Alcohols alkali fusion

Both the direct and the alcoholic alkali fusion methods gave recoveries of 90% or better with phenyl-containing silicones, the results obtained by the alcoholic alkali modification being generally higher. 

Alkali Fusion. Tha alkaU fusion of castor oil using sodium or potassium hydroxide in the presence of catalysts to spHt the ricinoleate molecule, results in two different products depending on reaction conditions (37,38). At lower (180—200°C) reaction temperatures using one mole of alkah, methylhexyl ketone and 10-hydroxydecanoic acid are prepared. The 10-hydroxydecanoic acid is formed in good yield when either castor oil or methyl ricinoleate [141-24-2] is fused in the presence of a high boiling unhindered primary or secondary alcohol such as 1- or 2-octanol. An increase to two moles of alkali/mole ricinoleate and a temperature of 250—275°C produces capryl alcohol [123-96-6] CgH gO, and sebacic acid [111-20-6] C QH gO, (39—41). Sebacic acid is used in the manufacture of nylon-6,10. 

Sophisticated instrumental techniques are continually being developed and gradually replace the classical wet chemistry analytical methods. Wet chemical analysis is destructive the sample is dissolved or altered. Nowadays the analyst is highly focused on instrumental methods and chemometrics. Yet, chemical work-up methods (e.g. hydrolysis with alcoholic alkali, alkali fusion, aminolysis, and transesterification, etc.) and other wet laboratory skills should not be forgotten. 

Halogen in organosilicon compounds may be either directly linked to silicon or may be part of a substituent group. Total halogen is usually determined by alkali fusion methods. Halogen attached directly to silicon is easily hydrolysable by aqueous alcohols and the halogen acid so produced can be estimated by direct alkali titration or by indirect procedures. 

The mixture of the two methine bases when treated with alcoholic alkali yielded a nitrogen-free compound which produced a tricarboxylic acid (m.p. 178°) on oxidation. For a number of years work was directed towards the identification of the tricarboxylic acid by degradative studies and by syntheses (50, 51, 52). Alkali fusion resulted in p-hydroxybenzoic acid, and on this basis it was concluded that the tricarboxylic acid must be one of the three isomeric acids LII, LIII, and LIV. All three were synthesized (50, 51, 52) by an Ullmann condensation of the appropriate compounds, and LIV (52) proved to be identical in all respects with that obtained from methylated isochondodendrine by degradation. Iso-chondodendrine was then assigned the structure LV or LVI. 

Ansell and Weedon have presented further reports on their studies of the alkali fusion of unsaturated acids, and of 0x0-, hydroxy-, epoxy-, and alkoxy-acids. The fission of 9(10)-hydroxy-10(9)-oxo-octadecanoic acid by alcoholic alkali at room temperature has been confirmed and shown to be an autoxida-tion reaction. ... 

G. Isopalmitinsaure R acide isopalmitique I. consists mainly of 2-hexyl decanoic acid. It is produced by alkali fusion of the corresponding 2-hexyldecan-l-ol (- Guerbet alcohol). 

Fusion with Alkali and Cupric Oxide in Nonaqueous Solvents. Alkali lignin was fused with potassium hydroxide and cupric oxide in methanol under conditions suggested by Tiemann (20) and in n-amyl alcohol as suggested by Klages (4). These procedures were very effective in earlier model compound studies in our laboratories (12). Ether extracts obtained were less than those from corresponding experiments in aqueous solution, and qualitative compositions were essentially the same. In the case of the amyl alcohol experiments, artifacts with the cupric oxide were obtained. Again, experiments were conducted under more dilute conditions in a bomb under superatmospheric conditions, but results were no better. 

Tin diphenyl oxide.— When the corresponding chloride or hydroxychloride in aqueous solution is digested with alkalies, or alcoholic or aqueous solutions of the chloride are treated with potassium or sodium hydroxides, ammonia or ammonium carbonate, the oxide is precipitated as a white powder, which resembles the hydroxychloride in solubility and properties. It does not melt, and decomposes without fusion on heating. 

To prepare carthamin, safflower is washed with water to remove the yellow dyestuff, and is then extracted with dilute soda solution, and filtered. Cotton yarn is immersed in the alkaline solution, and the liquid acidulated with citric acid. The cotton takes up the carthamin, which is removed with soda solution, and precipitated with citric acid. Obtained in this manner carthamin forms a lustrous green powder, sparingly soluble iu water and ether, readily in alcohol. It dissolves in alkalies with yellowish-green colour. On fusion with potash it gives oxalic acid and para-oxy-benzoic acid. Carthamin dyes animal fibres and unmordanted cotton from a slightly acid bath. It produces a beautiful pink colour on silk. 

---