Sumio Matsuda

Studies of organometallic compounds : XLIII. Reactions of organotin chlorides with sodium azide

Abstract Dialkyltin dichlorides R 2 SnCl 2 (R  CH 3 , C 2 H 5 , n-C 3 H 7 , and n-C 4 H 9 ) react with sodium azide in the presence of water to give hexaalkyl-1,5-diazidotristannoxanes N 3 R 2 Sn(OSnR 2 ) 2 N 3 , tetraalkyl-1,3-dichlorodistannoxanes also give the same products. The configuration of the tristannoxane compound was established by X-ray diffraction study. On the other hand, dioctyltin dichloride yielded octaoctyl-1,7-diazidotetrastannoxane. Hexamethyl-1,5-diazidotristannoxane was treated with boiling methanol to give tetramethyl-1-azido-3-methoxydistannoxane, N 3 (CH 3 ) 2 -SnOSn(CH 3 ) 2 OCH 3 .

Studies of organometallic compounds The five-membered ring structure of organotin containing dicarboxylic esters☆

Abstract Bis[(1,2-dialkoxycarbonyl)ethyl]tin dihalides (II) were synthesized by the direct method; the reaction between tin foil and dialkyl halosuccinates in the presence of accelerators. Besides the main products, [(1,2-dialkoxycarbonyl)ethyl] tin hydroxydibromide (III) was obtained as by-product. It was considered that (II) had two stereoisomers with a six-coordination containing 2 five-membered ring structures in which the oxygen atom of the CO at the γ-position with respect to the tin atom was coordinated to the tin atom. These isomers could be isolated with appropriate solvents and the by-products (III) on the basis of IR or NMR spectra, had the five-coordination with tridentate ligand in which the CO group at the γ-position was coordinated to the tin atom and another CO group in the β-position formed a hydrogen bond to the OH group. However, only one product (unstable in the air) was obtained by the direct reaction between other dialkyl halodibasic acid esters and tin foil. The properties of the direct reaction products were compared with those of hydrostannation of the unsaturated dicarboxylic ester with tri-n-butyltin hydride and of the subsequent bromination. The brominated products were considered to have the five-membered ring structure with the CO at the γ-position coordinated to the tin atom, also on the basis of IR and NMR spectra. In view of these observations, it is concluded that those coordinations where the CO at the γ-position coordinates to the tin atom must be caused by the electronegativity of the attached halogen atoms.

Studies of organometallic compounds XXXIII. Bromination of [2,3-bis(ethoxycarbonyl)propyl]tri-n-butyltin and hydrolyses of its monobromination product

Abstract [2,3-Bis(ethoxycarbonyl)propyl]-n-butyltin dibromide (III) was synthesized by the reaction between [2,3-bis(ethoxycarbonyl)propyl]tri-n-butyltin (I) and three equivalents of bromine in chloroform solution. It is believed that (III) contains a five-membered ring structure and has intramolecular interaction between the tin atom and the CO at the δ-position with respect to the tin on the basis of IR spectrum. [2,3-Bis(ethoxycarbonyl)propyl]di-n-butyltin bromide (II) was hydrolyzed. It was elucidated on the basis of elementary analysis, molecular weight data and IR spectrum, that the product of hydrolysis in hot aqueous alcoholic sodium hydroxide was a dimer with bridging structure.

A new route to [2-(alkoxycarbonyl)ethyl]tin derivatives and a study of their structures

Abstract Mixtures of methyl halide and β-halopropionates were brought into reaction with tin foil in the presence of additives. Distillation of such reaction mixtures afforded methyl[2-(alkoxycarbonyl)ethyl]tin dihalides. Starting from these compounds, some organotin derivatives having 2-(alkoxycarbonyl)ethyl groups were prepared. The identities of the derivatives were established by means of elementary analysis, infrared absorption spectroscopy and proton magnetic resonance spectroscopy. From the results of IR and NMR studies, it was concluded that a halogen substituent on the tin atom favors the formation of a five membered ring in which the oxygen atom of the carbonyl group coordinates to the tin atom.

Studies of organometallic compounds : XXXVI. Synthesis of [1,2-bis(ethoxycarbonyl)ethyl]tin trichloride

Abstract [l,2-Bis(ethoxycarbonyl)ethyl]tin trichloride (III) was synthesized by the reaction of bis[1,2-bis(ethoxycarbonyl)ethyl]tin dibromide and stannic chloride. Evidence is presented which indicates that (III) must be a five-coordinated structure containing a five-membered ring structure and there must also be intermolecular interaction between tin and the β-carbonyl group in the solid state.

THE GRIGNARD REACTIONS WITH ALKYL GLYCIDYL ETHERS

Beider Grignard-Reaktion der Glycidylverbindungen (I) mit den Alkylmagnesiumbromiden (II) entstehen die Alkohole (III), (IV), (V) und (VI) sowie die Alkylbromide (VII) und (VIII).

The Effect of Development Conditions on the Hydrogenation and Alkylation Activities of Raney Cobalt or Raney Iron Catalyst

The effect of development conditions of Raney Cobalt (R-Co) or Raney Iron (R-Fe) catalyst on the alkylation and hydrogenation activities was investigated in the case of the synthesis of N-ethylpyrrolidone from succinimide, hydrogen and ethanol. The synthesis of N-ethylpyrrolidone from pyrrolidone and ethanol was also studied to find out the effect of metal oxides which existed originally in R-Co or R-Fe catalyst or formed during the reaction.R-Co catalyst, developed so as to contain more alumina showed high alkylation activity as well as considerably high hydrogenation activity. R-Co catalysts, developed in the usual way, contained high and low hydrogenation active sites. The R-Fe catalyst which showed high alkylation activity, showed low hydrogenation activity. Much amount of ion oxide was produced during reaction and R-Fe catalyst showed very low hydrogenation activity. The alkylation reaction was remarkably contributed by the metal oxides in R-Co or R-Fe catalyst.

THE GRIGNARD REACTION OF PROPYLENE OXIDE

The reactions of propylene oxide with Grignard reagents (RMgX) in various ethers have been tested. Relations between the reaction conditions and compositions of obtained four alcohols (CH3CH(R)CH2OH, CH3CH(OH)CH2R, CH3CH2CH(R)OH and CH3C(R)(OH)CH3) were investi- gated, and the reaction mechanism was also studied. The Grignard reagents were prepared from ethyl bromide, ethyl iodide, isopropyl bromide, isopropyl iodide and bromobenzene; and diethylene glycol dimethyl ether, tetrahydrofuran, ether, n-butyl ether and anisole were used as solvents.The proportions of propylene oxide to Grignard reagent did not show any influence on the distribution of alcohols, while they affected the ratio of alcohols to halohydrins. Yields of halohydrin increased with increasing ratio of Grignard reagent to propylene oxide. Organic groups in Grignard reagents did not affect the proportion of four kinds of alcohols, but with regard to halogens in the Grignard reagents, the steric factor affected the compositions of two kinds of halohydrin (CH3CH(X)CH2OH and CH3CH(OH)CH2X). As a significant difference in the compositions of alcohol was observed between ether and tetrahydrofuran (solvents), product distributions against the reaction time were investigated in the reactions between propylene oxide and halohydrins in both solvents. Finally, possible two courses for the formation of alcohols were infered. The Grignard reactions of aldehyde or ketone were investigated to confirm the proposed mechanism.

The Effect of Development Conditions of Raney Nickel Catalyst for the N -Alkylation Reaction of Succinimide or Pyrrolidone with Ethanol

コハク酸イミド, 水素およびエタノールより, ラネーニッケル触媒を用いて,N-エチルピロリドンを合成する反応について, 合金末の展開条件が, アルキル化活性に与える影響について検討した。また, とくに触媒中に最初から含まれる, または反応中に生成する金属酸化物とアルキル化活性との関係について検討する目的で, ピロリドンとエタノールより,N-エチルピロリドンを合成する反応も行なった。その結果, コハク酸イミドを用いた反応において, ラネーニッケル触媒は強弱のアルキル化活性点を持ち, 強い活性点は高いアルカリ濃度で展開した触媒に多く含まれ, 弱い活性点は非常に低いアルカリ濃度で展開した触媒に多く含まれると推察された。ピロリドンを用いた反応において, 触媒中の金属酸化物量の変化とアルキル化活性の変化が, おおむね一致した傾向を示し, 酸化アルミニウムを多く含むように調製した触媒が, 高いアルキル化活性を示したことから, 触媒中に含まれる金属酸化物がアルキル化反応に大ぎく寄与すると推察した。

Polymerization of Propylene Oxide by Benzenestannonic Acids

(C6H5SnOOH)n を種々の条件下で加熱処理したのち, プロピレンオキシドの重合触媒として使用し, 加熱処理の重合触媒効果におよぼす影響を検討した。最も高い触媒効果を示したのは, 減圧下 (1mmHg) , 200℃ で1時間加熱した場合であり, 本化合物および加熱処理しない(C6H5SnOOH)n を触媒として, プロピレンオキシドの塊状重合における速度論的研究を行なった。加熱触媒の場合,重合は2段階的に進行した。しかし重合体収率およびその分子量と反応時間の特性より, 本重合は逐次重合反応であり, 触媒効率は加熱触媒および加熱しない触媒についてそれぞれ 0.0047, 0.55 であった。重合速度式はいずれの場合も, -d[PO]/dt=kp[Cat]1 で示された。モノマー消費速度定数 kp(1/hr) (80℃) および重合の見掛けの活性化エネルギー (kca1/mol) は, 加熱しない場合, おのおの0.37, 16.7, 加熱触媒の第1段階では 1.43, 1.69, 第2段階では 0.36, 17.8 であった。