close

Вход

Забыли?

вход по аккаунту

?

Naturally Occurring Cyclopropenone Derivatives.

код для вставкиСкачать
The much more efficient [@185=0.63+0.05] 185 nm photolysis of ( l a ) in pentane yields only 29% (3) and 15% (4), but
49% of 2,4-dimethylpenten-3-one, an isomer of (2a)1*1.After
almost two decades, we have eventually succeeded in completing the final step of Mock's elegant strategy for the generation of (Za)''"].
ilu)
(2a)
2
- N1
CD30D
[8]
DO OCD3
H3C&CH3
H3C
[7]
I91
[lo]
[I I ]
(5)
CH3
torr. b) The sample was placed at one focal point of the elliptical rhodiumcoated mirror of a PRA light source type ALH 220. At the second focal
point a 1ooO W Hg/Xe high pressure lamp Canrad Hanovia 977B0010 was
positioned. c) Focussed 500 W Hg high pressure lamp Osram HBO 500 W/
2, quart.? optics. d) Filter WG 335 (Schott und Genossen, Mainz). e) Filter
U G 1 (Schott und Genossen. Mainz).
a) C. H . DePuv. H . L. Jones. W. M . Moore, J. Am. Chem. SOC.95. 477
(1973); b) B. H. Bakker, T Reinrs Bok, H. Sternberg. T. J. de Boer, Rec.
Trav. Chim. Pays-Bas 96, 31 (1977)
W. Adam. A . Fuss. F. Mazenod. H. Quasr, J. Am Chem. SOC. 103. 998
(1981).
Method. R. Okazaki. K. Inoue, N . Inamoro, Tetrahedron Lett. 1979, 3673.
R. J. Bushby, M . D. PoNard. 1. Chem. SOC.Perkin Trans. 1 1979, 2401.
E. Schaumann. H. Behr, C. Adiwidjala, A. Tangerman. B. H. M . Lammerrnk.
B. Zwanenburg. Tetrahedron, 37, 219 (1981).
Naturally Occurring Cyclopropenone Derivativesf"]
By Ferdinand Bohhann, Jasmin Jakupovic, Lutz Miiller,
and Angelika Schusrer[*]
Dedicated to Professor Hans Herloff Inhoffen on the
occasion of his 75th birthday
The thione (Id) was prepared conveniently from dichlorodisulfane''] and the hydrazone ( l ~ ) [ Both
' ~ ] .n,m* absorptions of the C=-S- and Nz--N-chromophores of ( l d ) exhibit
the expected low intensity [ Aman(log&,in hexane): 234.5
(3.947), 302.5 (2.117), 342 (2.362), 529 (1.102)]. When (Ic)
was irradiated at 5 "C in [Di,]methylcyclohexane ( A = 350
nm)[6".c,el,up to 50% conversion, only one compound was
formed in 74% yield (in benzene: 65% yield at 29% conversion). NMR spectra (in [D6]benzene: & = I S 5 ( s , 2CH3),
1.69 and 1.79 (q, J=0.6 Hz, CH,); 6("C)=2I1l, 21.3 (CH,),
28.3 (2CH3),46.5 (quart. C), 114.4, 130.9 ( G - C ) ) and comparison with an authentic sample of (10)[4b1established the
isopropylidenethiirane structure (10) as the photoproduct.
On prolonged irradiation of (Id), unidentified products
emerged. In contrast to ( l a ) and (lb)[", the photolysis temperature ( - 60 to + 90 "C) had no significant influence. At
- 195 "C in [Di4]methylcyclohexane,however, (Id) was photostable. The photolysis of (Id) using light of wavelengths
>330 nm produced a single product only up to 26%conversion.
Moreover, on irradiation of I-pyrazolinethione-S-oxidesof
type ( l e ) at 0 ° C in benzene, the corresponding isopropylidenethiirane-S-oxides were obtained in 13-17% yields" 'I.
Received: June 10, 1980 12711 IE]
Revised: February 11. 1981
German version: Angew. Chem. 93, 293 (1981)
[ I ] P. S. Engel, Chem. Rev. 8U. 99 (1980).
121 H. Quast, A . FUO, A . Heublein, Angew. Chem. Y2.55 (1980); Angew. Chem.
Int. Ed. Engl. 19, 49 (1980).
[3] a ) W. L. Mock. Ph. D. Thesis, Harvard University 1964; b) P. S. Engel, L.
Chen. Can. J. Chem. 52,4040 (1974). C O and N2 were obtained in a 3: 1 ratio as photolysis products of ( f a ) .
141 a ) W. J. Middleron, J. Org. Chem. 34. 3201 (1969); b) A. C. Horrmann, A.
Bharracharjva, J. Am. Chem. SOC.98. 7081 (1976); c) E. Jongejan, 71 S. V.
Buys, H. Steinberg, T. 3. de Boer, Rec. Trav. Chim. Pays-Bas 97. 214 (1978).
d ) E. Block, R. E. Penn, M . D. Ennb. 71 A. Owens, S.-L. Yu, J. Am. Chem.
SOC.100,7436 (1978).
[ S ] H. J. Rodriguez, J:C. Chang. T F Thomas, J. Am. Chem. SOC 98. 2027
(1976).
[6] a ) 14 mg ( f a ) and 12 mg (Id), respectively, in 0.5 ml solvent were Irradiated
in Pyrex-NMR-tubes, which had been carefully degassed and sealed at 10-
292
0 Verlag Chemre CmbH, 6940 Wernherm, 1981
The overground part of Telekia speciosa (Schreb.) Baumg.
(Compositae, Tribus Innulae) contains, besides numerous
sesquiterpene derivativesI'l, two difficultly separable, relatively polar compounds of empirical formula Cj5H200
which, according to the IR spectrum, however, are not alcohols. The main component reacts with methanol in the presence of 4-pyrrolidinopyridine['I to give the well known methyl ester (3)I3]. IR ( Y= 1840 and 1588 cm-I) and 'H-NMR
spectroscopic data ( 6 = 8.46, d, J = 1.5 Hz) indicate presence
of the cyclopropenone derivative (1). The 'H-NMR signals
of ( I ) can be completely assigned by spin-decoupling. The
"C-NMR spectrum is also consistent with structure (1).
r
c1 _.
1
Since no data were available for monosubstituted cyclopropenones, we prepared cyclohexylpropenone (7) by addition of dichlorocarbene to (5). The dichloro compound (6)
probably occurring as an intermediate hydrolyzes even during work-up, giving moderate yields of (7), whose 'H- and
I3C-NMR spectroscopic data correspond very well with
those of the natural product (Table 1). The stereochemistry
at 7-H in ( I ) follows from the coupling constants and the stereochemistry of (3). Noteworthy is the extreme downfield
shift of the I3C-NMR signals of C-l 1 in the case of ( I ) and of
C-7 in the case of (7), which may be due, inter alia, to the dis-
['I
['I
["I
Prof. Dr. F. Bohlmann [ '1. Dr. J. Jakupovic. DipLChem. L. Miiller, A.
Schuster
Institut fur Organische Chemie der Technischen Universitat
Strasse des 17. Juni 135. D-1000Berlin 12 (Germany)
Author to whom correspondence should be addressed.
Naturally Occurring Terpene Derivatives, Part 353.-Part 352: A. Rusrazyan, C. Zdero, and F. Bohlmann, Phytochemistry 20 (1981). in press.
0570-0833/RI/~303-0242
S 02 50/0
Angew. Chem lnr. Ed. Engl. 20 (1981) N o 3
symmetry of the compounds. In disubstituted compounds it
is not so extremeL4].
The 'H-NMR signals'51for the cyclopropene protons, like those of the IR bandsf61,correspond to the
data of well-known compounds (Table 1).
Table 1. 'H-NMR data of (I), (21, (4). and (7) (CDCI,, 400 MHz, TMS as internal standard). ',C-NMR data of (I) and (7) (In CDCI,), and further physical
data of ( I ) , (2) and (4)
'H-NMR ( 6 values) [a]
(11
(2)
5.39 ddd
2.01 m
1.95 m
1.41 m
5.35 d (br)
2.2 m
1.95 m
1-H
2a-H
213-H
3-H 1
4-H J
5-H
6a-H
6P-H
7-H
8a-H
8P-H
9a-H
9P-H
13-H
14-H
1.56 dd
2.34ddd
3.05 ddddd
1.70 dddd
2.20 ddddd
2.07 d (br)
2.38 ddddd
8.46 d
0.88 s
15-H
089 s
1
i
-
1.65-1
5 m
1.58 dd
2.10 ddd
2.98 dddd
1.41 dddd
1.79 d (br)
2.33 d (br)
2.2 m
8.39 s
0.95 s
o.84
1
\
(71
165-1.35
2.79 dddd
1.98 m
1 73 m
2.1-1.9
m
rn
I
1.65-1.35
1
j
m
2.34 d (br)
1.98 m
1.73 m
1.62 m
J
\
141
-
2.78 dddd
1.62 m
2.0 m
1.62 m
8.40 s
0.78 s
4.76 ddd
4.44ddd
J
8.38 s
C-7
C-8
C-9
C-I0
C-ll
C-12
C-13
C-14
C-15
122.0
29.1
26.6
340
37.7
41.1
41.1
29.2
25.5
144.5
C-1
C-2,6
C-3.5
C-4
36.7
29.3
24.8
25.6
C-7
C-8
C-9
173.0
159.0
146.7
174.9
158.4
147.4
154
19.5
( I ) , IR (CCI,). Y= 1840. 1588 crn ' (cyclopropenone); MS: m/e=216 151 ( M + ,
14%). 201 (M-CH,.
13). 188 (M-CO, 13). 173 (201-CO. 45). 131
-78 (1=589 nrn),
(173-CHKH - C H > ,69. RDA [bl). 91 (C,H:. 100); [.I2"=
-81 (578). -93 (546). - 141 (436) (c=0.65. CHCI,)
(2). IR (CCI,): Y= 1830. 1585 cm ' (cyclopropenone); M S m/e=216.151 ( M +,
12%)
(4). IR (CCL): v= 1835. 1600cm ': MS: m/e=216.151 ( M i , 38). 201 (11). 188
(21). 173 (45). 91 (100); [.Iz4=
+ 2 2 (h=589 nm), +24 (578). +25 (546). +34
(434) ( c = O . l . CHCI,)
la] Coupling constants J [Hzl: (I): 1.2a=1.9=2; 1,2@=5; 2,9=2; 4,15=6.2,
6a,6P = 14; 6a.7 =6.68,7 = 2.5; 6&8@= 2.5; 7,8a =4.5; 7.8P =8P,9a =8P,9P = 2.4;
7,13=1.5; 8a,9a=4.5; 8a,9P=8a,8P=13; 9a,98=14; (2): 1.2=5: 4,15=6.5;
6a.7 = 1 I;
6p,7 = 3.5;
6p,Sp = 2;
7.8a = 13;
7,8P = 1;
6a,6P = 13 5.
8a,8P = 8a.9P = 13; 8a.9a =4; 9a,98= 15; (4): 3,15 = 5,15 = 15,15' = 1.5;
5,6p= 12.5;
6a.7 = 7,Ra = 4
6P.7 =7,8P = 12.5:
(7):
1.2a = 1.6a =3.5:
1.26 = 1.66 = 9.5. [b] RDA = Retro-Diels-Alder cleavage.
According to the 'H-NMR data (Table 1) the second component is undoubtedly the eudesmane derivative (4). Although, only few signals are interpretable by 1st order rules
the spectrum is, nevertheless, very similar to that of the corresponding eudesmane. The allyic coupling for 13-H is missing; however, the chemical shift of 13-H is almost the same
as that in the case of (1).
We have also isolated (1) from Lychnophora passerina
Gardn. (Compositae, Tribus Vernonieae), as well as an isomeric cyclopropenone which may have the structure (2). The
altered couplings for 7-H show that the cyclopropenone
moiety in (2) must be arranged equatorially. The 'H-NMR
data of (2) (Table 1) are similar to those of (1). Only the
In1
Ed Engl. 20 (1981) No. 3
The overground parts of the plants were extracted with
ether/petroleum ether and the extracts worked up by column
chromatography and by TLC (SO2). 1.5 kg of overground
parts of Telekia speciosa gave 25 mg of (1) and 3 mg of (4)
[TLC:ether/petroleum ether (1 :l)], 650 g of overground
parts of Lychnophorapasserina gave 10 mg of (1) and 6 mg of
(2), while 8 mg of (1) and 6 mg of (2) were isolated from 100
g of roots. (1) and (2) are colorless oils.
(7): To a solution of 100 mg of (5) (prepared by reaction of
l,l-dibromo-2-cyclohexylethylene with n-butyllithium at
-78 "C and subsequent treatment with chlorotrimethylsilane) in 5 cm3 CHC13 is added 15 mg of benzyl(triethy1)ammonium chloride and the stirred mixture treated dropwise at
20°C with 5 cm3 50% NaOH solution. After 2 h the mixture
is poured into 100 cm3 of H20, taken up in ether, and the residue obtained on evaporation purified by TLC (ether);
yield: 60 mg (5) and 8 mg (7).
Received. November 28. 1980 [ Z 710 IE]
German version Angew Chem Y3, 280 (1981)
Miscellaneous data
Angew Chem
Experimental
-
"C-NMR ( 6values)
(71
c-l
C-2
C-3
C-4
c-5
C-6
chemical shifts of 6-H and 8-H are somewhat different from
those of ( l ) ,since the deshielding effects operate differently
owing to the changed stereochemistry, as can be deduced
from Dreiding models. ( I ) , (2) and (4), are the first naturally
occurring cyclopropenone derivatives.
F. Bohlmann, J. Jakupovic, A. Schusrer, Phytochemistry 20 (1981). in press.
G. Hofle, W. Sfeglirh. Synthesis IY72. 619.
F. Bohlmann, C. Zdero, M. Silva, Phytochemistry 16, 1302 (1977).
E. V. Dehmlow, R. Zersberg, S. S. Dehmlow, Org. Magn. Reson. 7. 418
(1975).
151 P. Crabbe. H. Carpio, E. Velarde. J. H. Fried, J . Org. Chem. 38, 1478
(1973).
16) R. Breslow, L. J. Allman, J. Am. Chem. SOC.XX, 504 (1966)
[1]
121
[31
[41
Biosynthesis of Natural Porphyrins:
Studies with Isomeric Hydroxymethylbilanes
on the Specificity and Action of Cosynthetasel'.]
By Alan R. Battersby, Christopher J. R. Fookes,
George W. J. Matcham and Pramod S. Pandey'']
Dedicated to Professor Hans Herloff Inhoffen
on the occasion of his 75th birthday
Uroporphyrinogen-111 (4) is the precursor of the natural
porphyrins, chlorins and corrins and its biosynthesis from
porphobilinogen (1) requires the enzymes deaminase and cosynthetase"). The biosynthesis involves the building of an
(2), folunrearranged tetrapyrrole, the bilane derivativeL3.*]
lowed by a single intramolecular
An enzymic replacement of the amino function of (2), X=NH3
and of (1) by another nucleophile [shown as X in (2)] before
the final cyclization with rearrangement is discussed e. g.
in r31. With deaminase acting alone on porphobilinogen ( l ) ,
the product released is the unrearranged hydroxymethylbilane15.6.71 (3). Natural and syntheticr51(3) were identical substrates for cosynthetase and the product was uroporphyrinogen-111 (4).
The foregoing knowledge and synthetic methodology
made it possible to probe the action of cosynthetase by syn['I Prof. Dr. A. R. Battersby, Dr. c.J . R Fookes, Dr. G. W. J. Matcham, Dr P.
S. Pandey
University Chemical Laboratory
Lensfield Road, Cambridge, CB2 1 EW (England)
[**I
This work was supported by the Science Research Council and by Roche
Products Ltd.
0 Verlag Chemie GmbH. 6940 Weinheim. 19x1
0570-0833/8l/0303-0293
S 02.50/0
293
Документ
Категория
Без категории
Просмотров
0
Размер файла
242 Кб
Теги
occurring, naturally, cyclopropenones, derivatives
1/--страниц
Пожаловаться на содержимое документа