone
(6/[61in75"4yield:m.p. = 97.5-98"C;IR(KBr): 1665cm-';
'H-NMR (CDCI3): 6 = 1.6-2.2 (m, 6H), 2.5-2.7 (m, 2H),
2.9-3.5 (m, 3 H)and 7.0-7.7 (m, 5 H).The ketone ( 6 ) was
converted by treatment with bromine in dry carbon tetrachloride into the u,a-dibromoketone (7) in quantitative yield : viscous oil; IR (neat): 1695cm-'; 'H-NMR: 6=1.5-2.7
(m,
I'[
Prof. Dr. 1. Murata, Dr. K. Yamamoto. and Y. Kayane
Department of Chemistry, Faculty of Science, Osaka University
Toyonaka, Osaka 560 (Japan)
807
6 H), 2.8-3.3 (m, 3 H)and 7.0-7.7 (m, 5 H). Dehydrobromination of ( 7 ) to give the tropone ( 8 ) [ ' ] (in 66'x yield) was
accomplished by heating in hexamethylphosphoric triamide
(HMPA) with LiCl for 1 h at 95-100°C; ( 8 ) : yellow plates,
m.p.=90.0-90.5"C;
m/e=232 (M', 64%), 204 ( M + - C O ,
loo%), 203 (93%) and 202 (pyrene ion, 82%); IR (KBr): 1625,
1590,1580 cm-'. The absorption bands of the UV spectrum of
transition from the dihydroketone ( 8 ) to the fully conjugated
ketone ( 9 ) , all the vinyl protons move downfield by 0.22 to
0.53 ppm. The most plausible explanation suggests that these
downfield shifts arise from deshielding due to the existence
of a diamagnetic ring current induced in the periphery of
( 9 ) . The diatropic effect is enhanced when (9) is protonated.
Differences in the chemical shifts between the neutral and
protonated species of ( 9 ) are even larger than those observed
in the case of ( 8 ) ; this also underlines the significance of
the peripheral conjugation in (9).
Received: July 25, 1974 [Z 93a IE]
German version. Angew. Chem. 86, 861 (1974)
3 . KOH/C,H,OH
CAS Registry numbers: 14/, 518-85-4; f S ) , 53260-24-5, (61, 53260-25-6;
f 7), 53260-26-7; (S), 53260-27-8; (9). 53260-28-9; Methyl 4-bromocrotonate, 1117-71-1 ; Bromine, 7726-95-6
13r:
[I]
The Chemistry of the Phenalenium System. Part 18.-Part
K . Yamamofo, and 0.Hara, Tetrahedron Lett. 1974, 2047.
____)
CCI,
/
17: 1. M u r a f u ,
121 I . Murafu and K Yamamoro, Chem. Lett. 1973, 413.
131 I . Murara, K . Yumamoto, 7: Hirotsu. and M . Morioku, Tetrahedron Lett.
1972, 331.
[4] 1. M u r a f a , K . Yamumoro, and 71 Hirorsu, Tetrahedron Lett. 1972, 3389.
HSt PA
[ 5 ] L. F. Fieser and M . D. Gales, J. Amer. Chem. SOC. 62, 2335 (1940):
V Borkelheidr and C . E. Larrahee, ihid. 72, 1240 ( I 950): D. M Reid and
R. G. Sufherlund, J. Chem. SOC.1963, 3295.
[6] All new compounds described in this paper gave satisfactory elemental
analytical data.
[7] S. Julia and Y. Bonnef, Bull SOC.Chim. Fr. 1957. 1340.
(8) (A,,
(ethanol)= 243 (log E =4.38), 287 (4.33) and 344nm
(3.91)] are in good agreement with those of cyclohepta[a]naphthalen-7-0ne''~.
The conversion of ( 8 ) into the desired fully conjugated ketone
(9)[61was effected by treatment with 2,3-dichloro-5,6-dicyano1,4-benzoquinone in benzene solution in a sealed tube at
120°C for 20 h (yield 21 'x).The compound (9) was found
to be more readily accessible by treatment of ( 8 ) with triphenylmethyl tetrafluoroborate in refluxing acetic acid under
nitrogen for 2 h (33
yield): orange scales, m.p.= 144146°C; m/e=230 ( M + , 27%) and 202 ( M + - C O , 100%);
IR (KBr): 1600,1590and 1560cm-'; U V : h,,, (ethanol)=249
(Iog&=4.48), 311 (4.07), 321 (4.08) and 430nm (4.23); A,,
(cyclohexane)=246 (4.47), 31 1 (4.10) and 430nm (4.19).
The Cyclohepta[cd]phenalenium Ion[**]
By lchiro Murata, Kagrtoshi Yamamoto, and Yutaka Kajme[*]
Although there has been considerable interest in the neutral
nonalternant isomers of pyrene, the ionic 1471perimeter species
which are isoelectronic with pyrene have received little attention. According to theoretical predictions by Zahradnik['] the
cyclohepta[cd]phenalenium ion (4) ought to be quite stable.
14)
i
Tdble I IOO-MHz-'H-NMR data of ( 8 ) and ( 9 ) ( 6 values, T M S internal)
-.
~
~
in CDCI,
H- I .2,3
H-7.8.9
H-10.1 I
H -4
H-5
JI
II
(8)
(9)
7.30---7.78
7.68 -8.02
7.20-7.56
2.88- 3.35
7.96
8.24
9 0 Hz
8.18
8.77
9.0 Hz
_____
~
____
in CF,COOH
(8)
(9)
7.82-8.21
8.24-8.62
3.48-- 3 82
8.62
9.05
9.2 H z
9.23
9.74
9.2 Hz
The NMR chemical shifts and coupling constants of (8) and
( 9 ) are summarized in Table 1. It is apparent that in the
808
(3)
[*] Prof. Dr. 1. Murata, Dr. K. Yamamoto, and Y Kayane
Department of Chemistry, Faculty of Science, Osaka University
Toyonaka, Osaka 560 (Japan)
[**] The Chemistry of the Phenalenium System, Part 19.--Part 18. [I].
Angrw. Chum. internat.
Edit. Vol. 13 (1974) No. 12
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