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New Reactions of Metal Carbonyls and Cyano Complexes in Liquid Ammonia.

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controls was observed. The same action was shown when
application was effected both by spraying and via hydrocultures. No activity was shown against Phytophthoruinfestuns
on tomatoes. A similar but slightly weaker effect was exhibited by isonicotinic semicarbuxidc hydrochloride and by
free isonicotinic acid and its ethyl cster.
Among the products of alkylation of the terminal N-atoms of
isonicotinic hydrazide, a very slight increase in the inhibitory
effect on infection was observed only in the case of isonicotinic w-methylhydrazide hydrochloride. Quarternization
of the ring nitrogen atom with alkyl halides of varying
cdrbonchain length invariably resulted in complete loss of
systemic activity. Condensation of isonicotinic hydrazide
with aldehydes such as salicylaldehyde and glyceraldehyde,
and with glucose gave products of activily similar to that of
the starting material. Of the condensation products with
ketones, only the isonicotinoyl hydrazone of acetone had
activity comparable to that of INH. The systemic activity
observed on celery plants in the greenhouse could not be
reproduced in field experiments.
[VB 651/60 IE]
New Reactions of Metal Carbonyls and
Cyano Complexes in Liquid Ammonia
i) 4 FcO,(CO)lz
H.Behrens, Erlangen (Germany)
The reaction of Mnz(C0)lo in liquid NH3, on the other
hand, is characterized by the formation of a CO-containing
cation [Mn(C0)3(NH3)3]c, which is isoelectronic with
Cr(CO)3(NH3)3, which is obtained from Cr(CO)6 and liquid
NH3 at 120°C:
Reactions with liquid NH3 of mono- and polynuclear carbonyls of metals of the first long period proceed by the
a) Replacement of CO by NH.1 e.g. in Cr(CO)6 [I] and
N i(CO14 121;
b) Reduction to the carbonylomclallate anion and oxidation
of one CO molecule to CO(Nt12)2 e.g. in Fe(C0)s [1,3],
FeAC0)9 131;
c) Disproportionation to a hexamminemetal cation and a
carbonylometallate anion; the liberated CO reacts further
by b) e.g. with Co2(CO), and COJ(CO)I~
Recent investigations have shown that disproportionations
occur in the reactions of Fe3(C0)12 [31 and Mnz(C0)lo [41
with liquid NH3. With the formcr, the following stages are
known to occur:
18 NH3 + 3 [Fe+"(NH3kl [FCI-~I(CO)II] IS co
ii) [FGRIH~M
[Fei(C0)111+2 CO -P [Fe(NHikl [Fez(CO)sl+ Pe(C0)s
iii) FtO(C0)s 4 NH3 + (NH4)2[Fe-I1(CO)41 4- CO(NH2)z.
+ 3 NH3
+ [Mn+'(CO)dNH&] [Mn-kO)d
+ 2 CO.
Hexaearbonyls M(CO)6 and their substitution compounds
with 2,Y-dipyridyl of the type M(CO)4 dipy, react with KCN
in liquid NH3 at temperatures above 60°C, to form
cyanocarbonylometallate(0) complexes of compositions
K2[M(C0)4(CN)2] and K3[M(CO)3(CN)3], where M = Cr,
Mo,or W [5].
With KCN in liquid NH3, substitution products of Ni(C0)4
of the type Ni(C0)2L2 yield the dicyanodicarbonylonickellate(0) complex K2[Ni(CO)2(CN)*]; the reactions occur at
the following temperatures:
2 PI3
30 O C
[I] H. Eelrrens et al., Angcw. Chcm. 74, 120 (1962).
121 H.Behrens and J. Zidsperger, J. prakt. Chem. 14,249 (1961).
[3] H.Behrensand H.Wakamursu, thepress.
[4] Investigations by H. Behrens and H.Wakamatsu, to be
[Chemische Gesellschaft Erlangen (Germany),
November 22nd, 19621
[VB 663/64 JE]
reported soon in Chem. Ber.
[S] Unpublished work by
H.Vogl and H. Passnurr.
Resolution of l,l'-dimethylfernwr?ncZcarboxylic acid (I) .into
its optical isomers a and b is described by L.Westmun and
K.L.Rbelmrt, Jr. Their new synthcsis of I involves treatment
of 1,l'-dimethylferrocene with Ixityl-lithium followed by
carboxylation. The isomeric 3-carhoxylic acid is removed by
conversion into its bromobemyl cster and chromatography
on Al2O3. The racemate la, b (m.p. 108--109.5 "C)obtained
on hydrolysis is treated in aqimiis alcoholic solution with
Tbe oxidation of organic compounds with thallium triacetate is
reported by H.-J. Karbe. A comparison of the reactivity of
Pb(Iv) acetate, TI(II1) acetate, and Hg(lI) acetate on olefins,
cyclohexanone, diphenylmercury, glycols, and methanol
shows that TI(II1) acetate lies between the other two acetates
in its reactivity. Cyclohexene and thallium triacetate in
methanol produce the dimethylacetal of cyclopentylaldehyde
(62% yield), while in glacial acetic acid, the products are
diacetylcyclohexanediol and 2,3 diacetylcyclopentylalde
hyde (overall yield 35-50 %). In methanol, styrene yields
the dimethylacetal of phenylacetaldehyde while in glacial
acetic acid the product is diacetylphenylglycol (71 %). The
predominant product from isobutylene is diacetatylisobutyleneglycol (27 %), as well as some acetylisobutanol (5
o-Allylphenol gives the organothallium compound I,which
solutions of alkaloids. The sparingly soluble salts obtained
were purified by repeated fractional crystallization from
ethanol/water, best results being obtained with cinchonidine
and quinidine. Acidification of the cinchonidine fraction
givesI(+),m.p. 119-121"C, [al::'=+37.5f1.5"(~-0.8,
CHCb).The quinidine fraction yiclds I (-), m.p. 119-121 "C,
[a]$?= -36 f 1 (c = 0.8, CHCI.31. / Aced chem. scand. 16,
1199 (1962) / -Br.
[Rd 355/109 IEJ
Angew. Chem. internat. Edit. I Yol. 2 (1963) I No.2
forms a-acetoxymethylcoumaran on warming with glacial
acetic acid. Two intermediates containing thallium can be
isolated, which correspond with the Pbcontaining intermediates postulated previously in the Pb(1V) acetate oxidation (e.g. ~Hs-CH(OCH~)-CH~TI(OAC)~
from styrene). /
Liebigs Ann. Chem 656,204 (1962) / -Ma. [Rd 359/1 I0 iE]
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ammonia, carbonyl, reaction, metali, cyan, complexes, liquid, new
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