Bromide potassium, reaction amines

Extending the intermolecular coupling, dihydroindoles (Scheme 4), dihydroquinolines, and other N-heterocycles were successfully synthesized by simple intramolecular trapping reactions, starting from alkylamino substituted aryl bromides. [8] Intramolecular amination can be achieved in the presence of tetrakis(triphenylphosphine)palladium as catalyst and stoichiometric amounts of base in toluene. Here, best results are obtained with mixtures of NaOtBu and potassium carbonate. 

Anilines are converted into nitrosoarenes ArNO by the action of hydrogen peroxide in the presence of [Mo(0)(02)2(H20) (HMPA)] ", whereas catalysis of the reaction by titanium silicate and zeolites results in the formation of azoxybenzenes ArN (0)=NAr. Azo compounds ArN=NAr are formed in 42-99% yields by the phase-transfer assisted potassium permanganate oxidation of primary aromatic amines in aqueous benzene containing a little tetrabutylammonium bromide. The reaction of arylamines with chromyl chloride gives solid adducts which, on hydrolysis, yield mixtures of azo compounds, p-benzoquinone and p-benzoquinone anils 234. ... 

Saunders and co-workers (Amin et al., 1990) used E2 elimination reactions in the p-substituted 2-phenylethyl system to test the new criteria for tunnelling suggested by the above calculations. The actual substrates and base/solvent systems they used were (2-phenylethyl-2-f)-trimethylammonium bromide, [19], with sodium ethoxide in ethanol, 2-phenylethyl-2-f bromide, [20], with potassium t-butoxide in t-butyl alcohol and 2-(p-chlorophenyl)ethyl-2-f tosylate, [21], with potassium t-butoxide in t-butyl alcohol. When equation (57) was applied to the experimental secondary (kB/ S) KIEs in Table 39, the calculated /th h KIEs were 1.106 0.033 and 1.092 0.026 for [19] and [21],... 

The analogue, t-butyl methyl iminodicarboxylate 25, is obtained by the reaction of methanol with t-butyl oxamate (24) in the presence of lead tetraacetate. Its stable non-hygroscopic potassium salt is converted into alkyl derivatives 26 by the action of alkyl halides such as butyl bromide, allyl bromide, propargyl bromide and ethyl bromoacetate. The products are hydrolysed by trifluoroacetic acid to salts of primary amines, whereas... 

The reaction with ammonia or amines, which undoubtedly proceeds by the SNAr mechanism, is catalyzed by copper8" and nickel105 salts, though these are normally used only with rather unreactive halides.106 This reaction, with phase transfer catalysis, has been used to synthesize triarylamines.107 Copper ion catalysts (especially cuprous oxide or iodide) also permit the Gabriel synthesis (0-58) to be applied to aromatic substrates. Aryl bromides or iodides are refluxed with potassium phthalimide and Cu 0 or Cul in dimethylacetamide to give N-aryl phthalimides, which can be hydrolyzed to primary aryl amines.108... 

In addition, aryl chlorides, bromides, and iodides can be converted to arene-amines ArNH2 by the conjugate bases of amines. In fact, the reaction of potassium amide with bromobenzene is extremely rapid, even at temperatures as low as —33°, with liquid ammonia as solvent ... 

General Procedure.—Dissolve 0-2—0-5 gm. of the compound to be estimated in 200 c.cs. of water, using a slight excess of hydrochloric acid for amines or a similar excess of caustic soda in the case of phenols, carboxylic- and sulphonic-acids. To the solution thus prepared 10 c.cs. of a 20% solution of potassium bromide and 5—10 c.cs. of concentrated hydrochloric acid are added the mixture is brought to the required temperature and N/5 bromate solution run in slowly until a sample withdrawn gives a reaction on starch-iodide paper. The presence of free bromine should be again tested for after 5 minutes. 

Vinyl iodides are considerably more reactive than bromides in the vinylations. It may be presumed that chlorides are not generally useful, with one exception noted below, since they have not been employed in the reaction. The bromides are usually reacted with a palladium acetate-triphenyl- or tri-o-tolyl-phos-phine catalyst at about 100 C. The reaction will occur without the phosphine if a secondary amine is present. Vinyl iodides will react in the absence of a phosphine even with only a tertiary amine present.48 37 The iodides are so reactive, in fact, that reactions occur even at room temperature if potassium carbonate is the base and tetra-zi-butylammonium chloride is used as phase transfer agent in DMF solution when palladium acetate is the catalyst.88... 

The enantioselective complexation technique can also be applied as one step in the reaction sequence, providing chiral substrates for the next step. We will now discuss the example of Gabriel synthesis between potassium phthalimide 41 and alkyl bromide 42, which leads to optically active amines (Scheme 1) [51], Instead of the complicated preparation of chiral alkyl bromides (halides), imides (43), which are reaction intermediates, have been resolved. Upon treatment with hydrazine and KOH, these gave optically active amines. The chiral host (S,S)-(-)-6 or the chiral biaryl host (,S>(-j-40 was used for the effective resolution of the intermediates 43. Racemic mixtures 43a-d were resolved by complex formation with the host (S,S)-(-)-6 in a mixture of diethyl ether and light petroleum. 

The Gabriel synthesis is a classical but useful preparative method for primary amines. Reaction of an alkyl bromide (24) with potassium phthalimide (25) gives the corresponding A -alkylphthalinude (26), which upon treatment with hydrazine followed by KOH affords the primary amine (27). When a chiral alkyl halide is used in the Gabriel synthesis, a chiral primary amine is obtained. However, preparation of optically active alkyl halides is not easy. If optical resolution of 26 which has a chiral alkyl group can be done, a new preparative method for optically active amines can be established by a combination of the resolution with the Gabriel synthetic method. Some examples of the combination method are described. 

Aminopolyhydroxynaphthalenes. This NH, synthon was used to convert the protected bromopolyhydroxynaphthalene derivative I to the protected aminopolyhydroxy-naphthalene derivative 2, the aromatic nucleus of an ansamycin. One advantage of this amination is the satisfactory yield, which occurs in spite of the steric factors usually observed in the reaction of bromides with potassium azide. 

Sulfoxides. The complexes of bromine with tertiary amines have been used to convert sulfides to sulfoxides. The reaction can be conducted more conveniently with bromine and potassium hydrogen carbonate as the hydrogen bromide acceptor under two phase conditions (H2O-CH2CI2). Yields are in the range 80-100%. ... 

Alkylation of N-substituted trifluoroocetamides. N-alkyl or N-aryl trifluoro-acetamides can be alkylated by primary bromides or iodides by use of potassium hydride in combination with 18-crown-6 as base. This reaction is a useful route to secondary amines (equation I). ... 

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