Quaternary ammonium salts methiodides

A vigorously stirred suspension of 0.2 to 1 mole of sodium amide in 200 ml of xylene, in which were dissolved 0.1 mole of a,a-diphenyl-7-hexamethyleneimino butyronitrile was boiled for 12 hours. Thereupon the excess of sodium amide was decomposed with water and the xylene layer was separated, washed with water and extracted with hydrochloric acid. This acidic extract was made strongly alkaline with concentrated lye and the separated base was extracted with ether. After drying, the ether was evaporated and the l,l-diphenyl-3-hexamethyleneimino propane distilled in vacuo. The boiling point was 170-174°C/1 mm, the refractive index nD20 = 1.56 36, and the density d420 = 1.009. From the oil obtained several acid additions and quaternary ammonium salts can be obtained by reaction with acids containing a non-toxic anion or esters thereof. The hydrochloric acid salt, for instance, melts at 189-192°C, the methiodide at 174-177°C under decomposition. 

Paravallaridine (1) has been utilised as the starting point for the preparation of a number of steroidal quaternary ammonium salts which are exemplified by the bis-methiodides (2a) to (2d). These... 

Arecolidine, CgHi302N (80), which is isomeric with arecoline, was isolated in small quantity from the mother liquors from the technical preparation of arecoline hydrobromide (80). It crystallizes from ether as colorless needles, m.p. 105°, but after sublimation the base melts at 110°. It forms stable salts (Table 1) and a methiodide, yellow needles, m.p. 264° (dec.) which behaves towards alkalies as a quaternary ammonium salt. The methiodide may be transformed to a methaurichloride, m.p. 252° (dec.). Arecolidine is not hydrolyzed by alkalies and it was suggested by Emde (80) that it is probably 3,4-dimethoxy-l-methyl-l,2-dihydropyridine. However, the evidence is inadequate to support such a structure. 

Acetylpyridinium chloride H2NOH, HCl Methiodides Quaternary ammonium salt... 

Pyrroles of this type, where X is halogen, alcohol, or amine, and especially pro-tonated alcohol or quatemised amine, easily lose X generating very reactive electrophilic species. Thus ketones can be reduced to alkane, via the loss of oxygen from the initially formed alcohol (cf. section 13.1.7), and quaternary ammonium salts, typified by 2-dimethylaminomethylpyrrole methiodide, react with nucleophiles by loss of trimethylamine in an elimination/addition sequence of considerable synthetic utility. ... 

Hydrochlorides, Hydrobromides, Hydriodides Diisopropylamine hydrofluoride Dimethylamine -, Di-butylamine -, Prime thy lamine -, Tri-ethylamine -, Pyridine -y Quinoline hydrochloride Pyridine hydrobromide (CHg)2NCHF2,3HF Acetylpyridinium chloride H2N0H, HCl Methiodides Quaternary ammonium salt... 

Ene lactams can be obtained directly from quaternary phthalideisoquino-linium salts by treating them with concentrated ammonium hydroxide. In this way fumaramine (111) was synthesized from bicuculline (88) methiodide (121,124), fumaridine (113) from methiodides of both diastereomeric / - (91) and a-hydrastines (92) (5,124-126), and narceine imide (116) from narcotine (94) methiodide (122,127,128). In the case of the hydrastines (91 and 92) the Hofmann degradation of their methiodides in ammonia was not stereospecific but yielded the thermodynamically more stable Z isomer (113) (5). It seems, however, that from narcotine (94) a mixture of the Z and E forms was produced rather than a single isomer (123,127). 

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