Koji Matsui

The Reaction of Epichlorohydrin and Polyethyleneglycol Monoalkylether

三フッ化ホウ素エーテラートを触媒とし, エピクロルヒドリンとポリエチレングリコールモノエチルエーテル(C2H5 O〓CH2CH2O〓nH;n=1,2,3)およびエチレングリコールモノメチルエーテルの反応を検討し,反応機構について考察した。反応速度はn=1,2,3の順に減少したが大きな差はなく,活性化エネルギーおよび頻度因子にも大きな差を認めなかった。活性化エントロピーはn=1,2,3の順に-17.9,-16.7,-17.4であった。このことは本反応がSN2機構によって進むことを示している。

Azo Dyes Containing -SO2NHCH2CH2NCH3RRGroup, CH3

By the reaction of p-acetaminobenzene- and 4-acetamino-1-naphthalenesulfonylethylenimide with secondary amines (diethylamine, diethanolamine, pipe ridine, and morpholine), corresponding sulfonyl-β-dialkylaminoethylamide, and by their hydrolysis (1) and (2) were obtained.(1) H2N SO2NHCH2CH2NRR and (2), H2N -SO2NHCH2CH2NRR Using (1) and (2) (quarternary base in the case of (2)), as diazo component, a series of azo dye were obtained by combination with some of aromatic tertiary amines (such as dimethylaniline, bis(β-hydroxyethyl)-aniline), and 3-methyl-1-phenylpyrazolone-5 etc. These dyes thus obtained were then converted into their quarternary salts by use of methyl sulfate. These dyes dyed Orlon type polyacrylonitrile fiber well to yellow- orange- red. The effect of R on the absorbability was not great and the dyes obtained by using those secondary amines, such as piperidine and morpholine, gave better absorbability than those of using diethylamine and diethanolamine. The absorbability of (1) type dyes were in the order of neutral > acidic >alkaline, and similar results were obtained in the case of (2) type compounds. The fastness against the light were not satisfactory and all remained to be 3-4th. grades, and the fastness against washing were about 4th. grade.

Azo Dyes Containing -CH2CH(0H)CH2NRR Group. 1

By the reaction of epichlorohydrin followed by diethylamine on aniline and α-naphthylamine, respectively, N-type C6H5NHCH2CH(0H)CH2N(C2H5)2 (1) (yield 56.65%), by 154-5°c/2 mm, and 1-C10H7NHCH2CH(OH)CH2N(C2H5)2 (2) yield 65.5%, bp 210°c/2 mm, were obtained. Also, by the reaction of epichlorohydrin on N-acetyl-m-aminophenol, followed by the reaction of diethylamine and hydrolysis of the product 0-type compound, m-H2NC6H4OCH2CH(OH)CH2N(C2H5)2 (3) (yield 49.5%, by 202-204°c/5 mm mp, 33-35deg;c) was obtained. A series of N-type azo dyes were synthesized by use of (1) and (2), respectively, as azo component, and various atom aticprimary amines having no carboxyl and sulf onyl group, such as p-nitroaniline, self anylamide and others, as diazo component. Also, O-type azo dyes were synthesized by use of (3) as diazo component, and dimethylaniline, β-naphthol, Naphthol AS, and 3-methyl-1-phenylpyrazolone-5 as azo components. A monoazo dye of 0-type was also prepared using (3) as azo component and Fast Red B base as diazo component; further diazotation of this dye and coupling it with dimethylaniline, Naphthol AS, etc. gave 0-type disazo dyes. The O- and N-type dyes thus obtained are soluble in dilute acetic acid, and have good dyeing property for Orlon type polyacrylonitrile fiber (Exlan L, Vonnel W and Cashmilon) with color ranges of yellow- orange- red- brown- purple. The quarternary ammonium salts of above dyes also showed similar characteristics.