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Diazirines as Photochromic Valence Isomers of -Diazo Carbonyl Compounds.

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C 0 M M U N I C AT1 0N S
Synthesis of Bicyclic y-Lactones from ZCycloalkene1,4diols
By Kiyosi Kondo, Masakatsu Matsumoto, and Fumio MoriC*]
We have recently reported that the condensation of trans-2alkene-I ,4-diols with orthocarboxylic esters leads directly to
y-lactones bearing vinylic substituents in the P-position['].
The reaction has now been extended to cyclic alkenediols
(I) and found to be a simple and convenient method for the
preparation of bicyclic y-lactones. One of the products
is the well-known precursor ( 4 a ) for the synthesis of prostaglandins and jasmones[*'. The starting 2-cycloalkene-I,4-diols
( I ) can easily be obtained by photosensitized oxygenation
of cyclic 1,3-dienes followed by reduction of the resulting
1,4-endoperoxides with thiourea or LiAlHb
Thermal condensation of the diols ( 1 a)-( I d ) with triethyl
orthoacetate in the presence of a catalytic amount of a weak
acid, such as hydroquinone or phenol, and distillation of
the reaction mixture leads directly to the lactones (4a)-(4d)
(see Table 1). Though the distilled ( 4 a ) was essentially pure
judging from its NMR spectrum, careful analysis by GC-MASS
revealed that the cyclopentadienes (2) and (3) were present
as contaminants.
The analogous Claisen rearrangement followed by cyclization
can also be performed with the vinyl ether (5)13].Heating of
( 5 ) in xylene under an argon atmosphere for 4 h afforded the
bicyclic y-lactol 2-oxabicyclo[3.3.0]oct-6-en-3-ol( 6 ) directly
in 63 % yield ; b.p. 49 T / O . l S torr (44-45 oC/O.Ol torrt2'I).
OH
dH
2-0xabicyclo[3.3.0]oct-6-en-3-one (4 a )
A mixture of cis-2-cyclopentene-l,4-diol(I a ) (3.0g, 30mmol)
and triethyl orthoacetate (11.3 g, 70mmol) was heated with
hydroquinone (0.33g, 3mmol) at 140-150"C for 6h with
continuous removal of the resulting ethanol. The reaction
mixture was fractionally distilled under reduced pressure. The
first fraction was unreacted orthoester, and the second one
was the desired bicyclic y-lactone ( 4 a ) ; yield 3.08g (85%);
b.p. 74"C/0.3 torr (70-71 "(70.2 torr[2c1).
Received: September 23, 1974 [Z 122 IE]
German version: Angew. Chem. 87,109 (1975)
CAS Registry numbers:
( l a ) . 29783-26-4: ( l b ) . 53762-85-9: ( I c ) , 53762-86-0:
( I d ) . 37996-40-0: (4a). 26054-46-6; (4h). 34896-02-1 ;
( 4 ~ 1 ,53762-87-1 ; ( 4 d ) , 53783-45-2; (6). 53762-88-2; (7). 34636-26-1 :
triethyl orthoacetate. 78-39-7.
[l] K. Kondo and F. Mori, Chem. Lett. 1974, 741.
[2] a) E. J. Corey and R . Noyori, Tetrahedron Lett. 1970, 311; b) E. J.
Corey and T Raoindranathan, ibid. 1971,4753; c) P. A. Grieco. J. Org. Chem.
37, 2363 (1972); d) E. J. Corey and J. Mann, J. Amer. Chem. SOC. 95,
6832 (1973); e) J. J. Partridge, N . K . Chadha, and M . R. Uskokouic, ibid.
95, 7171 (1973); f) E. J. Corey and B. 8 . Snider, Tetrahedron Lett. 1973,
309 1.
[3] Refluxing of the diol ( l a ) in n-butyl vinyl ether in the presence of
a catalytic amount of mercury(I1) acetate for 2 h afforded a mixture of the
monovinyl ether (5) (91 %) and divinyl ether (9%). total yield 80%. The
ether ( 5 ) could easily be separated by column chromatography on neutral
alumina (Woelm, activity grade IV).
?H
/--
0
04
( a ) , n = 1;
(b), n
= 2; ( c ) .
Diazirinesas Photochromic Valence Isomersof cl-Diazo
Carbonyl Compounds[**]
n = 3; ( d ) . n = 4
By Erika Voigt and Herbert Meied']
Table 1. Bicyclic y-lactones (4) from diols ( I ) . Hydroquinone was used
as a catalyst.
[%I
IR (film)
[cm-'1
B. p.
T["Cl
14&150
140-150
140-150
15G160
85
85
83
43
1780
1775
1775
1780
7410.3
7810.16
9510.28
10310.22
Reaction conditions
f
(4a)
(4b)
(4c)
f4d)
PI
6
6
8
18
Yield
carbonyl compounds ( I ) .
["C/torr]
[*] Dr. K. Kondo and Dr. M. Matsumoto
Sagami Chemical Research Center, Nishi-Ohnuma 4-4-1, Sagamihara,
Kanagawa, 229 (Japan)
Dr. F. Mori
Central Research Laboratory, Kuraray Co. Ltd., Sakazu, Kurashiki,
Okayama, 710 (Japan)
Angew. Chem. internat. Edit. 1 Vol. 14 (1975) 1 No. 2
As cyclic valence isomers, the diazirines (2) and the 1,2,3-oxadiazoles ( 3 ) should be discussed in the context of the u-diazo
['I
Univ.-Doz. Dr. H. Meier and E. Voigt
Chemisches Institut der Universitat
74 Tubingen, Auf der Morgenstelle (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
103
Whereas heterocycles of type (3) are so far unknown, numerous alkyl- or aryl-substituted diazirines are known to
exist[']. In contrast to the a-diazo carbonyl compounds, which
are generally thermodynamically more stable than aliphatic
diazo compounds, the stability of the diazirines is lowered
by pseudoconjugation of the three-membered ring with a carbony1 function. Thus the half-life of 1-oxospiro[cyclohexane2,3'-diazirine] with regard to elimination of nitrogen is found
to be about one hour at room temperature['-31.
The ready thermal or photochemical elimination of nitrogen
from (1) and (2) imposes experimental limitations on the
valence isomerization (1)*(2). We have detected it for the
first time in the case of the thermally reversible photochromic
system 2-0x0-3-diazoindoline '(4)/2-oxospiro[indoline-3,3'diazirine] ( 5 ) .
picdata unequivocally indicate the structure ( 5 a). Compound
( 4 b ) behaves analogously. The UV spectra of ( 4 a ) and ( 5 a )
differ primarily in the absence of the longest-wave transition
[hm,,=440nm (~=21.3)],responsible for the red color of the
diazo compound ( 4 a ) , from the spectrum of ( 5 a ) . On complete retro-isomerization ( 5 a ) + ( 4 a ) , three isosbestic points
can be observed. The characteristic IR bands of ( 4 a ) and
( 5 a ) are listed in Table 1.
The 13C-NMRdata of ( 4 a ) and ( 5 a ) are compared in Figure
1.
Received: October 7, 1974 [Z 123 IE]
German version: Angew. Chem. 87, 109(1975)
CAS Registry numbers:
( 4 a ) . 3265-29-0; (Sa). 53762-89-3
[l]
pp.
[2]
[3]
[4]
[5]
[6]
E. Schmitr: Dreiringe mit m e i Heteroatomen. Springer, Berlin 1967,
114&
E. Schmitz, A. Stark, and Ch. Horig, Chem. Ber. 98, 2509 (1965).
E. Schmirz, XIII. IUPAC-Congress, Boston 1971, Vol. 2, pp. 2838
E. J. Moriconi and J. J . Murray, J. Org. Chem. 29, 3577 (1964).
G. Lowe and J. Parker, Chem. Commun. 1971, 1135.
R. A. Franich, G. Lowe, and J . Parker, J. C. S. Perkin I 1972, 2034.
Irradiation of ( ~ U ) [ ~ - ~inI methanol leads, by nitrogen elimination, via the carbene intermediate to the major products
3-methoxyoxindole ( 6 a ) and oxindole ( 7 a ) .
The Dimerization of Propylene to Linear Hexenes
By G. Henrici-Olive and S. Olive[*]
If the reaction is prematurely interrupted, a product can be
isolated by column chromatography which is itself photolabile.
On standing as the pure solid or in solution, the pale yellow
to colorless crystals are transformed back to the red starting
compound ( 4 a ) , even at room temperature.
According to cryoscopic molecular weight determination, the
crystalline compound must be an isomer of (4a). Spectrosco-
A homogeneous catalyst solution made up from pentanedionatopalladium, a tertiary phosphane, and ethylaluminum dichloride, in 1,2-dichIoroethane,dimerizes propylene selectively
(up to 95%) to linear hexenes, although at relatively low
reaction rate (Table 1). Replacement of the phosphane by
a phosphite increases the rate, but considerably lowers the
selectivity. As in all systems containing a Lewis acid such
as CzHsAICl2, special care must be taken to eliminate moisture
from the reaction solution. Otherwise highly active cationic
species will cause the polymerization of propylene.
Table 1. Characteristic stretching vibrations of ( 4 a ) and ( S o ) F [cm-'1.
Table I.Dimerization ofpropylene with Pd/AIcatalysts in the presence ofphosmol/l; [C,H,AICI,] =
phorus-containing additives. [Pd(acac),] = 2 x
22 x
mol/l: [P]/[Pd] = 2: [propylene] = 1.3 mol/l; T = 20°C: f = 3 h
Phosphorus
compound
Conversion
in KBr
[%]
linear
hexenes
Selectivity [XI
methylpentenes
dimethylbutenes
Bu3P
Ph,P
(Ph O),P
4
4
12
95.1
81.8
23.6
4.9
18.2
68.2
8.2
3100
3180
(40)
(Sa)
3430/3180
3380/3145
c!
1112311R
z
2
I
2085
-
-
1630
21 10
-
-
1620
/'\
1670
1740/1690
1685
1720
Four reaction modes are conceivable for the dimerization
of propylene at a transition metal center M, depending upon
the orientation of the monomer in the two insertion steps
(Scheme 1).
The first step is reversible, since P-hydrogen abstraction
regenerates a metal hydride and propylene. The second step
is irreversible; P-hydrogen abstraction at this stage gives the
product dimer and a metal hydride, which latter continues
the kinetic chain.
\
-j .-. 4i
0
a4
o-'
C_""NZ
z
0
Fig. 1 . "C-NMR signals of 2-oxa-3diazoindoline ( 4 a ) and 2-oxospiro[indoline-3.3'diazirine] (Sa). Data in ppm relative to TMS as internal standard.
104
-
['I
Dr. G. Henrici-Olive and Prof. Dr. S. Olive
Monsanto Research S.A.
CH-8050 Zurich, Eggbuhlstrasse 36 (Switzerland)
Angew. Chem. infernat. Edit. / Vol. 14 ( 1 9 7 5 )
No. 2
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