Reaction with aluminium bromide

COCH2Br - Preparation by reaction of aluminium bromide n with 2,4,6-trimethoxy-a-bromoacetophenone at... 

The higjily water-soluble dienophiles 2.4f and2.4g have been synthesised as outlined in Scheme 2.5. Both compounds were prepared from p-(bromomethyl)benzaldehyde (2.8) which was synthesised by reducing p-(bromomethyl)benzonitrile (2.7) with diisobutyl aluminium hydride following a literature procedure2.4f was obtained in two steps by conversion of 2.8 to the corresponding sodium sulfonate (2.9), followed by an aldol reaction with 2-acetylpyridine. In the preparation of 2.4g the sequence of steps had to be reversed Here, the aldol condensation of 2.8 with 2-acetylpyridine was followed by nucleophilic substitution of the bromide of 2.10 by trimethylamine. Attempts to prepare 2.4f from 2.10 by treatment with sodium sulfite failed, due to decomposition of 2.10 under the conditions required for the substitution by sulfite anion. 

Cross-alkylations have been reported on a number of occasions. Thus, ethylbenzene when treated with aluminium bromide and hydrogen bromide at 0 °C forms some benzene and diethylbenzene168, and in the sulphonation of durene some trimethyl- and pentamethyl-benzenesulphonic acids are formed as well as the tetra-methyl compound. It has been suggested169 that these transfer reactions involve an SN2 type process... 

Treatment of 19b with phenylmagnesium bromide gives diphenylacetylene (66) and the salt of benzenesulfmic acid Lithium aluminium hydride reacts with 19b similarly. These ring-opening reactions are similar to the reactions of organometallic reagents with the analogous thiirane dioxides (equation 17 above). 

Bromochloromethane was being prepared in a 400 1 reactor by addition of liquid bromine to dichloromethane in presence of aluminium powder (which would form some aluminium bromide to catalyse the halogen exchange reaction). The reaction was started and run for 1.5 h, stopped for 8 h, then restarted with addition of bromine at double the usual rate for 2.5 h, though the reaction did not appear to be proceeding. Soon afterwards a thermal runaway occurred, shattering the glass components of the reactor. 

A ubiquitous co-catalyst is water. This can be effective in extremely small quantities, as was first shown by Evans and Meadows [18] for the polymerisation of isobutene by boron fluoride at low temperatures, although they could give no quantitative estimate of the amount of water required to co-catalyse this reaction. Later [11, 13] it was shown that in methylene dichloride solution at temperatures below about -60° a few micromoles of water are sufficient to polymerise completely some decimoles of isobutene in the presence of millimolar quantities of titanium tetrachloride. With stannic chloride at -78° the maximum reaction rate is obtained with quantities of water equivalent to that of stannic chloride [31]. As far as aluminium chloride is concerned, there is no rigorous proof that it does require a co-catalyst in order to polymerise isobutene. However, the need for a co-catalyst in isomerisations and alkylations catalysed by aluminium bromide (which is more active than the chloride) has been proved [34-37], so that there is little doubt that even the polymerisations carried out by Kennedy and Thomas with aluminium chloride (see Section 5, iii, (a)) under fairly rigorous conditions depended critically on the presence of a co-catalyst - though whether this was water, or hydrogen chloride, or some other substance, cannot be decided at present. 

A scheme equivalent to our supposition 2 was put forward by Chmelir, Marek and Wichterle to explain the polymerisations initiated by aluminium bromide in heptane [11]. The fact that these reactions were of second order with respect to the initiator demanded an explanation in terms of a pre-initiation reaction between two molecules of initiator. 

The conductivity changes accompanying and following the polymerisation of five portions of norbornadiene added to an aluminium bromide solution at -63 °C are shown in Figure 6 (Experiment No. R4). The polymer, which was precipitated during the reaction, was subsequently found to be insoluble and therefore presumably crosslinked. Since this polymer was, therefore, unsuitable for radiochemical assay, another experiment (RIO) was done with norbornadiene in a mixture of methyl and ethyl bromide at -125 °C to prevent cross-linking. The polymer was soluble and the number of tritium atoms per molecule of polymer was much greater than for polyisobutylene. 

To ascertain whether tritium could have entered the polyisobutylenes by a process other than the hydrolysis of a carbon-aluminium bond, we tested the reaction of suitable polymers with aluminium bromide. The polyisobutylenes were dissolved in ethyl bromide, and phials of aluminium bromide were crushed into these solutions, which were subsequently kept at 0 °C for ca. 15 minutes, and then hydrolysed in the usual way with tritiated water. The three substances examined in this way were polyisobutylenes of high and low DP, and nonadecane. The polyisobutylenes contain approximately one double bond per molecule. The results in... 

In the case of either substance the bromine is doubtless first added on at the double bond. Whilst the reaction takes place easily with the reactive double bond of the olefines, carriers such as iron, iron halide, and aluminium bromide are required for the sluggish double bond of the benzene ring ... 

After termination of the reaction, heat flask I strongly with the flame of a burner and distil the obtained aluminium bromide in a stream of carbon dioxide into receiver 3. To remove traces of bromine, repeat the distillation in the apparatus shown in Fig. 122h... 

The reduction of methyl 6-methoxy-2-naphthyl acetate with lithium aluminium hydride in refluxing ether gives 2-(6-methoxy-2-naphthyl)ethanol, which by treatment with PBr3 in refluxing benzene is converted into 2-(6-methoxy-2-naphthyl)ethyl bromide. Further reaction with KCN in refluxing ethanol-water affords 3-(6-methoxy-2-naphthyl) propionitrile, which is finally treated with methylmagnesium iodide in refluxing ethanol. 

Fig (10) The iron complex (80), prepared from methyl abietate (79) is converted to compound (81) utilizing standard organic reactions. It was converted to allylic alcohol (82) by treatment with iodine and potassium bicarbonate. The ketone (83) obtained from (82) undergoes aromatization on bromination and dehydrobromination. Yielding (84) whose transformation to lactone (87) is accomplished following the similar procedure adopted for the conversion of (68) to (74). It is converted to pisiferic acid (1) by treatment with aluminium bromide in... 

Protopine has been isolated from Bocconia frutescens,110 Fumaria judaica,111 F. schleicheri,112 and Papaver bracteatum,146 cryptopine from F. schleicheri,112 and allocryptopine from B. frutescens110 and Zanthoxylum nitidum.141 The protopine ring-system has been prepared from tetrahydrobenzindenoazepines (75) by photo-oxidation to the amides (76) followed by reduction with lithium aluminium hydride and re-oxidation with manganese dioxide.148-150 The tetrahydrobenzindenoazepines have been prepared from A-chloroacetyl-/ -phenylethylamines (73) by cyclization to the lactam (74) followed by reaction with a benzyl bromide and phosphorus oxychloride. -Protopine (77 R R2 — CH2)148 and fagarine II (77 R1 = R2 = Me)149 have been synthesized in this way. 

The Leukart reaction has also been used in the conversion of dehydroepiandro-sterone into 17/3-formylamino-3/3-formyloxyandrost-5-ene, which on reduction with lithium aluminium hydride afforded 3/3-hydroxy-17/3-me thylaminoandrost-5-ene. Acylation with isocaproyl chloride then furnished the N-methyl-N-isocaproyl steroid (197), after selective ester hydrolysis of the initially formed ON-diacyl derivative. The amide (197) was further converted into its 3,5-cyclo-6-ketone via the 3,5-cyclo-6/3-alcohol and thence by reaction with hydrogen bromide into the corresponding 3/3-bromo-5a-6-ketone which upon dehydrobromination furnished a A2-5a-6-ketone and ultimately the 2-monoacetate of the 2/3,3/3-diol (198) after reaction with silver acetate and iodine. Hydrolysis to the 2/3,3/3-diol (198) gave a separable mixture of the 2/3,3/8-dihydroxy-5a- and -5/3-ketones.88... 

---