Search

The less volatile components of the[diethyl aluminum(III)chloride?water(20: 1)]system were deduced from mass spectrometry. Ions which bear two aluminum atoms were classified to one of the proposed skeletal structures on the basis of several established facts: (1)aluminum atoms hardly change their valence during fragmentations, (2)the stability of bridge bondings increases in the order ethyl

An attempt to approximate the peak height determined by magnetic scanning from the intensity of ions detected on a photographic plate through the use of a mass spectrograph of the Mattauch-Herzog type has been empirically studied. The approximation has been performed by the use of calibration plots of logarithm of exposures against the reciprocal of the transmittance determined by a photodensitometer and by the use of a mass correcting factor . Thevalidity of the procedures was examined for the spectrum of choresterol which was measured according to a routine manner, giving an acceptable compromise between the two intensities.

Radiant heat transfer in a fluidized bed was investigated experimentally by means of two kinds of heat exchange pipes. It was found that the contribution due to radiant heat transfer would be insignificant at temperature levels in fluidized beds up to 1000°C. The results are interpreted in terms of a model based on the behaviour of bubbles in the fluidized bed.

The procedure by which the peaks arising from the background can be checked and subtracted has been reported. The mass spectra of the background and sample were detected in separate runs of the plate under controlled conditions, and were stored in separate dimensions in a computer. The checks and subtractions were carried out on the basis of difference in exact masses and of the ratio of intensities. A similar procedure was also be applied to the checks and subtractions of the reactants(sample background)in a reaction mixture to afford only a spectrum of the species produced by the reaction. The subtractions of the background and sample background were examined for a mixture of benzophenone(I), 2, 4-dinitrophenylhydrazine(II)and2, 4-dinitrophenylhydrazone of I being taken I and II as sample backgrounds. The utility and limitation of the procedure have been described and discussed.

無水重金属塩とLiAlH4との反応によって生成する黒色の物質がテトラヒドロフランに均一に分散し,高いオレフィン水素添加触媒活性を有し,かつその触媒活性がLiAlH4と重金属塩のモル比に依存していることを見出した。塩化鉄(III),塩化ニッケル,塩化コバルト(II),塩化クロム(III)および塩化ロジウム(III)などがLiAlH4と反応したときに生ずる黒色物質の触媒活性について検討した結果,これらの物質の触媒活性は,従来の,グリニャール試薬を用いて合成した重金属水素化物の触媒活性によく対応していることを明らかにした。また,鉄触媒について,反応混合物の変色点,触媒活性の現われ始める点および触媒活性が最大になる点の3点に関して,これらの点に達するまでに消費されるLiAlH4の量とグリニャール試薬の量との間に対応関係があることを示し,さらに,鉄触媒の保有水素をジエチルケトンまたはスチレンへ導入させ,その還元生成物を定量してこの鉄触媒の主体は鉄水素化物であると結論した。

Some information on the mechanism of iron hydride formation in the reaction of iron (III) chloride with phenylmagnesium bromide under a hydrogen atmosphere has been presented. When the molar ratio (C6H5MgBr/FeCl3) is larger than 5, 3–4 (mol./mol. FeCl3) of hydrogen is absorbed during the synthesis of hydrides. The amounts of benzene, one of the by-products formed in the synthesis, have also been determined. The treatment of these hydrides with styrene under a nitrogen atmosphere has given ethylbenzene in amounts which correlate well with the amounts of hydrogen absorbed during the hydride synthesis. These observations can be taken as support for the formation of iron hydride. On the other hand, a mixture prepared by the reaction of iron(III) chloride with phenylmagnesium bromide under a nitrogen atmosphere evolved about 0.5 (mol./mol.FeCl3) of hydrogen on hydrolysis. When the hydride prepared under a hydrogen atmosphere was hydrolyzed with dideuterosulfuric acid, D2 as well as HD was evolved. These result...

The titled catalyst systems were found to be active and convenient for the hydrogenation of olefins and to be selective toward 1,3-COD. The catalyst was transformed to some extent during the hydrogenation of 1,3-COD: cyclooctene was formed preferentially and thereafter was hydrogenated to cyclooctane successfully.

ジフェニルマグネシウムと塩化鉄(III)を用いて鉄水素化物の生成過程を研究し,従来,水添触媒として有効であると考えられていた水素吸収量3以下の範囲について,塩化鉄(III)に対するグリニャール試薬の当量比と鉄水素化物の水素吸収量との間の関係を明らかにした。また,ジフェニルマグネシウムを用いたときの方が,フェニルマグネシウムブロミドを用いたときよりも水添活性を有する水素吸収量の範囲が広いことを認め,さらにコバルトおよびロジウム塩から合成した場合には,合成反応中に異常吸収が起こることを見出した。フェニルマグネシウムブロミドとニッケル塩と水素との反応によって生ずるニッケル水素化物についても詳細に検討し,水素化物合成の過程およびオレフィン水添の傾向が鉄水素化物の場合と同様であることを認め,さらに水またはアルコールを多量に添加した場合に活性となる特異な水添触媒を見い出した。

The reaction of anhydrous nickel(II) chloride with methylhydropolysiloxane has been found to give an active catalyst for the hydrogenation of olefins. These two reagents react readily at 120–170°C, with the evolution of hydrogen, to form a black-colored substance which has been used as the catalyst. The catalytic activity has been found to depend on the amount of hydrogen evolved during the reaction and on the methylhydropolysiloxane : nickel chloride ratio. The most active catalyst has been obtained by using the reagents in the Si : Ni ratio of 25 : 1 and by intercepting the reaction as soon as the hydrogen evolution amounted to 1.0 mol per mole of nickel chloride. Cyclohexane has been successfully used as a solvent. However, the presence of diethyl ether or tetrahydrofuran has considerably deactivated the catalyst. The catalyst deactivated by ether has, though, been highly activated by adding a large excess of water.

Catalysts composed of anhydrous iron(III) chloride, cobalt(II) chloride, or nickel(II) chloride plus triethylaluminum have been used for the hydrogenation of olefin. The catalytic activity has changed with the Al(C2H5)3/MCln ratio. The optimum ratios for the hydrogenation of styrene have been found to be 1–7 for the iron catalyst, 0.2–1 for the cobalt catalyst, and 0.3–2 for the nickel catalyst. Cyclohexane has been used satisfactorily as a solvent. Tetrahydrofuran could be used for the nickel catalyst, but its presence was unfavorable for the iron and cobalt catalysts. The gas evolved in the reaction of the transition metal chlorides with triethylaluminum has been found to be essentially ethane, and sluggish gas absorption was observed when the atmosphere was switched to hydrogen. Ethylbenzene was formed in the treatment of the catalyst with styrene under nitrogen; the amount increased considerably if the catalyst was pre-treated with hydrogen. Ethane was formed in the hydrogen-treatment of the reaction ...

The possibility of mass spectral analysis of less volatile and air sensitive organometallic compunds has been studied with an electron-impact, Muttauch-type mass spectrograph. Several organotitanium compounds, (C5H5)2Ti, (C5H5)2Ti-methylacetylene complex, (C5H5)2Ti-allylchlorideand (C5H5)2TiCl2-AlEt2Cl complex, have been subjected to mass spectral analysis, and the parent ion has been detected for each compound. The (C5H5)2Ti-methylacetylene complex gave a parent ion of (C5H5)2Ti(C3H4)2+; NMR and IR suggested the structure as a five-membered cyclic diene complex of (C5H5)2Ti. The (C5H5)2Ti-allylchloride gave a parent ion of (C5H5)2-Ti(C3H5)+ which proves the existence of allyl complex of (C5H5)2Ti. The (C5H5)2TiCl2-AlEt2Cl complex gave a parent ion of (C5H5)2TiCl2AlEtCl+ which is in agreement with the composition reported in the literature.