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Organic Aluminum Heterocycles.

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The 6'-demet hyldehydrogriseofulvin (I) was hydrogenated
over palladium on charcoal followed by treatment with zinc
and acetic acid [4]. The resulting product was separated into
35 % of the alkali soluble benzophenone derivative I1 and a
tane. On deuterolysis, this yields o-deutero-3-deuteropropylbenzene as the only hydrocarbon and is thus likely to have
the structure:
Alkyl-exchange reactions between bis-boryl-alkanes 151 and
trialkylaluminum in molar proportions of 1 :3 to 1:4 produce
1 -alkylaluminacyclopentaneswhich are distillable in V ~ C U :O
H3CO
I
+ Al(CH3)3 +
neutral moiety, which was chromatographed on alumina and
which yielded 70-80 % of pure 6'-demethylgriseofulvin (IV,
m.p. 227-228 "C) as the major component, together with a
minor amount of 6'-demethyl-2',3'-dihydrogriseofulvin.
Received, June 12th. 1962
[Z 304/137 IE]
[l] D. Taub et al., Chem. and Ind. 1962, 557.
[2] N. M.Cullinane and B. F. R . Edwards, J. chem. SOC.(London)
1957, 3016.
[3] C. H. HussaIl and J. R. Lewis, J. chem. SOC. (London) 1961,
2312.
[4]C. H . Kuo et al., Chem. and Ind. 1960,1627.
3H3CAI
(), +
2B(CH3)3
These liquids are colorless and can be distilled under reduced pressure; in cyclohexane, they exist as dimers but are
x > A L
CH3
Al
/\,
CH3
\/\
converted above 100 "C into polymeric compounds, which
solidify to glass-like substances at room-temperature.
Received, July 3rd. 1962
[Z 309/138 IE]
[l] Cf. J. J. Eisch and W.C . Kaska, J. Amer. chem. SOC.84, 1501
(1962).
[2] Cf. R. Polster, Liebigs Ann. Chem. 654, 20 (1962).
[3] Cf. R. Koster and G. Bruno, Liebigs Ann. Chem. 629, 89
(1960).
[4] R . Koster and K . Reinert, Angew. Chem. 71, 521 (1959).
[S] R . Koster, Angew. Chem. 71, 520 (1959).
Organic Aluminum Heterocycles
By Dr. R. Koster and Dr. G. Benedikt
Max-Planck-Institut ftir Kohlenforschung,
MiilheimiRuhr (Germany)
Five- and six-membered organic aluminum heterocycles [ 1,2]
have been obtained in exchange reactions involving boronand aluminum-alkyls [3].
When one mole of B-ethylboraindane or -tetralin 141 is
heated (not above 100 "C) with 1 to 1.5 mole of triethylaluminum and all the boron removed as triethylborane by distillation under reduced uressure, 1-ethylaluminaindanes or
-tetralins are obtained. Numerous new aluminum heterocycles were obtained as colorless crystals.
Photoisomerisation of 1.3-Cyclohexadienes
By Dr. H. Prinzbach and Dipl.-Chem. J. H. Hartenstein
Chemisches Laboratorium der Universitat
FreiburgIBrsg. (Germany)
Photochemically excited derivatives of 1.3-cyclohexadieneare
usually stabilised by ring fission according to A [l].
R
R
R
R
BR;
R'
e.g.
R'
R'
R = -CH&Hz--.
-CHzCHMe-CHz-CHZCHZCHZ-
=
CzH5. G H ,
Table 1. l-AIkylduminaindanes and -tetrdins
~
~
~
Compound
M. p. [ T I
1-Propylduminaiidane
I-Ethyl-3-methylaluminaindane
1-Propyl-3-methylaluminaindane
1-Propylaluminatetralin
52
102
103
liquid
Angew. Chern. internat. Edit.
Vol. 1 (1962) I No. 9
4"
R
R
Up to the present, intramolecular isomerisations according to
B have only been observed with rwo polycyclic systems 121.
and according to C only in the cases of dehydroergosterol acetate [l] and of pentaphenylcyclohexadiene[3].While investigating the conjugated addition of photochemically produced carbenes onto dienes [4], we observed that isomerisation according to B is also possible with simply substituted 1.3-cyclohexadienes. On irradiation (Hg high pressure arc, S 81 Hanau) in
etheral solution, in the presence of CHzNz as sensitiser, I [R =
C02CH3, Ama,(ethanol) = 309 mp (E = 13000); proton magnetic resonance spectrum: one singlet each at T = 2.42 (2
507
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