Monoacetylation

The monoacetylation of alpha-omega diols can be accomplished in excellent yields. ... 

Dioctyl sulfo-succinate codeine, morphine, monoacetyl-mor-phine, heroin stabilization dipping solution, 20% in ethanol [94]... 

Dicentrine, CgoHjjOjN. (Items 36, 37, 39, 40 list, pp. 172-3.) This alkaloid crystallises, from ether, alcohol, or ethyl acetate in prisms, m.p. 168-9° [a]i) + 62-1° (CHCI3), and yields well-crystallised salts. It contains two methoxyl groups and yields a monoacetyl derivative, colourless leaflets, m.p. 202°, which is not hydrolysed even by boiling alcoholic potash. 1 The methiodide, B. CH3I. HjO, has m.p. 224°, and according to Manske, yields a methine base, m.p. 158-9°, the methiodide of which with potassium hydroxide solution decomposes into trimethylamine and a crystalline substance, presumably a substituted phenanthrenyl-ethylene, which polymerises on recrystallisation. 

Meroquinenine, CgHjjOaN (meroquinene), formed by the oxidation of all four alkaloids and of cinchoninone or quininone and by the hydrolysis of quinenine or cinchenine (p. 489), crystallises from methyl alcohol in needles, m.p. 223-4° (dee.), [ajp -f- 27-5° (H2O). It gives a nitrosoamine, m.p. 67°, and a monoacetyl derivative, m.p. 110°, and can be esterified the ethyl ester hydrochloride has m.p. 165°. When oxidised by chromic acid it yields formic and cincboloiponic acids. On reduction with zinc dust and hydriodic acid, it adds on two atoms of hydrogen forming cincholoipon, CgH jOaN, and when heated with hydrochloric acid at 250-60° gives 3-ethyl-4-methylpyridine ()3-collidine). 

EtOH). No methoxyl is present. It forms a series of crystalline double chlorides with cadmium, zinc or copper, does not give the thalleioquin reaction, and solutions of its sulphate are not fluorescent. It is diacidie and forms two series of salts of which the nitrate, B. HNOj, crystallises in minute prisms, m.p. 196°, insoluble in water. Cinchonamine hydrochloride, B. HCl, laminae or B. HCl. HjO, cubical crystals, has been suggested for use in the estimation of nitrates. When warmed with strong nitric acid the alkaloid furnishes dinitrocinchonamine. It gives an amorphous, monoacetyl derivative, and forms a methiodide, m.p. 208 , which with silver oxide yields an amorphous methylcinchonamine. Raymond-Hamet found that cinchonamine ves typical indole colour reactions and is probably an indole alkaloid. This seems to have been... 

Tetrahydrostrychnine, CgjHggOgNg. HgO. This substance, also formed by the electrolytic reduction of strychnine, crystallises from alcohol in prisms, m.p. 202°, gives colour reactions of the strychnidine type, and yields both neutral and acid salts the hydrochloride, B. HCl, occurs in small needles readily soluble in water and the dihydriodide, B. 2HI. 2HjO, in pyramidal crystals. The base yields an amorphous nitrosoamine, the hydrochloride of which crystallises from warm water in lustrous, yellowish prisms. It also furnishes a crystalline monoacetyl derivative, and on heating with hydrochloric acid or phosphorus oxychloride is dehydrated to strychnidine. 

The A-monoacetyl derivative is formed from acetic anhydride and pyridine at 100° higher temperatures give the 7V,A-diacetyl compound which does not react with peracid. In either case, there is a complete shift of the double bond from C-20(22) to C-17(20), with no evidence for any C-20(21) olefin. 

The acetylation of isotripiperideine by means of a ketone in nonpolar media affords a compound which decomposes in acidic media to piperideine and a monoacety.l derivative of the enamine form of tetrahydro-anabasine (195). This monoacetyl derivative is identical with the alkaloid amodendrine (312). A similar acylation with cinnamoylchloride affords the alkaloid orensine (196) (313), the optically active form of which is the natural alkaloid adenocarpine (314). The hydrolysis of alkaloid santiaguine gives a-truxilic acid (314). 

Diacetyl derivatives 473 after a short reflux with potassium carbonate in DMF provided high yields of 475 (82JOC2214). On the other hand, the corresponding monoacetyl derivatives 476 under the same conditions gave good yields of phenothiazines 478 (Scheme 76) (78JHC1137). 

Singer and co-workers have investigated the acylation reactions of ferrocene in ionic liquids made from mixtures of [EMIMJI and aluminium(III) chloride (Scheme 6.1-5) [9, 10]. The ionic liquid acts both as solvent and as source of the Friedel-Crafts catalyst. In mildly acidic (X(A1C13) > 0.5 [EMIM]I/A1C13, the monoacetylated ferrocene was obtained as the major product. In strongly acidic [EMIM]I/AlCl3 X(A1C13) = 0.67 the diacylated ferrocene was the major product. Also, when R = alkyl, the diacetylated product was usually the major product, but for R = Ph, the monoacetylated product was favored. 

The method of predicting pK a values by Clarke and Perrin (1) was tentatively applied to determine the structures of the two monoacetylated compounds, and the results indicate that kasugamycinic acid is 4-N-carboxyformyl-kasuganobiosamine (9a). 

Fig. 1 Concentrations reported for opiods and cannabinoids in surface water of different European countries. MOR morphine Nor-MOR nor-morphine 6ACM 6-monoacetyl morphine HER heroin MET methadone EDDP 2-ethylidene-l,5-dimethyl-3,3 diphenylpyrrolidine THC A9-tetrahydro-cannabinol THC-COOH 11-nor 9-carboxy-THC N/A Values not availabe, not measured...

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