Methyl, alcohol chloride

Conversion of (3- into a-glucose penta-acetate. Add 0-5 g. of anhydrous zinc chloride rapidly to 25 ml. of acetic anhydride in a 200 ml. round-bottomed flask, attach a reflux condenser, and heat on a boiling water bath for 5-10 minutes to dissolve the solid. Then add 5 g. of the pure P glucose penta-acetate, and heat on a water bath for 30 minutes. Pour the hot solution into 250 ml. of ice water, and stir vigorously in order to induce crystaUisation of the oily drops. Filter the solid at the pump, wash with cold water, and recrystaUise from methylated spirit or from methyl alcohol. Pure a-glucose penta-acetate, m.p. 110-111°, will be obtained. Confirm its identity by a mixed m.p. determination. 

The formaldehyde may be replaced by methylal CHjlOCH,), or by chloro-methyl ether CHjOCHjCl, produced from paraformaldehyde, hydrogen chloride and methyl alcohol ... 

Methyl p-toluenesulphonate. This, and other alkyl esters, may be prepared in a somewhat similar manner to the n-butyl ester with good results. Use 500 g. (632 ml.) of methyl alcohol contained in a 1 litre three-necked or bolt-head flask. Add 500 g. of powdered pure p-toluene-sulphonyl chloride with mechanical stirring. Add from a separatory funnel 420 g. of 25 per cent, sodium hydroxide solution drop by drop maintain the temperature of the mixture at 23-27°. When all the alkali has been introduced, test the mixture with litmus if it is not alkaline, add more alkali until the mixture is neutral. Allow to stand for several hours the lower layer is the eater and the upper one consists of alcohol. Separate the ester, wash it with water, then with 4 per cent, sodium carbonate solution and finally with water. Dry over a little anhydrous magnesium sulphate, and distil under reduced pressure. Collect the methyl p-toluenesulphonate at 161°/10 mm. this solidifies on cooling and melts at 28°. The yield is 440 g. 

Dissolve 7 g. of pure oleic acid in 30 ml. of dry ethyl chloride (chloroform may be used but is less satisfactory), and ozonise at about —30°. Remove the solvent under reduced pressure, dissolve the residue in 50 ml. of dry methyl alcohol and hydrogenate as for adipic dialdehyde in the presence of 0 5 g. of palladium - calcium carbonate. Warm the resulting solution for 30 minutes with a slight excess of semicarbazide acetate and pour into water. Collect the precipitated semicarbazones and dry the... 

Example 86 A 0.10 mole amount of the starting 3-(4-hydroxyphenyl) propylene, 0.25 mole of methyl nitrite, 0.5 liter of methyl alcohol, and 0.006 mole of a palladium chloride catalyst were charged into a reaction vessel. Then, the reaction was carried out at a temperature of 20.degree. C. for 1.5hours."... 

The physical properties of methylene chloride are Hsted in Table 1 and the binary a2eotropes in Table 2. Methylene chloride is a volatile Hquid. Although methylene chloride is only slightly soluble in water, it is completely miscible with other grades of chlorinated solvents, diethyl ether, and ethyl alcohol. It dissolves in most other common organic solvents. Methylene chloride is also an excellent solvent for many resins, waxes, and fats, and hence is well suited to a wide variety of industrial uses. Methylene chloride alone exhibits no dash or fire point. However, as Htde as 10 vol % acetone or methyl alcohol is capable of producing a dash point. 

Paprika oleoresin (EEC No. E 160c) is the combination of davor and color principles obtained by extracting paprika with any one or a combination of approved solvents acetone, ethyl alcohol, ethylene dichloride, hexane, isopropyl alcohol, methyl alcohol, methylene chloride, and trichloroethylene. Depending on their source, paprika oleoresins are brown—red, slightly viscous, homogeneous Hquids, pourable at room temperature, and containing 2—5% sediment. 

The most common impurities are the corresponding acid and hydroxy compound (i.e. alcohol or phenol), and water. A liquid ester from a carboxylic acid is washed with 2N sodium carbonate or sodium hydroxide to remove acid material, then shaken with calcium chloride to remove ethyl or methyl alcohols (if it is a methyl or ethyl ester). It is dried with potassium carbonate or magnesium sulfate, and distilled. Fractional distillation then removes residual traces of hydroxy compounds. This method does not apply to esters of inorganic acids (e.g. dimethyl sulfate) which are more readily hydrolysed in aqueous solution when heat is generated in the neutralisation of the excess acid. In such cases, several fractional distillations, preferably under vacuum, are usually sufficient. 

Factors affecting laboratory polymerisation of the monomer have been discussed" and these indicate that a Ziegler-Natta catalyst system of violet TiCl3 and diethyl aluminium chloride should be used to react the monomer in a hydrocarbon diluent at atmospheric pressure and at 30-60°C. One of the aims is to get a relatively coarse slurry from which may be washed foreign material such as catalyst residues, using for example methyl alcohol. For commercial materials these washed polymers are then dried and compounded with an antioxidant and if required other additives such as pigments. 

Phosphoryl chloride converts protopine into the quaternary salt isoprotopine chloride, C20H18O4NCI, m.p. 215° (dec.), which on treatment with potassium hydroxide in methyl alcohol yields anhydroprotopine, C2qH4,04N, m.p. 114-5°,1 just as crj ptopine is convertible into iso-cryptopine chloride and this into anliydrocryptopine. Similarly, protopine forms protopine methosulphate, CjoHigOjN. Me2S04, m.p. 252°, which is converted by potassium hydroxide in methyl alcohol, into two methyl-protopines, a-, m.p. 145°, and y-, m.p. 112°, corresponding with the two methyleryptopines, a-, m.p. 153°, and y-, m.p. 110°, respectively. 

Chondrofoline, CgjHgjOjNj, 2H2O, crystallises from methyl alcohol in triangular plates, m.p. about 135°, [ajffg — 280-6° (dry base N/10. HCl). It is a phenolic base, contains three methoxyl groups, does not give a Millon reaction, but in methyl alcoholic solution gives a faint, pink-purple colour with ferric chloride. The nitrate forms needles m.p. 225° (dec.). 

The base boiled in methyl alcoholic solution with methyl iodide and potassium hydroxide, forms a gelatinous methiodide, which was converted by silver chloride into the methochloride. The latter when boiled with 20 per cent, solution of sodium hydroxide, produced a mixture of methine bases, which were separated as the methiodides into 0-methylbebeerine-methine methiodide B, m.p. 237° (cf. p. 375), and a lasvorotatory form, m.p. 190°, which proved to be the lasvo-enantiomorph of d-O-methyl-bebeerinemethine methiodide (form C, p. 375). Chondrofoline therefore belongs to the bebeerine type represented by formula (III). In it R = H, the single phenolic hydroxyl is at ORj or OR4 and the remaining groups, OR2, OR 3, OR or alternatively ORj, OR2, OR 3 are methoxyl groups (King,i 1940). 

The process of isolation finally adopted by the former authors consists in precipitating as reineckates the water-soluble bases contained in a methyl alcoholic extract of the curare. The mixed reineckates are further purified, by solution in acetone and precipitation with water as often as may be necessary. The product so cleaned represents the bulk of the biological activity of the crude drug the mother liquors may contain curine (p. 374), which indicates a menisperm as one of the components of such curares. The mixed reineckates are then fractionated chromato-graphically over alumina and the components isolated as chlorides by the use of silver sulphate and barium chloride in succession. This process has been modified in detail by Schmid and Karrer, who have also found that with their curare, the more soluble reineckate fraction includes less potent quaternary alkaloids. 

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