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Azuleno [4 5 6-cd] phenalene; A Novel Nonalternant Isomer of Benzo [a] pyrene.

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CHzOH
[I] R. J . Ferrirr. Adv. Carhohydr. Chem. 20, 67 (1965): 24. 199 (1969):
B. Frusrr-Reid. Acc. Chem. Res. 8. 192 (1975): referenccs cited therein.
[2] R. J . Ferrier, N. Pmsad, J. Chem. Soc. C 1969,570: J . Threm. J . Schwcntiirr,
Tetrahedron Lett. 1976, 3117: K . H r y s , .I.
I. Park, Chem. Ber. 109,
3262 (1976).
131 Prepared from cyclooctatetraene according to the method of R. M.
Carlson. R. K . Hill, Org. Synth. 50, 24 (1970).
[4] D.L mixture.
[5] Analogously as described here for ( 3 ~ )the
. a-erythro-hex-2-enopyranosides of type ( I ) can by synthesized from ( 4 ~ ) :R. R. Schmidr. R.
Angerbuirer, unpublished work.
[6] R. R. Schmidt, P. Hrrmentin, Angew. Chem. 89, 58 (1977): Angew. Chem.
Int. Ed. Engl. 110. 48 (1977).
H O W O R
(1)
BUOOC,
,c =o
H
AcO+oAc
-
COOBu
COOBu
OOR
" ' O f i-
+ AcO -
OR
13)
0
II
( a ) : R = C-CH3
( b ) : R = CH3
IC):
(el: R
=
R = CzH,
(d):R =
(41
Azuleno[4,5,6-cd]phenalene ; A Novel Nonalternant
Isomer of B e n z o [ a ] p y r e n e [ * * ]
x
0
0
(f):R
=
0
By Kazuhiro Nakasuji, Eishiro Todo, and Ichiro Murata[*]
Polycyclic arenes such as benzo[a]pyrene (Z)[']
are an
important class of carcinogenic compounds. Our interest lies
in the area of comparative studies on the properties of (1)
w
-CHzO
0
X
wH2Ph
0
Table 1. Synthesized a-threo-hex-2-enopyranosides [a]
Yield
[ "41
1-H
2-H
3-H
'H-NMR data [c]
4-H
5-H
J1.2
Jz.3
54.5
53.4
~
37 [el
38 re1
98
96
98
52
50
66
16
[a]
[b]
[c]
[d]
[el
6.41
6.37
5.07
5.19
5.31
5.19
5.19
5.06
4.96
6.06
6.28
5.88-5.9X
5.99
6.14
6.00
6.15
5.96
6.12
6.00
6.15
5.96
6.15
5.73
5.98
5.15
6.02
5.33
5.54
5.27
5.28
5.27
5.27
5.27
4.73
4.38
4.72
4.76
4.78
4.76
4.76
PI
PI
Id1
[dl
3
e 1.5
2.5
2.5
2.5
2.5
2.5
3
3
10
[dl
5.5
2
5
4.5
5
5
4.5
5
5
10
10
10
10
10
10
10
3
9.5
3
3
3
3
3
[dl
[dl
All compounds gave correct elemental analyses and mass spectra consistent with the structure.
( 2 d ) , m.p. 98°C; all other compounds are viscous oils.
100-MHz spectra in CDCl3 with TMS as internal standard: 6 values, coupling constants in Hz
Not determinable from the spectrum.
Yields referred to 1,3-hutadienylene diacetate used
pletely isomerizes to ( 3 a ) under the reaction conditions; under
milder conditions the p-anomer can be isolated in low yield.
(3 a) reacts almost quantitatively with aliphatic alcohols
and in good yields with D-ribose derivatives in anhydrous
acetonitrile in the presence of boron trifluoride ether catalyst; it
affords the glycoside uronic acid esters (3 b ) to (3f ) (see Table
1). The stereospecificity is attributed to the anomeric effect
and possibly to the influence of the carboxyl group[61.Reduction of ( 3 d ) and ( 3 f ) with LiAIH4 in ether gives the unsaturated r-glycoside (2 d ) and the a-disaccharide (2f), respectively.
and its nonalternant isomers. Azuleno[5,6,7-cd]phenalene
(2)[21 is a carcinogenr31, while its nonalternant isomer, azuleno[ t ,2,3-cd]phenalene (3)t4I, exhibits only weak carcinogeni~ity[~].
We have now synthesized azuleno[4,5,6-cd]phenalene ( 4 ) , which on account of the topology of its 7c-electron
system [similar to that of (2)] and its molecular geometry
[which closely resembles that of (Z)] can be expected to
display substantial biological activity.
Procedure
A mixture of 1,3-butadienylene diacetate (9 g, 53 mmol),
n-butyl glyoxylate (9 g, 69 mmol) and hydroquinone (20 mg)
is dissolved in lOml anhydrous benzene and heated in an
autoclave for 60h at 125°C. The reaction mixture is then
chromatographed on silica gel (eluent: benzene/acetone 9 : 1).
Yield 5.9g ( 3 a ) and 6.1 g ( 4 a ) .
Received: August 8, 1977 [Z 817 IE]
German version: Angew. Chem. 89, 822 (1977)
We selected the pentacyclic alcohol ( 1 0 ) as a precursor
for our synthesis, reasoning that it might be converted to
-
CAS Registry numbers:
( 2 d ) . 64035-97-8: ( 2 J ) , 64035-99-0: ( 3 u ) , 64035-87-6: ( 3 u j (p-anomer), 6403588-7; ( 3 b ) , 64035-89-8; ( 3 c ) , 64035-90-1: ( 3 d ) , 64035-91-2: ( 3 e ) , 64035-92-3;
(3J), 64035-93-4; ( 4 n ) , 64035-94-5; trans,truns-l,3-hutadienylenediacetate,
15910-1 1-9; ti-hutyl glyoxylate, 6295-06-3: methanol, 67-56-1; ethanol, 64-175; cyclohexanol. 108-93-0; methyl 2,3-0-(1methylethylidene) P-D-ribofuranoside, 4099-85-8: phenylmethyl 2.3-0-(1 methylethylidene) p-D-ribofuranoside.
23276-32-6
784
[*] Dr. K. Nakasuji, E. 'Todo, Prof. Dr. 1. Murata ['I
Department of Chemistry, Faculty of Science, Osaka University
Toyonaka, Osaka 560 (Japan)
['I Author to whom correspondence should be addressed.
[**I The Chemistry of Phenalenium Systems, Part 2 6 . ~ Part 25: 0. Huru,
K . Tunoka, K . Yrriiiamolo, 7: niahuzawa. 1. Muratu, Tetrahedron Lett. 1977,
2435.
Angew.
Chrm. I n t . Ed. Engl. 16 (1977) No. 11
( 4 ) by dehydrogenation in view of the known thermal stabilities of (2)[*l and (3)[41.
(S), R' = R 2 = H
161. R' = COzCzH,, R 2 = H
(7), R' = C O z C 2 H 5 , R2 = C H 2 C s C H
m ) , R' = C O ~ C ~ I I , , R~ = C H ~ C O C H ,
f9).
x=
( 4 ) complete analysis of the 'H-NMR spectrum could not
be made.
The diamagnetic susceptibility of ( 4 ) (measured with a
Cahn balance) is xM= 147+7['1 which is comparable with the
value found in the case of (3)I4].
0
x = ,'HO H
Ethoxycarbonylation of the tetracyclic ketone (5jL6]
((C2H50)2C0,NaH, diglyme, reflux 2 h) furnished 89 % of
the 0x0 ester (6). Reaction of (6) with propargyl bromide
(NaOC2H5/C2H50H,reflux 2h) gave the alkyne (7), which
was subjected to hydration in the usual way (HgS04, H2S04,
HOAc, 95 "C, 3 h) to give the diketo ester ( 8 ) in quantitative
yield. Intramolecular aldol condensation ( 5 % aq. KOH, dioxane, reflux 6 h) yielded a mixture of the stereoisomeric cyclopentenones ( 9 ) which on chromatographic separation (Al2O3,
benzene) afforded the isomers (Yo) and (Yb) in 28 % and
43 % yield, respectively. Reduction of the mixture ( 9 ) with
LiAIH4 provided a mixture of the cyclopentenols (10) in
95 % yield. Final conversion of (10) into ( 4 ) was achieved
in 18% yield by heating (10) with sulfur in trichlorobenzene
at 210--220°C (for properties of intermediates see Table 1).
Table 1 . Some properties of the compounds prepared
( 4 ) . m.p. 168---169"C (benzeneihexane); IR (KBr): V = 3040w, 1 6 1 0 ~1575
.
m,
1525m. 1440m. 1390m.1345m, 1185m. 850s 740s. 6 9 5 c m - ' m ; A,.,(cyclohexane)=25Onm (log&=4.17), 354 (4.69), 397 (3.87). 409 (3.88), 432 (4.20),
458 (4.49), 714 (2 69). 792 (2.62),840 (2.30).900 (2.25); H-NMR: 2 AB-quartets
at 6 ~ 8 . 6 5and 7.83 (J6.i=10.0Hz, 7-H and 6-H) and at 9.15 and 8.11
( J I I . 1 2 = 9 . 5 H z ,11-H and 12-H), 7.66 (dd, Js.9=4.0, J6.10=2.0H2. 8-H).
8.35 (br. d. J q I O = 4 . 0 H r , 10-H) [a], 7.75--8.25 (m, I-H t o 5-H.9-HI
As would be expected for a compound containing an azulene
moiety, ( 4 ) is markedly basic and is protonated reversibly
in degassed trifluoroacetic acid to a mixture of the cations
(1 1 ) and ( 12) in the ratio of 4 : 1. The preferential formation
of (11) can be explained by the postulation that relief of
the strain associated with a nonbonded interaction between
hydrogens H-10 and H-11 of ( 4 ) provides the driving force
for protonation at C-10. The pronounced basicity of ( 4 ) is
attributed to the substantial thermodynamic stability of the
cyclohepta[cd]phenalenium ion[*].
Studies on the carcinogenicity and mutagenicity of ( 4 ) ,
which will provide insight into the biological properties of
polycyclic arenes, are currently in progress['].
Received: August 8, 1977 [Z 818 IE]
German version: Angew. Chem. 89, 821 (1977)
CAS Registry numbers:
( 4 ) , 64036-33-5; ( 5 1 , 53260-25-6; (6). 64036-34-6; ( 7 1 , 64036-35-7; ( N i ,
64036-36-8; (Ya j, 64036-37-9; ( 9 h ) , 64036-38-0; ( l o ) , 64036-39-1 ; ( I I ) ,
64045-02-9; ( 1 2 ) , 64045-03-0
-
See ' - 9 . . D. M. Jurina, H. Yhgi, 0. Hemundez, P. M . D u i w t t e , A. W
Wad, W Lui,in. R. L. Ckang, P. G. Wislocki, A. H. Conriey in R. Frrudenthrrl
and P. Joiius: Polynuclear Aromatic Hydrocarbons. Raven Press, New
York 1976, pp. Y1--113.
Ch. J u t z , R. Kirclileclmrr, Angew. Chem. 7 X , 493 (1966); Angew. Chem.
Int. Ed. Engl. 5, 516 (1966); Ch. Jutz, R . Kird?lechner. H . - J . Seidrl,
Chem. Ber. 102, 2301 (1969).
N . P. Buu-Hoi, D.P. Hieri, Ch. Jut;, Naturwissenschaften 54,470 (1976);
N. P. Buu-Hoi, N. B. Ciao, Ch. Jut:. ibid. 57, 499 (1970).
I . Muruta, K . Nukusuji, K . Yamamoto, 7: Nakazaw, Y Kuyune, A . Kiniuru.
0. Huru, Angew. Chem. X7, 170 (1975); Angew. Chem. Int. Ed. Engl.
14, 170 (1975).
Private communication from Prof. Y Sakamoro, Osaka University, Medical School.
1. Murutu, K . Yamumoto, Y. Kayanr. Angew. Chem. 86, 861 (1974);
Angew. Chem. Int. Ed. Engl. 13. 807 (1974). We wish to thank Dr.
K . Kimamoro and Mr. Y Kujune for the preparation of ( 5 ) .
We thank Prof. R. Kiriyoma and Dr. 7: Asui. Osaka University, for
carrying out this measurement.
I . Murata. K. Yumamoto, !I Kuyarie, Angew. Chem. K6, 862 (1974):
Angew. Chem. Int. Ed. Engl. 13, 808 (19741.
Prof. 7: Sugimura and Dr. M. Naguo, Biochemical Division, National
Cancer Research Institute, Tokyo (Japan) are currently engaged with
the mutagenicity test of ( 4 ) .
( 6 ) . colorless oil, 'H-NMR: 6=1.40 (t. 3 H , J = 7 H z , -CH3),
1.7 -3.4 (m,
9 H),4.20(q. 2H, J = 7 Hz,-OCH2-),
7.0-7.8(m, 5 H), 12.6(s, 1 H. ,C-OH)
(7). m.p. 138-139°C; IR (Nujol): 0=3250 (=C-H),
1720. 1660cm-'
(C=O); ' H - N M R : 6=1.00 (t. 3H. J = 7 . 0 H z , -CH3), 1.7-3.3 (m, 12H),
4.10(q. J=7.0Hz,-OCHZ-).
7.1--~7.9 (m, S H )
(XI, m.p. 130--131"C; 1R (Nujol): V=1720. 1700, 1660cm-' (C=O); 'HNMR: 6 = 1 . 1 3 ( t , 3H. J = 7 . 0 H z , -CH,), 1.7-2.5 (m. SH), 2.12 (s, 3H.
7.3-7.8
-COCH3), 2.8 -3.7 (m, 6H), 4.17 (q, 2 H , J = 7 . 0 H z , -OCHz-).
(m, S H )
( 9 a ) [b], m.p. 130 -133°C: 1R (Nujol): V=1690cm-' (C=O); 'H-NMR:
6 = 1.6 -3.3 (m, 12H), 6.10 ( s . 1 H, =CH-),
7.0--7.7 (m, 5H)
( Y h l [h]. m.p. 96 -Y7"C; IR (Nujol): 0=1680cm-' (C=O); 'H-NMR:
6=1.6- 3.6(m, 12H).6.30(s, lH.=CH-),7.0--7.7(rn,5H)
( l O l , IR (CC14):V=3600. 3340cm-' ( O H )
( l I i ~ C F 3 C 0 0 -'H-NMR:
,
6=4.82 (br. s, 2H), 7.70 (dt. J = 5 . 5 and 1.2Hz.
1 H). 7.75 (dt. J = 5 . 5 and 1.7Hz, I H), 8.66--9.62 (m)
(I?).CF3COO-, 'H-NMR:6=4.51 ( b r . s , 2 H ) , 7.6-7.9(m,ZH). 8.66-9.62
(m)
[a] Assignment of previously enumerated signals by double resonance experiments. Irradiation at 6=9.15 (11-H) and 8.65 (7-H) converted the signals at
S=8.1 1 and 7.83, respectively, into singlets. Irradiation at 6=8.35 (10-H)
converted the double doublet at 6=7.66 into a doublet with J = 4 . 0 H z .
[b] The stereochemistry has not been investigated.
Azuleno[4,5,6-cd]phenalene ( 4 ) crystallizes as stable green
leaflets. Its structure was confirmed by elemental analysis and
spectroscopic properties (Table 1). In the electronic spectrum
three major bands can be discerned, as in the spectra of
(2)l2] and (3)[41. Due to the lack of a symmetry axis in
A n y r ~ Chem.
.
I n ! . E d . Engl. 16 ( 1 9 7 7 ) No. 1 1
Base-Stabilized Silyleneiron Complexes[']
By Giinter Schmid and Eckhard Welz[']
While germylene, stannylene, and plumbylene complexes
can be prepared with comparative ease, attempts to synthesize
['I
Prof. Dr. G. Schmid, Dip!.-Chem. E. Welz
Fachbereich Chemie der Universitgt
Lahnberge, D-3550 Marburg (Germany)
785
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