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Interaction of Triphenylmethyl Salts and Quaternary Cycloimmomium Salts with Pyridine and Aromatic and Aliphatic Amines.

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mitted to gas chromatography, the separated fractions
were cracked to methane, and their radioactivity was
measured in a continuous-flow proportional counting
5. The 14CO2 assimilation or a vine was investigated
using experimental arrangement I11 without reaction
units. Gas samples were removed from the closed experimental chamber after equal time intervals and analysed by gas chromatography (Fig. 8).
6. The efficiency of hydrogenation catalysts at different
temperatures can be investigated by hydrogenating over
the catalyst in a reaction tube, separating the products
by gas chromatography, and determining their radioactivities after cracking to methane [4].
tube. Propionates were shown to transesterify with the
labelled acetic acid (Fig. 7).
Fig. 7. Transesterificationof esters of propionic acid with [14C]-acetic
a) Gas chromatogram; b) Radiogram; 1 = Methyl acetate; 2 = Ethyl
acetate; 3 = Methyl propionate; 4 = Propyl acetate; 5
propionate. Column: 5.20 m long, Packing: Polywax 2000/Kieselguhr
(65 mesh) (20
100); S O T ; 52 rnl of Hz/min. Radiation detector:
Arrangement 111; 17.4 ml of CHdmin; Hz:CHq = 3 : l ; 3.6 kV.
Ordinates: Recorder potential ImV]
Abscissae: Time [minl
Fig. 8. Course of assimilation of 14COz (initial concentration 0.913
yC/ml of COz) by a vine in a closed chamber..The gas mixture was
initially 13.7 1 of air and 20 ml of COz.
Ordinate: 14CO2 remaining in the reaction chamber [coun~s/min/ml]
Abscissa: Time [min]
Our investigations show that results of good reproducibility are obtained using hydrogen with methane or
helium with methane as carrier and as counting gases, if
the fractions separated by gas chromatography are converted into either methane or C02 prior to radiometry.
Increases in the sensitivity and precision of radiometry
in the gas phase effected corresponding reductions in
the amounts of labelled material required. Apart from
the often considerable savings in the costs of materials,
the radiation level in biological investigations is reduced.
Complete destruction of the xnalysed material can be
avoided by applying stream splitting and measurement
of the radioactivity in parallel.
The authors wish to thank Prof. Husfeld for his interest in
their worlc, which was carried out with the support of the
Bundesministerium fur Atomkcrnenergie and the Deutsche Forschurigsgemeinschaft.
Received, March Ilth, 1963
[A 306/108 IE]
German version: Angew. Chem. 75, 716 (1963)
Interaction of Triphenylmethyl Salts and
Quaternary Cycloimmomium Salts with Pyridine
and Aromatic and Aliphatic Amines
By Prof. Dr. G.Briegleb, Dr. W. Ruttiger, and Dr. W. Jung
Institut fur Physikalische Chemie der Universitat Wurzburg
Dedicated to ProJ Dr. F. Krohnke on the occasion of his
60. birthday
Compounds of the n-electron-donor type (D), e.g. pyridine,
add onto the triphenylmethyl cation (Tro), which is formed
from triphenylmethyl halides in solvents of high dielectric
constant without pronounced n-donor properties [I], and thus
bring about the disappearance of the characteristic visible
absorption bands (halochromic bands) at 435 and 415 mp
+D +
+D +
Angew. Chem. internat. Edit. / Vol. 2 (1963) / No.9
These processes are reversible equilibria that are dependent
on theconcentration and solvent, as has been shown by means
of spectroscopic and conductivity measurements with triphenylmethyl bromide [2]. The association constant K1 for
TrD@...XQ in 1,1,2,2-tetrachlorocthaneat 20 "C is between
1.1 x 105 and 6.6 x lo5 I/mole. Triphenylpyridinium bromide
can be isolated as a colorless salt [3].
In order to investigate the eleci ron-accepting capacity of
resonance-stabilized aromatic cations more fully, the behavior of the N-2,6-dichlorobenzylquinolinium cation
(2,6-DClBQN*) was studied. Optical measurements indicate
that aromatic amines, even N,N, N', N'-tetramethyl-p-phenylenediamine, exhibit electron donor-acceptor interaction only
at very high concentrations (revcrsible concentration-dependent red coloration, e.g. in CHCIj and CH3CN at Csalt
=3x 10-3 mole/l and carnine= 2x I 0 -1 --I .O mole/l). Aliphatic
amines (n-butylamine, ethanolamine, piperidine, triethylamine), on the other hand, yield completely reversible complexes very readily in CHC13 [3,4]. These are solvent- and
concentration-dependent equilibria which, on addition ofHC1,
CH30H, or HzO (i.e. on raising the dielectric constant) shift
toward the free cations. The ultraviolet spectra of the complexes are largely independent of the nature of the solvent
or the amine [6] and are extremely similar to that of 1,2-dihydroquinoline [ 5 ] .
On addition of increasing amounts of n-butylamine to solutions in CHC13 of 2,6-DClBQNoXQ salts, the absorption
band at 317 mp, which is characteristic for the cation, decreases to the same extent as the amount of complex formed.
A new absorption band (340 mp) due to the complex appears
with two isosbestic points at 341 and 291 mp.
The association constants K for a few anions XQ are given
in Table 1. The increase in the value of K with decreasing
size of XO can be attributed to steric causes, since the amine
reacts in CHCI3 as an electron donor with the ion pair
2,6-DCIBQNQX@.The infrared spectra of complexes of type
( I ) show broad diffuse bands between 3000 cm-1 and
2000 cm-1, which are typical for hydrogen bonds of the
NH@-XQ type [6] and, thus, confirm structure ( I ) .
K (llmole)
r [A"]
1 I 1 1
[l] A . G. Evunset al., Trans. Faraday SOC.47, 711 (1951); 50, 16,
470, 568 (1954); 51, 481 (1955); 52, 332 (1956); J. chem. SOC.
(London) 1957, 1021.
[2] W. Riiftiger, Ph. D. Thesis, Universitat Wurzburg, 1957.
[3] G. Briegleb and W. Jung, unpublished data.
[4] F. Krohnke, Liebigs Ann. Chem. 600,21,176 (1956), suggests
the possibility of 2- or 4-addition of piperidine onto cycloimmonium salts.
[ 5 ] W . Jung, Ph. D. Thesis, Universitat Wiirzburg, 1963.
[6] G. Briegleb and H. Delle, Z. Elektrochem. 64, 347 (1960);
R . Mecke and W . Kufzelnigg, ibid. 64, 1108 (1960).
124-125 "C), was obtained by saponification of the ester
with methanolic KOH and was converted via the acid
chloride into the amide, m.p. 195°C ([2] gives 192°C).
Hydrolysis of (3) by heating with hydrochloric acid affords
CliH1602 (6), m.p. ca. 200"C, a readily sublimable, camphor-like, isotropic substance. The reactions and nuclear
magnetic resonance spectrum of (6) characterize it as a ylactone, resulting from a Wagner-Meerwein rearrangement,
via a P-hydroxy carboxylic acid.
Compound (5), colorless needles m.p. 126"C, can be
recrystallized unchanged from methanol, even after prolonged
boiling, and is thus readily separated from (3). A diamino
derivative C23H4103N3S. colorless needles, m. p. 224 "C from
methanol, is obtained with cyclohexylamine. Redoxhydrolysis [l] of (5) in methanol/water results in an almost quantitative yield of a y-lactam C1IH170N (7), platelets, m.p.
190 'C (isotropic) from hot water; the crystals contain water
of crystallization and effloresce readily. It is hydrolysed only
on prolonged boiling with conc. hydrochloric acid to yield the
hydrochloride of an amino acid CllH1902N (m.p. 210 to
220°C, with decomposition), whose ethyl ester reforms the
lactam (7) when heated with sodium ethoxide. The Ncarbamyl-lactam (fine needles from methanol, m.p. 185 "C,
anisotropic) obtained by hydrolysis of the reaction product
obtained from interaction of (7) and ( I ) is not rearranged
to a dihydrouracil derivative on heating with conc. hydrochloric acid, and an alternative p-lactam structure is thus
excluded. In addition, the nuclear magnetic resonance
spectra of (5) and (7) clearly favor the five-membered ring
Received, June 4th, 1963
[Z 521/348 IEI
German version: Angew. Chem. 75, 858 (1963).
[l] R. GruL Liebigs Ann. Chcm.'661, 1 1 1 (1962).
[2] M . G. Langlois, Ann. Chimie (9) 12, 193 (1919).
The Reaction of Camphene with
N-Carbonylsulfamyl Chloride
By Dr. habil. R. Graf and Dr. H. Biener
Farbwerke Hoechst AG. formerly Meister Lucius & Bruning,
Frankfurt(Main)-Hochst (Germany)
Dedicated to Prof. Dr. Karl Winnacker
on the occasion of his 60th birthday
The reaction of camphene with N-carbonylsulfamyl chloride
( I ) in ether or liquid SO2 affords a 70 % yield of a mixture
of two isomeric crystalline compounds CllH1603NSC1, the
constitutions of which have been elucidated. The hypothetical
primary adduct (2) [I] is stabilized either by migration of a
proton from the methylene group to the nitrogen atom to
give an cr,P-unsaturated carboxamide-N-sulfonyl chloride
(3) or by a Wagner-Meerwein rearrangement via (4) to a ylactam-N-sulfonyl chloride (5).
Compound (3), obtained from the crude mixture as the lesssoluble component, forms interlinked prisms, m.p. 137 OC
(with decomposition). On prolonged boiling with methanol,
(3) gives an almost quantitative yield of methyl campheneo-carboxylate, b.p. 70-72 'ClO.2 mm, an oil of terpene-like
odor. The free carboxylic acid, m.p. 126-127°C ([2] gives
Organotin Phosphides
By Dr. H. Schumann, DipLChem. H. Kopf, and
Prof. Dr. Max Schmidt
Institut fur Anorganische Chemie der
Universitat Marburg (Germany)
A publication on organogermanium compounds [l] prompts
us to report briefly on thc synthesis of the corresponding
organotin compounds, for only a single representative of
these has been mentioned to date [2]. When tetraphenyltin
is treated with elementary phosphorus, various organotin
phosphides are formed, depending on the temperature and
concentration ratio of the starting materials. These can also
be prepared in three other ways: 1. From diorganyl-lithium
phosphide and an organotin halide, 2. from diorganylphosphines and an organotin halide in the presence of a tertiary
amine, and 3. from a lithium triorganyltin and an organochlorophosphine. Methods 1 and 2 yield, for instance,
( I ) , m.p. 126 "C, and (CsH&P-Sn(C4H9)3 (2), m.p. 6OoC, while method 3 leads, for example,
to (3), m.p. 64°C.
Angew. Chem. inicwmt. Edit. I Vol. 2 (1963) / No. 9
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salt, pyridin, triphenylmethyl, cycloimmomium, aliphatic, interactiv, quaternary, amines, aromatic
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