Amines infrared spectra, 519 table

The membrane having the sulfonyl chloride groups was treated by an aqueous n-butyl amine solution for 2 hours, washed with water, heated in air for 24 hours at 90°C and then dipped in 10% methanol solution of sodium hydroxide. The reflective infrared spectrum showed that absorption band ascribable to the sulfonyl chloride disappeared and new absorption bands appeared at 1620, 1680 and 3400 cm l, The electric resistance and the electrolysis results of both of the treated and untreated membranes are shown in Table II respectively. 

A solution of 145 / 1 (3 mmoles) of freshly distilled hydrazine hydrate in 15 ml of dioxane is added to a solution of 915 mg (3 mmoles) of iV-hydroxysuccinimide ester of 2-nitro-4-azidobenzoic acid in 100 ml of dioxane, and the mixture is stirred for 1 hr at 0 . It is necessary to add hydrazine hydrate in the same molar quantity as the ester, since the azide group would be decomposed by an excess of hydrazine (the 2100 cm" band disappears in the infrared spectrum). The mixture is evaporated to an oil under reduced pressure, and the oil is crystallized by addition of light petroleum ether (40°-70°) and repeated evaporation. Recrystallization is from water or aqueous ethanol. Yield, 420 mg (58%) m.p., 163°-165° (decomposition) IR (KBr), cm 3300-3400 (amide), 2100 (-N3), 1530 (-NO,) UV spectrum (H,0) A, ax 250 nm ( = 21,000), Amin 227 nm (e = 11,000). The product is chromatographically and elec-trophoretically homogeneous (see the table). The compounds are detected in UV light and darken under irradiation by UV or visible light. 

Measurements of potential barriers to internal rotation have been made by far-infrared studies. Hadni measured the frequency of the first torsional transition in methyl amine and found it at 269.5 cm Gray and Lord studied methyl amine and its deuterium derivatives and obtained the torsional frequencies shown in Table I. The spectrum of 1,1,1,2-tetrafluorethane was obtained. The band at 120 cm was interpreted as the torsional frequency for this molecule [ ]. A study of the far-infrared spectrum of propylene was also made [ ]. 

Table 3 summarizes the results of the polymerization employing benzyl-amine as an initiator. The control reaction without any initiators proceeded slowly to give an insoluble product, whose infrared spectrum was identical to that of the soluble polymer produced with the initiator. The insolubility can probably be ascribed to a physical character of this polymer. The soluble polymers produced with the initiator also became insoluble after they were stored for some days even in a nitrogen atmosphere. 

The reaction of III with two or four equivalents of n-butyllithium resulted in the formation of a new product, N, N-di-n-butyl-terf-butylamine (VI), in yields up to 16% of theory. This previously unknown tertiary amine was identified by infrared and mass spectrometric analyses. A comparison of the mass spectrum of VI with that of the known tri-n-butylamine (Table I) shows thait the same major peaks appear but in quite... 

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