Alkyl, amines Preparation

Refluxing linoleic acid and a primary or secondary alkyl amine with -toluenesulfonic acid in toluene for 8—18 h also yields the substituted amides (32—34). The reaction of methyl esters with primary or secondary amines to make substituted amides is catalyzed with sodium methoxide. Reactions are rapid at 30°C under anhydrous conditions (35). Acid chlorides can also be used. Ai,A/-dibutyloleamide [5831-80-17 has been prepared from oleoyl chloride and dibutyl amine (36). 

In addition to the nitrile and alcohol routes for fatty amine preparation, processes have been described by Unocal and Pennwalt Corporation, using an olefin and secondary amine (14—16) by Texaco Inc., hydrogenation of nitroparaffins (17—20) by Onyx Corporation, reaction of an alkyl haUde with secondary amines (21,22) by Henkel Cie, GmbH, reduction of an ester in the presence of a secondary amine (23) by catalytic hydroammonolysis of carboxyhc acids (24) and by the Hofmann rearrangement (25). 

Cl Disperse Blue 87 (107) and related dyestuffs are also prepared from l-oxo-3-imino-4,7-diamino-5,6-phthaloyhsoiQdoline [13418-50-3] (111) by alkylation with corresponding alkyl haUdes (122), sulfonic esters (123), or alkyl amines (124), ie, X of RX = halogen, -toluenesulfonyloxy, or NH2. 

Sulfonamides (R2NSO2R ) are prepared from an amine and sulfonyl chloride in the presence of pyridine or aqueous base. The sulfonamide is one of the most stable nitrogen protective groups. Arylsulfonamides are stable to alkaline hydrolysis, and to catalytic reduction they are cleaved by Na/NH3, Na/butanol, sodium naphthalenide, or sodium anthracenide, and by refluxing in acid (48% HBr/cat. phenol). Sulfonamides of less basic amines such as pyrroles and indoles are much easier to cleave than are those of the more basic alkyl amines. In fact, sulfonamides of the less basic amines (pyrroles, indoles, and imidazoles) can be cleaved by basic hydrolysis, which is almost impossible for the alkyl amines. Because of the inherent differences between the aromatic — NH group and simple aliphatic amines, the protection of these compounds (pyrroles, indoles, and imidazoles) will be described in a separate section. One appealing proj>erty of sulfonamides is that the derivatives are more crystalline than amides or carbamates. 

Bis(bromomethyl)-5//-dibenz[/), / ]azepines, e.g. 12, prepared by free-radical bromination of the 10,11-dimethyl compound with yV-bromosuccinimide, on treatment with a primary alkyl-amine followed by alkaline hydrolysis, yield l,2,3,8-tetrahydrodibenzo[. /]pyrrolo[3,4-<7]-azepines, e.g. 13, which possess useful pharmacological properties.91,163... 

Alkylnickel amido complexes ligated by bipyridine have been prepared that undergo reductive elimination of V-alkyl amines (Equation (54)).207,208 Unlike the phosphine-ligated palladium arylamides, these complexes underwent reductive elimination only after oxidation to nickel(III). Thermally induced reductive elimination of alkylamines from phosphine-ligated nickel complexes appears to occur after consumption of phosphine by arylazides 209... 

By means of substitution reactions, derivatives containing alkoxide, alkyl, amine, and other groups can be prepared as illustrated by the following equations ... 

This method is essentially that described by Pollard and Par-cell.8 No other procedure appears to have been used to prepare N-(2-bromoallyl)ethylamine. A number of N-(2-haIoaIIyl)alkyl-amines have been prepared by treatment of a 2,3-dihalopropene with a primary alkylamine in water,8-4 ether,8-4 or benzene.5... 

Unsymmetrical secondary aliphatic amines have been prepared by reaction of alkyl halides with benzylidene amines and subsequent hydrolysis 814 by reaction of alkyl halides with alkyl amines 5 by reduction of amine-aldehyde adducts 8-8 and by dealkylation of tertiary amines with dibenzoyl peroxide. ... 

Of the 3 possible types of peroxy carbonate esters-dialkyl monoperoxy carbonates, dialkyl diperoxycarbonates and dialkyl peroxydicarbonates-, the latter are by far the least stable group. Several of the 16 alkyl and substituted-alkyl esters prepared decomposed violently or explosively at temperatures only slightly above the temperature of preparation (0-10°C), owing to self-accelerating exothermic decomposition. Several were also explosive on exposure to heat, friction or shock [1], Amines and certain metals cause accelerated decomposition of dialkyl peroxydicarbonates by a true catalytic mechanism [2], Individually indexed compounds are ... 

The usefulness of this reaction for the preparation of heterocycles under mild conditions became apparent in 1978, when chemists from Merck, Sharp Dohme reported the synthesis of bicyclic 3-lactams by intramolecular carbene N-H insertion [1179]. Intramolecular N-alkylation of P-lactams by carbene complexes is one of the best methods for preparation of this important class of antibiotic and many P-lactam derivatives have been prepared using this methodology [1180 -1186] (Table 4.11). Intramolecular N-H insertion can also be used to alkylate amines [1187-1189], y-lactams [1190], and carbamates [1191-1193] (Table 4.11). 

Also, it can be prepared by the reaction of iron(ll) chloride with cyclopentadiene in the presence of an alkyl amine or a similar base. 

PREPARATION OF a -ALKYLATED AMINES FROM OXIME SULFONATES WITH TRIALKYLALUMINUM - DIISOBUTYLALUMINUM HYDRIDE... 

As an alternative to the Glu and Asp scaffolds, the A-(dialkyl)amide of diglycolic acid has been proposed (13). This is readily prepared by heating equivalent amounts of diglycolic anhydride and, for example, bis(octadecyl)amine in refluxing toluene for 48 hours followed by recrystallization from chloroform (mp 81-82 °C)J178 In a similar mode, polyoxyethylene of selected chain length has been used to prepare dicarboxylic acids which, upon mono-amidation with bis(alkyl)amines, yield lipo moieties (e.g., 14) that are coupled to selected amine groups of peptides to produce the peptide amphiphiles. 179180 ... 

The dibasic side chain at position 7 can be alternatively provided by a substituted amino alkyl pyrrolidine. Preparation of that diamine in chiral form starts with the extension of the ester function in pyrrolidone (46-1) by aldol condensation with ethyl acetate (46-2). Acid hydrolysis of the (3-ketoester leads to the free acid that then decarboxylates to form an acetyl group (46-3). The carbonyl group is next converted to an amine by sequential reaction with hydroxylamine to form the oxime, followed by catalytic hydrogenation. The desired isomer (46-4) is then separated... 

Alkyl carbamates prepared from the carbamyl chlorides also react with amines to give semicarbazides [15, 17] (Eq. 25). 

Monoureas can also be prepared using COS and an alkyl amine, or an arylamine in the absence or presence of a catalyst, where R = H, alkyl, or aryl (39) ... 

The preparation of N-alkyl imides by exchange reaction of an imide with an alkyl amine was documented [104] well before the application of this chemistry to the preparation of polyimides [105], see Scheme 30. Although no experimental details are provided, the initial reaction of pyromellitimide with p,p-methylene dianiline in NMP takes place at reflux temperatures to apparently yield a poly(amic amide). Subsequent heating of this intermediate at elevated temperatures ( 300 °C) provides the desired polyimide with evolution of ammonia. The final polyimide is quoted to be thermally and chemically stable, however, no mechanical properties are given. 

The dyes may be prepared by treatment of l,4-diamino-2,3-dicyanoanthraquinone with sulfuric acid followed by alkylation of the imide by primary alkyl amine exchange. Alternatively, the sulfuric acid treatment may be carried out in the presence of a secondary alcohol (Scheme 11). 

TERTIARY AMINE PREPARATION BY REDUCTIVE ALKYLATION OF ALIPHATIC SECONDARY AMINES WITH KETONES... 

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