As the factors influecing on the process of reaction (1) of cyanuric chloride with alcohols, the reactivities of alcohols and the effect of-OR in (2) and (3) on the reactivity of residual chlorine atom have been investigated from estimation of reaction velocity constant and evolved CO2in the presence of CaCO2 The reactivities of alcohols were found to be decreased in the order of CH3OH>C2H5OH>η-C4H9OH>η-C3H7OH>iso-C3H7OH, and the deactivation effect of the substituent groups were in order of -NH2 (-NHAr)>-OR>OAr, -0C2H5>-OCH3.The reactions (1) with various alcohols have been observed at various temperatures and reaction curves were obtained.The results indicated that the reactions were proceeded stepwise.Optimum temperatures for obtaining (2) and (3) were clarified.
Cyanuric chloride and methanol react at low temperature without addition of alkali such as NaHCO3 and give (4)(See part (I);similarly in the case of (1), (2).and On.The reason is that the reaction of (2) or (3) with methanol is accelerated by the acid and this is explained by comparing the reaction velocity of (1), (2), and (3) with methanol in the presence or absence of HC1.On the other hand, the alkalis used in the reaction with methanol are divided into two of the following: i) Kinds of slowing the reaction such as NaHCO3 andCaCO3 than without the addittion of alkali, and ii) kind of giving mor vigorous acceleration such as NaOH.i) acts as an acid-removing agent and prevents rapid formation of B and C (See part (I)), it is a controlling agent for proceeding of stepwise reaction of A, B and C, and it is suitable for syntheses of (2) and (3).ii) has a tendency of accelerating the reaction of alcohol and it is suitable for synthesis of (4).
In the reaction for formation of monovinylacetylene (MVA) from acetylene, the Niewland catalyst showed catalytic activity by addition of NII, Cl to CuCl. Although it has been considered that the maximum catalytic activity is obtainable when it has a constituent of CuC1.NH4Cl, the catalytic activity of CuClNH4Cl is the greatest when it has the concentration up to 400% of NH4Cl in water at 90°C but the maximum activity shifted towards the catalyst containing more CuCI than CuCl. NH2Cl in case of the concentration of NH4Cl exceeded 400%. In other words, the limit of concentration of NH4Cl in water for showing the maximum catalystic activity is up to 40%. However, the above limit of concentration is disappeared by reacting at low temperature such as at 40°C or by adding dimethyl sulfoxide (DMSO) in the reaction at 90°C in order to increase the saturated concentration of acetylene in the catalyst and to show the maximum catalytic activity of CuCl. NH4Cl even though the concentration of NH4Cl in CuCl. NH4Cl is reached above 40%. The presence of the limit of concentration is considered to be due to result of two counter-acting factors of showing positive effect by the increase in concentration of complex salt with the increase of NH4Cl in water and the negative effect by the decrease in concentration of acetylene.