Saburo Komori

Synthesis of polyoxyethylene derivatives of diesters of sucrose with long-chain fatty acids

SummarySince the long-chain fatty acid sucrose diesters inevitably produced in the synthesis of monoesters are only slightly soluble in water, no important use can be found for them at the present time except as oilsoluble emulsifying agents.In order to exploit new uses we have attempted to improve their solubility in water by introducing oxyethylene radicals into the molecule.The addition reaction of ethylene oxide with the sucrose diesters was carried out in an autoclave in the presence of alkaline catalysts. With the reaction temperature maintained between 100–130° the pressure decreased as the reaction proceeded, and one to two hours were required to consume the ethylene oxide used.The addition products are yellow or orange oily materials soluble in water. Aqueous solutions showed good surface-active properties.

Syntheses and properties of surfactants containing organometals: IV. Organo silicone

The authors synthesized nonionic surfactants containing dimethylpolysilane, dimethylpolysilmethylene and dimethylopolysiloxane as the hydrophobic groups, and investigated their surface activities. In their ability to lower the aqueous surface tension, the polysiloxane surfactants were the most active, and there is little reason to choose between the other two kinds of surfactants. With regard to the ability of lowering the interfacial tension between water and silicone oil, the polysilmethylene surfactants were most effective when the concentration of aqueous solution was below 0.5 wt %. Above this concentration, however, the polysiloxane surfactants were superior. Also investigated was the lowering of surface tension of nonaqueous polyols and their ability to wet low energy hydrophobic surfaces such as polyethylene.

The reaction of N,N-dichloroethanesulfonamide with 1-olefin

Abstract The competitive ionic and radical reactions of N,N-dichloroethanesulfonamide and 1-olefins yielded two isomers of the 1:1 adduct under the normal indoor lighting, but the predominant formation of the anti-Markownikoff adduct was observed under photoirradiation. By photoirradiation of the products obtained in the reaction under the normal indoor lighting, two corresponding rearranged products were obtained. These 1:1 adducts and rearranged products were converted to N-ethanesulfonylaziridine derivatives by alkali treatment. A mechanism for the participation of N-monochloroethanesulfonamide has been proposed.

Preparation of tertiary amine derivatives from commercially available alcohols and their properties as surfactants

Higher tertiary amines were prepared by transalkylation of triethylamine with commercially available alcohols such as Tergitol 15-S-3 and tridecyl alcohol. This reaction carried out at 250–300 C and 20 kg/cm2 initial hydrogen pressure, using Cu−Cr−Mn−O catalyst, gave about 80% yield of higher alkyl tertiary amines. Tertiary amine hydrochlorides, quaternary ammonium bromides and amine oxides were prepared from these tertiary amines. Specific surface tension, wetting power, foaming power and foam stability were measured. The characteristic properties with respect to tertiary amine derivatives containing ether linkages were observed. These products have excellent wetting power, reduced surface tension, low foaming power and unstable foam.

An investigation of the oil of laemonema morosum matsubara

SummaryIt has been shown that the oil ofLaemonema Morosum Matsubara, a deep sea fish, contains a large amount (31–34%) of unsaponifiable matter. The main component (ca. 50%) of which is 11-docosen-1-ol, has an m.p. 31.7–32.3°C. This alcohol has not been previously reported in the literature. From this alcoholtrans-11-docosen-1-ol having m.p. 52.4–52.8°C. was prepared. The infrared spectra of these two alcohols are given.

Synthesis of cationic surfactants with alkenyl group

Quaternary ammonium chlorides with long chain alkenyl groups were synthesized by the reaction of tert-amines with alkylallyl chloride which, in turn, were obtained by the allylic chlorination of 1-olefins with N-tert-butyl- or N-cyclohexyl-N-chloro-ethanesulfonamides. Of the two kinds of alkylallyl chlorides prepared by the allylic chlorination of 1-olefins, the γ-alkylallyl chlorides(I), were found to be reactive with tert-amines, while the secondary chlorides, α-alkylallyl chlorides(II), were not so reactive and, when the allylic chloride mixture was reacted with tert-amine under suitable reaction conditions, the γ-alkylallyl chloride could be selectively converted to a quaternary ammonium chloride while the α-alkylallyl chloride was recovered unreacted. The quaternary ammonium chlorides thus obtained were identified as γ-alkylallyl ammonium chlorides from their spectra, and they were shown to possess almost the same surface tension lowering ability as their saturated homologs, although larger critical micelle concentration values and greater water solubilities were observed.

Reaction between Alcohols and Amines. VI.

Reaction between 2-octanol and triethylamine was carried out at the optimum condition, which was reported in our previous paper, but the yield in this reaction was only 36%. This may be due to steric hindrance effect of α-methyl group of 2-octanol.Authors then attempted the reaction after converting the sec-alcohol to primary alcohol by oxyethylation, and the resulted alcohol was reacted with triethylamine using Cu-Cr-Mn-O catalyst under moderate temperature and pressure of H2. In this reaction, it was confirmed that there was no decomposition of oxyethylene chain unless the reaction temperature was over 270°C and 72.2% yield of tertiary amine containing monoalkylether was obtained under the reaction temperature of 270°C.By applying this result for trioxyethylene glycol alkyl (C12C17, except C15) ether, five kind of tertiary amines having these alkyl group were obtained. By using these tertiary amines as the raw material, various new cationic surfactants and amine oxides were prepared. Of these surfactants, N, N-diethyl-N-trioxyethylene alkyl amine oxide (R(OCH2CH2)3N(C2H5)2) showed especially very interesting surface activity.

The 1: 1 Copolymerization of Ethylenimine and Propylene Oxide

BF3・OEt2を触媒とするエチレンイミン(EI)とプロピレンオキシド(PO)の1:1共重合過程を残存モノマーのガスクロマトグラフィーによる定量によって追跡した。常圧下および封管中での塊状重合ならびに常圧下での溶液重合について追跡したところ,まずEIが重合し,生成したポリエチレンイミンにPOが付加し,オキシプロピル基になることが明らかになった。反応中,N-(2-オキシプロピル)エチレンイミンの生成も認められたが, 主反応でなくEIがほぼ消滅してから重合する傾向を示した。EIとPO 消費速度の差は封管塊状重合

Synthesis and Identification of Tetraalkylpyrone

無水カプロン酸を酸化ホウ素の存在下で,220～300℃に加熱し,縮合させテトラアルキルピロンを合成し,ガスクロマトグラフィーを用いて生成物を分析した。反応生成物中には主生成物のテトラアルキルピロンの外に多くの中間生成物ならびに副生物が存在することがわかり,テトラアルキルピロンにも,α,γ-ピロンの両異性体が存在していることを認めた。これらα,γ-ピロンをそれぞれ純粋に単離確認し,その性質を調べた。α-ピロンを加水分解して得られる酸(VI)を加熱すると,脱炭酸してケトン(VII)になるが,BF3を作用させると再びα-ピロンに戻ることを認めた。

Studies on the Rust Preventive Powers of Sucrose Fatty Acid Esters

ショ糖長鎖脂肪酸モノエステル,ジエステル,ポリエステル,ならびにショ糖と,二塩基性酸メチルとのエステル交換によって得た一種のポリエステルの長鎖脂肪酸エステルを,不乾燥性油状防食油(米軍規格P-7,P-8,P-9またはP-10型)添加剤として用いた場合の軟鋼板に対する防食効果を,湿潤試験ならびに塩水噴霧試験によって調べた。ショ糖長鎖脂肪酸モノエステルは基油として用いる潤滑油への溶解度が悪く,防食添加剤としては不適当であったが,ジエステル以上のポリエステルはかなり良好な防食効果を示し,とくにトリエステル程度のものが最も優秀であった。脂肪酸基としては,ミリスチン酸,パルミチン酸などの飽和脂肪酸,エルカ酸などの長鎖の脂肪酸エステルが良好であり,ラウリン酸のような鎖長の短かいものや,リノール,リノレン酸のような不飽和結合を多く含む脂肪酸のエステルは,やや効果が劣っていた。また,ショ糖-二塩基性酸ポリエステルの誘導体は非常にすぐれた効果を示し,他の添加剤を加えなくても,単独で良好な防食油が得られることが確かめられた。