Kyoichi Suga

Reactions of glycerol derivatives with N,N-diethyl-1,1,2,3,3,3-hexafluoropropanamine

Fluorination of mono- and disubstituted glycerols with N,N-diethyl-1,1,2,3,3,3-hexafluoropropanamine (PPDA) was attempted. Instead of the expected fluoroglycerol derivative from a disubstituted glycerol, the major product was the fluorinated propyl ester. Thus, 2,3-dibromopropyl 2,3,3,3-tetrafluoropropionate was isolated in 52% yield from the reaction of 2,3-dibromo-1-propanol with PPDA. With a monosubstituted glycerol, a cyclic adduct was obtained. Thus, 4-allyloxymethyl-2-diethylamino-2-(1,2,2,2-tetrafluoroethyl)-1,3-dioxolane was isolated in 68% yield from 3-allyloxy-1,2-propanediol and PPDA. Shielding by the bromine atoms in the former reaction and intramolecular nucleophilic attack by the vicinal hydroxyl group in the latter reaction are possible explanations for the reaction results.

Products from the reaction of fatty acids with ketones and their characteristic properties as cutting fluids additives

Hydroxy acids were synthesized in good yields from ketones and fatty acids by the use of lithium naphthalene in the presence of diethylamine. For example, from cyclohexanone and undecylenic acid (I), 2-(1-hydroxy-1-cyclohexyl)-10-undecenoic acid (III) was obtained in 92% yield. Hydroxy acids were treated withp-toluenesulphonic acid to give corresponding unsaturated fatty acids. From the reaction of (III), 2-(1-cyclohexenyl)-10-undecenoic acid (IV), a 3,4-unsaturated acid was obtained (yield 59%). Corrosion and lubricity tests for these products as water-based cutting fluid additives were carried out. We have found that triethanolamine salts of 2-cyclohexenyl and 2-hydroxycyclohexyl fatty acids showed effective rust-inhibiting and antiwear properties for water-based cutting fluids.

A convenient preparaton ofγ-lactones and dialkyltetrahydrofurans from the reaction of fatty acids with epoxides using lithium naphthalenide

Fatty acids reacted with epoxides using lithium naphthalenide in the presence of diethylamine to give corresponding 4-hydroxy acids. These 4-hydroxy acids easily tended to cyclize into their correspondingγ-lactones by refluxing in benzene. Reduction of theseγ-lactones with lithium aluminum hydride followed by intramolecular dehydration with potassium bisulfate afforded corresponding dialkyl tetrahydrofuran derivatives in high yields. For example, 4-methyl-2-(8-nonenyl)γ-butyrolactone (III) was obtained from 10-undecylenic acid and propylene oxide. 2-Methyl-4-(8-nonenyl) tetrahydrofuran (IV) was produced from (III). 2-Methyl-4-(8-nonenyl) and 2-ethyl-4-(8-nonenyl) tetrahydrofurans are woody smelling and may be used as perfumery materials.

New additives for water-based cutting fluids

Abstract Fatty acids containing a carboxymethylthio group were prepared from the reaction of fatty acids and mercaptoacetic acids. Corrosion and lubrication tests for these products as water-based cutting fluid additives were carried out. We have found that triethanol amine salts of 11-(carboxylmethylthio)undecanoic acids and other similar products showed effective rust-inhibiting and anti-wear properties for water-based cutting fluids.

REACTIONS OF GLYCEROL DERIVATIVES WITH N,N-DIETHYL-1,1,2,3,3,3-HEXAFLUOROPROPANAMINE

Fluorination of monoand disu bstituted gtycerols with N, N-diethyl1,1, 2, 3,3, 3-hexafluoropropanamine (PPDA) was attempted. Instead of the expected fluoroglycerol derivative from a disubstituted glycerol, the major product was the fluorinated propyl ester. Thus, 2,3-dibromopropyl 2,3,3,3-tetrafluoropropionate was isolated in 52% yield from the reaction of 2, 3-dibromo-1-propanol with PPDA. With a monosubstiruted glycerol, a cyclic adduct was obtained. Thus, 4allytoxym ethyl-2-dlethylamino-2-( 1,2, 2, 2-tetrafiuoroethyl)1, 3-dioxolane was isolated in 68% yield from 3-allyloxy-1, 2-propanediol and PPDA. Shielding by the bromine atoms in the former reaction and intramolecular nucleophilic attack by the vicinal hydroxyl group in the latter reaction are possible explanations for the reaction results.

Formic Acid Rearrangement of Ethynylcarbinols.

エチニルヵルビノールの酸による転位は一般にRupe反応と呼ばれ, α-,β-不飽和ケトンを生成するとされている。著者らはメチルエチルエチニルカルビノール (I), エチニルカルベオール(V) などのギ酸転位について研究し, Iからは3-メチル-3-ペンテン-2-オンおよび3-メチル-2 -ペンテン-1-アールを, Vからは1-メチル-2-アセチル-4-イソプロペニル-1, 5-シクロヘキサジエンの生成をそれぞれ確認した。