Aqueous Caustic Soda Research Articles

The effect of pressure up to 12,000 kg/cm 2 on reactions in solution

In a previous publication it was shown that pressure was capable of exerting a considerable influence on the rate of reactions in solution. Two reactions were studied; the first, the interaction of sodium ethoxide and ethyl iodide in alcohol solution, was a typical example of the “normal” class, in which the number of molecules reacting is approximately equal to the number of collisions with the requisite activation energy, while the second, the interaction of pyridine and ethyl iodide in acetone solution, was a typical “slow" reaction, in which the number o f molecules reacting is several powers of 10 less than the number of collisions with the requisite activation energy. The rates of both reactions were increased by pressure, but while the first was accelerated 1.6 times at 3000 kg/cm 2 , the second was accelerated 7.2 times at 3000 kg/cm 2 , and much more at higher pressures. It seemed desirable to investigate other reactions falling into these two classes, to see whether this behaviour was general. With this end in view, the hydrolysis of sodium monochloracetate by aqueous caustic soda, another typical “normal” reaction, has been studied up to 12,000 kg/cm 2 , and the work on the sodium ethoxide and ethyl iodide reaction has also been extended to this pressure.

カワカワの成分(第二報) : メチスチチンの構造

Winzheimer (Arch. Pharm. 246, 338) assigned to methysticin the constitution (I) and observed also when treated with alkali it was saponified to methysticinic acid (II), which by the action of mineral acids gives methysticol (III). (I) [chemical formula] (II) [chemical formula] (III) [chemical formula] The authors (M. and Sh.) showed that when methysticin C15H14O5 was warmed with aqueous caustic soda, an isomeric compound called isomethysticin (m.p.186°), is formed which is prcbably identical with the methysticinic acid of Winzheimer. By the action of mineral acids not only the isomethysticin, but also methysticin itself are converted into methysticol. An important fact hitherto overlooked is that methysticin is optically activ, whereas isomethysticin totally inactiv. On the basis of these observations the authors assigned to methysticin the constitution IV and to isomethysticin V. [chemical formula] Experimental. The material employed for this investigation was crude crystalline mixture containing mainly yangonine and methysticin. On recrystallization several times first from alcohcl and then from acetone pure methysticin m.p.135-137°was obtained. Analysis : -[table] Methoxyl number (Zeisel's method). [table] The optical rotation : [α]<〓/D>=+94.30 (in 5% aceton solution). Action of aqueous Caustic Soda. (Isomethysticin). 10 grams of methysticin were mixed with 100 ccm of aqueous caustic soda (10%), warmed on a water bath for 7 hours, on cooling the reaction mixture the yellowish bright crystals of sodium compounds were 〓eparated, which were collected and agitated with dilute acetic acid (%) in order to isolate the reaction product. Recrystallized from acetone it was obtained in yellow needles melting and decomposing at 180° It is called isomethysticin. Analysis : - [table] Methoxyl number (Zeisel's method). [table] Optical rotation : - α=±0 Isomethysticin is insoluble in cold sodium carbonate solution, soluble in hot carbonate and on cooling a krystalline sodium compound separated, from which the isomethysticin again regenerated by means of acids. Action of dilute Sulphuric Acid on Methysticin. 5 grams of methysticin were mixed with 300 ccm of 5% sulphuric acid, warmed on a water bath for 6 hours, when resinous matter were obtained which solidified on cooling. It was recrystallized several times from alcohol, melted at 94° and proved to be identical with methysticol as described by Winzheimer. Analysis : - [table] The methysticol was also obtained from isomethysticin by the same manner as described in the case of methysticin. (April 1925 Tokio Hygienic Laboratory of Department of Home Affair).

カワカワの成分(第一報)カワ酸に就て

In a preliminary note on the subject one of the authors and K.Mayeda (this Journ. No.477, Nov.1921) described an acidic compound C15H16O5 or (C6H5·C7H7O2) (OCH3)·COOH. which was obtained by treating kawa resin with aqueous caustic potash at ordinary temperature. Borsche and Roth (Ber. 54, 2229) obtained a compound named kawaic acid (C13H12O3) from kawa resin by heating it with aqueous caustic soda, wich on distillation in vacuo lost CO2 and yielded cinnamalaceton. hThey considered the constitution of their kawaic acid to be C6H5CH : CH·CH : C (CH3) CO·COOH or C6H3·CH : CH·CH : CH·CO·CH3·COOH, but an attempt to synthesize it gave no deffinite result. When kawaic acid of M. and S. (C15H16O3) was treated with aqueous caustic potash at 100° a compound C14H16O3 or rather C14H14O3 (m.p. 175-177°) was obtained, which yielded cinnamalaceton on warming with dilute sulphuric acid. The latter was also obtained directly from kawaic acid by treating with dilute sulphuric acid or on distillation under diminished pressure. Probably the kawaic acid of Borsche (m p. 164-165°) may be identical with the alkali decomposition product of the kawaic acid of M. and S., as the latter at first melts at about 165°, which by repeated recrystallisation attains the constant m.p. 177-179°. The authors demonstrated the chemical constitution and transformation of the kawaic acid as follows : [numerical formula] The further confirmation of this formula is at present in pragress. Kawaic Acid. To prepare this acid 100g of the kawa resin was shaken with 300 c.c. of 6% aqueous caustic potash for 5-7 hours. The separated crystalline substances were fiitrated off and the filtrate was acidified with 5% acetic acid fractionately. At first a yellowish crystalline substance (m.p. 177-179°) and then the crude kawaic acid are presipitated. The latter, dissolved in chloroform, was shaken several times with sodium carbonate solution, which was acidified with acetic acid. The kawaic acid, after recrystallisation from absolute ether melted at 87°. The yield was 0.5% of the root. [table] The optical rotation was [α]20D-4000 in 10% alcoholic solution. Alkali Decomposition of Kawaic acid. 10g of kawaic acid was mixed with 100cc. of 10% sodium hydroxide solution and warmed on the water bath for 7 hours. The reaction mixture was acidified with dilute acetic acid, when resinous decomposition products were separated. On repeated recrystallization from acetone, a yellowish bright krystalline substance m.p. 175-177° (formerly 164°) was obtained. It is in soluble in cold sodium carbonate solution, soluble in hot carbonate solution and on cooling a krystalline sodium compounds separated out, from which the original substance may be isolated by the acid. Hnalysis : -[table] Methoxyl number (Zeisl's method) [talbe] The alkali decomposition product m.p. 175-177° was warmed with dilute sulphuric acid. The reaction mixture was distilled with steam, when yellow krystals passed over which were collected and dried on porous plate. It melted at 67-68° after recrystallization from absolute ether. [table] Action of dilute Sulphuric acid on Kawaic acid. 10g of kawaic acid was mixed with 400cc. of 5% sulphuric acid and warmed on the water bath for 2-3 hours. The reaction mixture was distilled with steam, the oily distillate was converted into semicarbazone in the usual manner. [the rest omitted]

On thallium

After discussing the occurrence and distribution of the new meta in different parts of the globe, the author proceeds to describe the method adopted by him for extracting it from its ore. Thalli-ferous pyrites is distilled at a bright red heat, in quantities of about 1 cwt. at a time, in cast-iron retorts. The resulting sulphur, varying from 13 to 17 per cent, of the pyrites taken, is then dissolved in aqueous caustic soda, which leaves the sulphide of thallium as an insoluble black precipitate; this is filtered off, dissolved in acids, and the thallium precipitated in the form of iodide. This is then converted into sulphate, and the metal reduced from the solution by electrolysis. It is obtained in the coherent form by fusion under cyanide of potassium.