close

Вход

Забыли?

вход по аккаунту

?

Gas-Chromatographic Separation and Analysis of Isomeric Halogenated Hydrocarbons.

код для вставкиСкачать
quantitatively separated by gas chromatography on a Ucon
LB 550 X Golay column (200 m ; internal diameter 0.5 mm).
A capillary chromatograph with a flame-ionization detector
was used. The carrier gas was helium (4.5 ml/min), and the
temperatures used are shown in Table 1 .
Table 1. Temperatures of flash heater, column, and detector.
Isomers
Chloro-n-heptanes
Bromo-n-heptanes
Chloro-n-octanes
Bromo-n-octanes
Chloro-n-decanes
5-Aralkyl derivatives of (3) have been obtained in almost
quantitative yields by catalytic hydrogenation (10
Pdcharcoal; dioxane; room temperature; 10 h) of the yellow
5-arylidene derivatives ( 4 ) which are readily available by the
condensation of aldehydes with the active methylene group of
(3), R = H. The following compounds were prepared:
m. p.
m.p.
m.p.
m. p.
m.p.
m.p.
m.p.
m.p.
170 "C
170-175 "C
175--179°C
230 ' C
232 OC
70 "C
90 ' C
90 "C
90 "C
I20 "C
The retention times of the isomeric halogenated hydrocarbons
and the resolution obtained for each individual pair of isomers are set out in Table 2.
The quantitative evaluation of the chromatograms was confirmed by the analysis of test mixtures. The maximum relative
error found was about 5 %, so that the use of correction factors is unnecessary.
The gas-chromatographic analysis of the unstable bromo-ndecanes still presents difficulties.
176 "C
ca. 290 "C (decomp.)
183 " C
230 "C
197 "C
181 "C
ca. 290 " C (decomp.)
= 116°C
Table 2.
70 "C
90 "C
90 "C
90 "C
120 "C
Retention times (tr) and effective resolution (8)[*I for the isomeric halogenated
Bromo-nheptanes
tr
8
[mini
['%I
135
94
91.5
85
100
98.7
Bromo-noctanes
Chloro-noctanes
Chloro-ndecanes
tr
[minl
8
100
100
100
151
114
-
103
101
100
94.4
100
94.4
tr
[minl
8
tr
8
[%I
[mini
[%I
168
113
110
102
100
98.9
100
170
119
115
-
105
-
[";I
~~
I-X-R
2-X-R
3-X-R
4-X-R
5-X-R
164
114
100
96.1
110
103
-
100
-
Compounds (3), R = H or alkyl, have anti-inflammatory
activity. They are stable towards hydrazine and amines,
whereas alkali hydroxide cleaves the ring and liberates hydrazobenzene. Also, the attempted alkylation of f 3 ) with alkyl
halide and NaOH resulted in the formation of hydrazobenzene.
100
-
-
-
110
Received, September 7th, 1964
[Z 827/657 IE]
German version: Angew. Chem. 76, 890 (1964)
-
[ I ] Li-Hoan Kung, Ph. D. Thesis, Technische Hochschule Aachen
1964.
[2] H. Kaiser: Chromatographie in der Gasphase. Bibliographisches Institut, Mannheim 1960, Vol. 11, p. 32.
Received, September 9th, 1964 [Z 822/652 IE]
German version: Angew. Chem. 76, 920 (1964)
[ l ] Sr. Goldschrnidt, Liebigs Ann. Chem. 437, 213 (1924).
[2] While this work was in progress, a patent has appeared,
describing the synthesis of (3), R=H, from sulfoacetic acid dichloride and hydrazobenzene without reporting the yield: R .
Doson and V. Papesch, U.S.-Patent 3037027; Chem. Abstr. 57,
12502 (1962).
[3] A . Michaelis and F. Schmidt, Liebigs Ann. Chem. 252, 308
(1889).
Gas-Chromatographic Separation and Analysis of
Isomeric Halogenated Hydrocarbons
By Dr. Elisabeth Bendel, cand. phys. W. Meltzow, and
Dr. Li-Hoan Kung
Institut fur Technische Chemie der Technischen Hochschule
Aachen (Germany)
After chlorination or bromination of high-molecular, straightchain hydrocarbons with, for example, N-chloro- or Nbromosuccinimide, t-butyl hypochlorite or hypobromite [ I ]
the isomeric chlorides of n-heptane, n-octane, n-decane and
the isomeric bromides of n-heptane and n-octane were
750
An External Magnetocatalytic Effect
By Doz. Dr. W. Haberditzl and Dipl.-Chem. Klaus Muller
Physikalisch-Chemisches Institut der Humboldt-Universitit
Berlin (Germany)
The existence of external magnetocatalytic effects, i. e. alterations of catalytic activity within external magnetic fields, has
been the subject of much controversy. We have now detected
such an effect with the enzyme glutamic dehydrogenase
(GI DH).
GIDH catalyses the reaction:
a-Oxoglutarate
+
NH,
+
DPNH
+
Glutamate
+ DPN +
H2O
The changes in the concentration of DPNH with time were
followed by spectrophotometry [l], and the catalytic activity
was calculated in units per ml [2]. The reaction mixture comprised 3 mi of 0.05 M triethanolamine buffer (pH 8.0),
0.045 ml of 0.01 M DPNH, 0.03 ml of 0.26 M EDTA, 0.1 ml
of 3 M ammonium acetate, and 0.03 ml of 10-7 M GIDH.
After addition oF0.06 ml o f 0.4 M sodium E-oxoglutarate, the
extinction of the solution at 366 m p was measured at one-
Angew. Chem. internat. Edit. I Vol. 3 (1964)
NO. I 1
Документ
Категория
Без категории
Просмотров
0
Размер файла
104 Кб
Теги
separating, hydrocarbonic, chromatography, analysis, halogenated, gas, isomeric
1/--страниц
Пожаловаться на содержимое документа