Hydrogen chloride, viii

In order to determine whether other secondary alcohols would give phosphorofluoridic esters of high potency, dicycio-hexyl phosphorofluoridate (VIII) was prepared by the action of phosphorus oxydichlorofluoride on cyciohexanol. In this preparation it was essential to remove all the hydrogen chloride before distillation, otherwise decomposition took place. The... 

VIII. Hydrogen chloride will add first to the nitrogen with which it will give the lowest dissociation pressure. 

Generalization VIII was put in almost as an after-thought to account for the behavior of succinimidine, which we have not yet tested ourselves. According to the literature this compound adds only one hydrogen chloride... 

Catalysts from Group VIII metals have given unsatisfactory results. In the polymerization of butadiene with soluble cobalt catalysts tritium is not incorporated when dry active methanol is employed [115], although it is combined when it has not been specially dried [117, 118]. Alkoxyl groups have been found when using dry alcohol [115, 119] but the reaction is apparently slow and not suited to quantitative work [119]. Side reactions result in the incorporation of tritium into the polymer other than by termination of active chains [118], probably from the addition of hydrogen chloride produced by reaction of the alcohol with the aluminium diethyl chloride [108], Complexes of nickel, rhodium and ruthenium will polymerize butadiene in alcohol solution [7, 120], and with these it has not been possible to determine active site concentrations directly. 

Cytisine (VIII) was the starting point in a synthesis of angustifoline. Tetrahydrocytisine (XLI) was converted to the A -chloro derivative (XLII) with hypochlorite. The elimination of hydrogen chloride from the latter leads specifically to the Schiff hase (XLIII) which is stereospecifically alkylated with allyl magnesium chloride. The approach of the reagent from the under side of the molecule is sterically very improbable (52). 

We then directed/our attention to the properties of fluoro-methyl cyanide, as it seemed likely, on theoretical grounds, that it would undergo certain addition reactions very readily. Alcohol and dry hydrogen chloride readily converted it into Jluoroacetimino ethyl ether hydrochloride (VI), which was converted into the amidine (VII) by means of alcoholic ammonia. Similar condensation of the cyanide with 2-fluoroethanol and phenol yielded jluoroacetimino 2 jluoroethyl ether hydrochloride (VIII R = CHj CHjF) and the corresponding phenyl imino ether hydrochloride (VIII i2 = Ph) respectively. Analogous experi-... 

To a reaction flask are added the carbonyl compound and an equivalent amount of dithiol along with 10 ml of freshly distilled dry dioxane. The solution is placed in an ice bath while dry hydrogen chloride is bubbled through for varying lengths of time. In all cases the reaction is exothermic and a pink color develops. The mixture is cooled and 20 ml of cold methanol added to precipitate the polymer. The polymer is dried under reduced pressure (approximately 1 mm Hg) at room temperature and the results are shown in Table VIII. 

Two syntheses of dihydronitidine, starting from the ketone VII, have been reported 10, 11). This ketone, which was prepared by a method previously explored 12), was converted to its oxime whose acetate on heating with acetic acid, acetic anhydride, and hydrogen chloride generated VIII (R = Me). Oxidation gave VIII (R = C02H) which was decarboxylated, converted to methosulfate, and reduced to dihydronitidine (I R -I- R = CH2, X = H2). 

The action of ferric chloride and hydrogen peroxide on isopropyli-dene and benzylidene derivatives of 2-hydrazinoselenazole yields deeply colored compounds of the 2,2 -dioxo-A -biselenazol-5,5 -inylidene bis-hydrazone type. (Cf. Table VIII.)... 

Scheme 18. Reagents and Conditions (i) Immobilised poly-(L)-leucine, urea hydrogen peroxide, DBU, THF, 12 h, 76%, 94% e.e. (ii) mCPBA, CH2CI2, 94%. (iii) HCl (g), CH2CI2, 66%. (iv) Amberlite IRA-420 ( OH), THF, 80%. (v) NaNj, MeOH, H20,94%. (vi) H2, Pd/C, EtOAc. (vii) NH3,MeOH. (viii) benzoyl chloride, (ix) trifluoroacetic acid, CH2CI2,74%...

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