Alkyl tert, amines, reaction with

The most conspicuous property of aliphatic amines, apart from their fishy smell, is their high basicity, which usually precludes N-alkylations under acidic reaction conditions (last reaction, Scheme 6.3). Hence, alkylation of amines with tertiary alkyl groups is not usually possible without the use of highly stabilized carbocations which can be formed under basic reaction conditions. Rare exceptions are N-alkyla-tions of amines via radicals (Scheme 4.2), copper-catalyzed propargylations (Scheme 6.3), and the addition of amines to some Michael acceptors and allyl palladium or iridium complexes. Better strategies for the preparation of tert-alkylamines include the addition of Grignard reagents to ketone-derived imines [13] or the reduction of tert-alkyl nitro compounds. 

At this point the conversion of /i3-(chloromethylidyne)-tris-(tricarbonylcobalt) is complete, and its reactions with a wide variety of nucleophiles, such as alcohols, thiols, amines, alkylating agents, and the more nucleophilic aromatic compounds, may be carried out. The reaction with tert-butanol is described here. 

The first route was rather straight forward introducing first the nitrogen containing side chain by reacting the epoxide with methylamine in methanol at 120 °C under pressure to the amino-alcohol 215 and N-alkylation of this intermediate with 1-bromoheptane in ethanol to the tertiary amine 216. This same product was prepared directly by reaction of the epoxide with N-methylheptylamine in ethanol with a catalytic amount of hydrochloric acid at 120 °C under pressure. O-alkylation was performed according to the method used by J. Fried69) that is reaction of 216 with tert. butyl-oj-iodohexanoate (NaH in DMSO). Compound 217 was charac-... 

When l,2,3-tris(rf rt-butylsulfanyl)cyclopropenylium tetrafluoroborate (29) was treated with anilines, one of the tert-butyl groups was replaced by the phenylamino group to give the 1-arylamino-2,3-bis(mrr-butylsulfanyl)cyclopropenylium salts 30. The reaction with alkyl-amines of higher basicity, however, caused cleavage of the cyclopropenylium ring, giving rise to vinylazomethine-type iminium salts. 

MONOHYDROXYMETHANE (67-56-1) Forms explosive mixture with air (flash point 50°F/10°C). Violent reaction with strong oxidizers, acetyl bromide, alkyl aluminum salts, beryllium dihydride, bromine, chromic acid, l-chloro-3,3-difIuoro-2-methoxycyclopropene, cyanuric chloride, diethylzinc, isophthaloyl chloride, nitric acid, perchloric acid, potassium-tert-butoxide, potassium sulfur diimide, Raneynickel catalysts, 2,4,6-trichlorotriazine, triethy-laluminum, l,3,3-trifluoro-2-methoxycyclopropene. Incompatible with strong acids, strong caustics, alkalineearth and alkali metals, aliphatic amines, acetaldehyde, benzoyl peroxide,... 

Carboxylic nitrile liquid and solid elastomers are used to prepare elastomer-modified epoxy liquid and solid resins when it is desirable to have the modifier in the epoxy portion of the system. This is effected through alkyl-hydroxy esterification reactions. This is covered in the literature for uncatalyzed liquid resins (9), for tert-amine catalyzed systems (10), for tert-phosphine catalyzed systems (11), for low molecular weight solid resins advanced from the liquid state (12) and for liquid and solid resins where an additional rubber vulcanization step is carried out in addition to the alkylhydroxy ester adducting step (13). Such adduct preparations offer formulation stability with a wide range of hardener types amines, anhydrides, catalytic, Lewis acids/bases. 

Di-tert-butyl dicarbonate, B0C2O Unfortunately, most of the known methods for transforming amines into isocyanates are not mild enough and furnish undefined products as a result of uncontrolled side reactions. However, 4-dimethylaminopyr-idine (DMAP)-catalyzed reaction with activated carbonates as Ci building blocks constitutes a convenient laboratory method for the phosgene-free isocyanation of amines. A procedure has been described whereby alkyl- and arylamines are converted into isocyanates in high yields by reaction with activated carbonates (for... 

By reaction of 2-alkyl-4,6-dichloro-l,3,5-trimethylborazines (alkyl = methyl, ethyl, i-propyl) with bis(trimethylsilyl)amine the tetrameric borazine ring systems 4-6 are produced (Fig. 2) they can be purified by several successive vacuum sublimations (yields 4-60%). If the borazines carry n-propyl and tert-butyl groups in the 2-position or if methylbis(trimethylsilyl)amine is used to bridge the borazine molecules, the macrocyclic ring formation is inhibited [17, 18]. 

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