Bleached cotton fabric is treated with an aqueous solution of tetramethylammonium hydroxide (TMAH) or with sodium hydroxide in various concentrations with or without tension. The degree of "mercerization" is characterized by the crystallinity, iodine sorption capacity, water retention values before and after drying, dye uptake, and color strength. The shrinkage of the slack mercerized fabrics is also measured. The "mercerizing" effect of TMAH is higher than that of NaOH, and all changes caused by swelling are
A process based on gas chromatographic separation and on the computerized evaluation of the results has been developed for the determination of the distribution and distribution coefficients of alkyl polyglycol ethers, formed in the competitive, consecutive reaction of fatty alcohol and ethylene oxide. A comparison of experimental and theoretical distributions showed that the distribution is the Weibull-Nycandcr-Gold type for potassium hydroxide catalyst, and the Flory type in the antimony pentachloride catalyst. The characteristic of the distribution does not change with reaction parameters in either type of distribution, though actual distribution is slightly modified by temperature. In determinations of Weibull-Nycander-Gold's c and Natta-Mantica's c i -s distribution coefficients, the Weibull-Tornquist effect, i.e., the changing of the distrihution coefficients with ethoxylation, has been experimentally proven in the example of ethoxylation catalyzed with potassium hydroxide.
Ethoxylation of dodecyl alcohol catalyzed by alkali hydroxides are accelerated by adding complexing agents for the alkali ions. The rate of ethoxylation could be increased by crown ether and dodecyl alcohols of a higher degree of ethoxylation. The effect is more pronounced with the crown ether; thus, reactions not taking place under other circumstances could also be carried out. The complexing additives have no significant effect on the molar mass distribution, The reaction could also be accelerated by using more bulky organic cations (e.g., triethylbenzylammonium ion) instead of the alkali cation.
standard. The following abbreviations are used: (br) broad, (w) weak, (ex) exchangeable with D20, (s) singlet, (t) triplet, (q) quartet, (m) multiplet.The following procedures are illustrative of the reductions carried out. DL-Mandelic Acid Methyl Ester (3b). To a solution of methyl phenylglyoxalate (3a) (1.6 g, 10 mmol) in THF (25 mL) was added potassium carbonate (2 g, 14 mmol) and Pd/C (5%, 50:50 water wet, 300 mg). The stirring mixture was heated to reflux, and a solution of sodium hypophosphite (2 g, 18 mmol) in water (20 mL) was added dropwise. The reaction mixture was stirred overnight, and the next day, a TLC analysis (70:20:10 toluene/CH2Cl2/EtOAc) showed the reaction to be complete. The reaction mixture was cooled and filtered and the filtrate diluted with diethyl ether. The organic layer was separated, washed with saturated NaCl solution, dried (MgS04), filtered, and concentrated to yield DL-mandelic acid methyl ester (3b) ~1.2 g (--75 % ), mp 53-54 °C. The product could be recrystallized from cyclohexane to yield material which was identical (IR, NMR, mp) with an authentic reference standard: IR (CH2C12) 3550 (br), 3080, 1740 (s) cm"1; NMR (CDC13) 7.4 (s, 5, Ar), 4.3 (Ab q, 1, CH), 3.7 (s, 3, OCH3).3-Chloro-1,3,4,5-tetrahydro-2J?-l-benzazepin-2-one (15b). A mixture of the dichloro lactam 15a6 (20 g, 0.087 mol), Pd/C (10%, 1.2 g), sodium acetate (20 g, 0.24 mol), and sodium hypophosphite (9.2 g, 0.244 mol) in glacial acetic acid (200 mL) was heated to 56 °C for 24 h. The reaction mixture was filtered and the filtrate concentrated to a residue; water (200 mL) was added, and this was stirred as the product precipitated out. The product 15b was filtered, washed with water, and dried in vacuum to yield 15.1 g (~89% 1st crop), mp 164-167 °C.; this material contained ~1.7% lactam which was completely reduced and no detectable starting material: NMR (CDC13) 8.8 (m, 4, Ar), 4.5 (m, 1, CH), 2.8-2.5 (m, 4, aliphatics).Acknowledgment. We thank Drs. B. Ganem and S. Hanessian for their helpful consultation and encouragement in this work. Also, we would like to acknowledge the help of the members of the Analytical Services Group:
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