вход по аккаунту


The Behavior of Modifications of Arsenic Sesquioxide.

код для вставкиСкачать
Chemiluminescence of Cyclic Diacylhydrazides
and Diazaquinones
luminescence of luminol and related compounds, which
postulated decomposition of a peroxide of type ( I S ) as energy-releasing step.
By K . - D . Gundermann[*l
Dialkylamino groups in the 3-position of the phthalhydrazide
system are sterically resonance-hindered, and thus compounds
of type ( I ) show only very weak chemiluminescence o n hemin-cataIyzed oxidation in aqueous-alkaline H202.
Lecture at Gottingen (Germany) on February 1 , 1968 [VB 150 IEI
German version: Angew. Chem. 80,494 (1968)
[*] Prof. Dr. K.-D. Gundermann
Institut fur Organische Chemie der Technischen Universitat
3392 Clausthal-Zellerfeld, Leibnizstr. 6 (Germany)
[l] K.-D. Gundermann, Angew. Chem. 77, 572 (1965): Angew.
Chem. internat. Edit. 4, 566 (1965).
[2] K.-D. Gundermann, Lecture at GDCh-Hauptversammlung
Berlin, September 1967.
[31 M . M . Rauhut, A . M . Semsel, and B. C. Roberts, J. org.
Chemistry 31, 2431 (1966).
Compounds of type ( 2 ) [vinylogs of ( I ) in the wider sense]
are more effective than luminol (3-aminophthalhydrazide) in
purely aqueous systems. However, in mixtures of DMSO and
water, hydrazides of type (3) [I] and (4) [vinylogs of ( I ) in,
respectively, the wider and the narrower sense] are much
superior t o luminol and hydrazides of type (2). Compound
( 4 ) with R' = cyclohexyl and n-pentyl was synthesized from
dimethyl 3-methylphthalate (5) by way of the steps (6)-(11].
(10): R =
(9): R
= CH~CH:
(11): R = CHzCHO
Dehydrogenation of the monosodium salts of the corresponding hydrazides with fert-butyl hypochlorite in dimethyl ether
leads t o the azaquinones (12)-(14).
Compounds ( 1 3 ) and (14) are deep violet in the crystalline
state and chemiluminesce when their acetone solutions are
mixed with aqueous sodium hydroxide. The light yield is a
function of the amount of H202 present, which, however,
can also be replaced by oxygen 121. The quantitative findings
support the mechanism proposed b y Rauhut 131 for the chemi-
The Behavior of Modifications of Arsenic
By I . N. Stranski[*]
The behavior of arsenolite (cubic) and claudetite (monoclinic)
offends against some of the rules for polymorphic substances,
e.g., against the rule that crystals cannot be heated above
their transition point (or melting point) and also against
Ostwald's stepwise rule. The fundamental assumption [1-51,
which has been confirmed by structural analysis of claudetite,
is that the two forms differ basically in the nature of the
lattice components and in their mode of union: claudetite has
a layer lattice with cross-linkage by primary valences within
the layers and by van der Waals bonding between the layers;
arsenolite, however, contains a molecular lattice of diamond
type formed from saturated, isolated As406 molecules.
All the anomalies in the phase transitions (evaporation,
condensation, dissolution, crystallization, melting, and solidification) are caused by the fact that the units of the initial
phase must be rearranged t o units of the product phase.
Appreciable activation energies are required in practice for
this process, and particularly so when primary valences have
to be cleaved.
The condensation as arsenolite instead of as the stable
claudetite that is observed above and below the transition
point (ca. -3O'C) results because u p to ca. 800°C arsenic
oxide vapor consists almost exclusively of saturated As406
particles, whose bonding must be at least partly destroyed before incorporation into the claudetite lattice. Correspondingly,
the evaporation of claudetite is hindered in comparison with
that of arsenolite, and its rate of evaporation at comparable
vapor pressure is lower by many powers of ten, because only
secondary valences need to be broken during destruction of
the claudetite lattice.
For dissolution and for crystallization from solutions the
decisive factor is whether the solvent can (e.g., HzO) or cannot
(e.g., AsBr3) set up a n equilibrium between the units composing the various phases. In the negative case measurements of solubility can lead to totaliy false conclusions about
the transition point. That arsenolite can be heated unchanged,
not merely above its transition point, but even above its
melting point, arises because the melt has a claudetite-like
structure, so that cleavage of the lattice is necessary also for
conversion into the molten state. Whereas in many cases
the activation energy can be lowered catalytically (e.g., by
entry of H 2 0 into the action), it is often added as thermal
energy or ion impact in enforced condensations. However, in
such cases amorphous, glassy condensates usually result, and
Angew. Chem. internat. Edit.
/ Vol. 7 (1968) 1 No. 6
crystalline claudetite is formed only under special experimental conditions.
The modifications of arsenic oxide provide a clear model
system for the study of phase transitions that are influenced
by structure.
The constitution of the yellow crystalline, optically inactive
r-indomycinone ( I ) was proved by K. H . Dahm [21, by ozone
degradation of dihydro- and tetrahydro-a-indomycinone
(2) to 9,10-dihydro-l,8-dihydroxy-3-methy1-9,1O-dioxo-2anthracenecarboxylic acid, chrysophanic acid ( 3 b ) , and
Lecture at Hamburg (Germany) on February 2, 1968 [VB 148 IEl
German version: Angew. Chem. 80, 495 (1968)
[*I Prof. Dr. I. N. Stranski
Fritz-Haber-Institut der Max-Planck-Gesellschaft
1 Berlin 33, Faradayweg 4-6 (Germany)
[l] K. A . Becker, K. Plieth, and I . N . Stranski, Progr. inorg.
Chem. 4,1 (1962).
[2] K. A . Becker, W. Kollmitt, and I. N . Stranski, Z . physik.
Chem. N.F. 37, 314 (1963).
[3] K. A . Becker, H . Karge, and I. N . Stranski, Z . physik. Chem.
N.F. 44, 1 (1965).
[4] K. A . Becker, H . Karge, and I. N . Stranski, 2. physik. Chem.
N.F. 44, 7 (1965).
151 I . Klipping, 2. physik. Chem. N.F. 54, 68 (1967).
Indomycins and Indomycinones
By H. Brockmann [*I
From the mycelium of Streptomyces sp. Ind. 927, J. SchneN[ll
has isolated: indomycin A, yellowish-red, provisional molecular formula C40H52N2010 [6 C-CH3, NH-CH3, N(CH3)z.
5 active H atoms], [a]’,” = +345 (CHC13), bacteriostatic
against B . subtilis t o a dilution of 1:2.5 x 105, carcinostatic
against Ehrlich ascites tumor at 2 mg/kg mouse; indomycin
B, brownish-yellow, provisional formula C3gH4&010
[5 C-CH3, NH-CH3, N(CH&, 5 active H atoms], [a]: =
+319 (CHCI3), bacteriostatic against B. subtilis t o 1 : 2.5 x
106, carcinostatic against Ehrlich ascites tumor at 2 mg/kg
mouse; and indomycin C, brownish-red crystals, provisional
formula C41H52N2011 [6 C-CH3, NH-CH3, N(CH3)2,
7 active H atoms], [a]; = +254 (CHCI3), carcinostatic
against Ehrlich ascites tumor at 30 mg/kg mouse.
The indomycins have a bitter taste, are yellowish-red in
organic solvents, violet in methanolic alkali hydroxide, and
red in concentrated sulfuric acid, give a red vat with dithionite, and contain a quinone group with a chelated hydroxyl
group. Further, biologically inactive, yellow indomycinones
were also isolated from the mycellium; these are either the
indomycin chromophores or compounds resembling them
very greatly in structure.
(30): R = COzH
(3b): R = H
2-methylhexanoic ( 4 ) or butyric acid respectively, supplemented by 1H-NMR and mass spectra of (21,of dihydroa-indomycinone, and of their acetates. The configuration of
the side chain has not yet been established.
Lecture at Clausthal-Zellerfeld (Germany) on January 26, 1968
[VB 156 1El
German version: Angew. Chem. 80, 493 (1968)
[*] Prof. Dr. H. Brockmann
Organisch-Chemisches Institut der Universitat
34 Gottingen, Windausweg 2 (Germany)
[l] J. Schnell, Dissertation, Universitat Gottingen, 1963; in the
present report, the indomycins are designated A, B, C and n o t
a-, fL,
y-, as they are in Schnell’s work.
[2] K . H. Dahm, unpublished
Olefins were converted into aldehydes by H . C . Brown,
R. A . Coleman, and M. W. Rathke by hydroboronation of the
olefins, treatment of the trialkylboranes with C O and
LiAIH(OCH& at atmospheric pressure and room temperature, a n d subsequent careful oxidation. Examples: 1 hexene + heptanal (yield 98 %); isobutene + 3-methylbutyraldehyde (91 %) ; norbornene -+ 2-norbornanecarbaldehyde (87 %). / J. Amer. chem. SOC.90, 499 (1968)/ -Kr.
[Rd 840 IE]
Microbiological conversion of 3-methylpyrocatechol into 2hydroxy-6-oxo-trans-Z-trans-4-heptadienoic acid ( I ) is described by D . Catelani, A . Fiecchi, and E. Galli. After incubation of 3-methylpyrocatechol with a Pseudomonas desmolyticum culture in phosphate buffer of p H = 7, a yellow
Angew. Chem. internat. Edit. / Vol. 7 (1968)
/ No. 6
rI’ c - o r r
compound of m.p. 122-124OC (decomp.) could be isolated
from the culture liquid; this product was identified as ( I ) . /
Experientia 24, 113 (1968) / -Ma.
[Rd 850 IE]
Exchange of oxygen and hydrogen atoms of o-nitrotoluene was
observed by E. K. Fields and S . Meyerson. On pyrolysis of
a solution of o-nitrotoluene in methanol at 6OO0C (11 sec
contact time) methyl anthranilate was formed as principal
48 1
Без категории
Размер файла
203 Кб
behavior, modification, arsenic, sesquioxide
Пожаловаться на содержимое документа