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Fulminate Complexes.

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thiopyrimidones. The corresponding derivatives of phenoxycarbonyl isothiocyanate decompose with loss of phenol and
yield thiouracil derivatives. This new pyrimidine synthesis
has so far proceeded smoothly in all cases.
-
":
R'NCS
,C=CH-R~
K~HN
R,!
,c=c
R~HN
= C O ~ K 1t3
, = CH,
(2), K' = NH2, K3 = C 0 2 K
I";:'
11; /
=C-R3
I
s
'2
'NHd
(11, K'
12' -C
,R3
R'-C -C-R3
II
I
R2-N, S,C=NR4
II
N,S,C-NBR4
13)
(41
The von Pechmann synthesis of substituted 5-amino-1,2,3thiadiazoles may be extended to diazoacetic ester, diazoacetamide, and diazoketones, when acyl isothiocyanates are employed. I n the simplified procedure, the appropriate acid
chloride is added dropwise to a solution of the diazoacetic
ester and sodium thiocyandte. The use of phenoxycarbonyl
isothiocyanate with subsequent mild alkaline hydrolysis
affords primary 5-amino-l,2,3-thiadiazoles,which may be
acylated, sulfonated, and diazotized.
Imidoyl isothiocyanates (prepared from imidoyl chloride and
alkali thiocyanate) dimerize spontaneously to red high-melting compounds, for which structure (5) is assumed. This is
another case of 1,4-addition of a n X=&-N=C=Y system.
Fulminate Complexes
W. Beck, Miinchen (Germany)
All the fulminato-complexes of transition metals known [I]
have the same type of structure as the homologous cyanocompounds. Recent examples include [ C O ( C N O ) ~ ~ - ,
[Ru(CNO).#-, and [Hg(CNO)$ -.A mixed cyano-fulminatocomplex, Na4[Fe(CN)sCNO], is obtained from pentacyanoammino- or pentacyanoaq uoferratr(I1)- and alkali fulminate.
Judging from the absorption spectrum of [Fe(CNo).#in the
visible region and from magnetic measurements, the fulminate ion has a strong ligand field which is only slightly less
than that of the cyanide ion. The infrared spectra of simple and
complex metal fulminates contain the CN stretching vibration
of the CNO ligands at 2200 2000 cm I and the NO stretching
vibration at 1200-1050 cm I. The C N - 0 bending vibrations appear at 500- 450cni 1. The C N stretching frequency
in fulminato-complexes appears at higher wave-numbers than
that in alkali fulminates. This leads to the conclusion, that the
structure M - C r N - 0 (M = metal ion) is favored in the
complexes. The infrared spectra indicate linear M-C-N-0
groupings. Aryl- and alkyl- metal fulminates such as RHgCNO
(R = C6H5, CH3C6H4, or C&sCH2), (C~HS)~TICNO,
and
( C ~ H S ) ~ S ~ Chave
N O been prepared [2]. Phenylmercury fulminate is obtained from diphenylmercury and mercury fulminate. Arylmercury fulminates can also be prepared by
treating mercury fulminate with arylmagnesium bromide. Triphenylsilyl fulminate, which is readily prepared from triphenylchlorosilane and silver fulminate, has a lower C-N
frequency than triphenylacctonitrile-N-oxide.This lowering
of the frequency can be explained by interaction of the x-electrons of the C N bond with the free d-orbitals of the silicon
atom.
[GDCh-Ortsverband Nordbayern, Erlangen (Germany),
June 20th, 19631
[VB 7331102 IE]
German version: Angew. Chem. 75,872 (1963)
[GDCh-Ortsverband Nordwiirttemberg,
Stuttgart (Germany), June 27th, 19631
[VB 7321100 IE]
German version: Angew. Chem. 75, 941 (1963)
[I] Cf. W. Beck and E. Schuicwr, Chim. Ber. 95, 3048 (1962).
I21 Investigations with E. Schrtierer.
SELECTED ABSTRACTS
The sex attractant of the male bumble bee is farnesol (I),
according to G. Stein. Substance (I) arises in the mandibulary
glands and can be extracted with pentane from the heads of
male bumble bees. The heads of worker bees contain only
traces of ( 1 ) ; extracts of the bodies of males and of workers
do not contain any. Compound (I) was isolated by chromaH , C ~ C = C H - - C H I - - C H ~ - C = C H ~CHz~-CHz-C=CH--CH?OH
CH 3
I
CH3
(I)
I
CH s
tography and investigated by ultraviolet and infrared spectroscopy. The physical characteristics are in complete agreement with those of farnesol. The drone presumably takes in
the farnesol in his diet as it occurs in almost all flower oils. /
Naturwissenschaften 50, 305 (1963) / --Kr. [Rd 609/180 IE]
Mass spectroscopy of non-volatile substances with molecular
weights of up to 800 was achieved for the first time by C.
Djerassi and co-workers by vaporizing the sample in the
electron-stream of the mass-spectrometer. Direct introduction
of the sample into the ionization chamber without releasing
the vacuum of the spectrometer is achieved using an attachment which is in the form of an introductory system made of
glass and which can be evacuated. Dimeric indole alkaloids,
porphyrins, and steroid antibiotics were investigated, and the
structure of cephalosporin was verified. / Experientia 19, 21 1
[Rd 615/1741E]
(1963) / - Re.
694
Pyridinepolycarboxylic acids and picolinecarboxylic acids have
been separated on paper chroniutograms by F. Kuflner and
F. Schindler. The separation is valuable for the determination
of the structure of heterocyclcs, especially alkaloids. 2-Butanol/cineol/hydrochloric acid ( I : I : I ) proved to be a good solvent system. The RF-values of 28 pyridinecarboxylic acids
are given. The spots on the chromatograms were made visible
with a new reagent which contains silver acetate, acetic acid,
and hydrazine. The limit of detection lies at less than 1 pg. /
[Rd 61 3/ 184 1El
Mh. Chem. 94, 252 (1963) / Re.
Quinonoid hydantoin dyestuffs were synthetized by Richurd
Kuhn and W. Bltru as models for a bacterial pigment which
probably contains a hydantoin residue. 5-(pDimethylaminopheny1)hydantoin (I) can be dehydrogenated with Pb02 in
acetonitrile/pyridine to give a red, crystalline dyestuff (2)
which decomposes above 150 " C . Dehydrogenation of 5-(3,4dihydroxypheny1)hydantoin iilso yields a red dyestuff as
crystals which become dark above 250°C without melting. /
Liebigs Ann. Chem. 662, 67 (1963) 1 Kr. [Rd 6071173 1El
Angew. Chem. intwnctt. M i i . I Vol. 2 (1963)
1 No. 11
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