Alkyl, amines anilines

Mj primary and secondary alkyl amines, anilines, primary alcohols... 

The 4,4 -MDA is sold commercially with a diamine assay of 98 —99%. The major impurity is the 2,4 -MDA isomer, which can be present in amounts up to 3%. PMDA products are normally defined by hydrogen equivalent weight and viscosity. Typical products exhibit a 50 hydrogen equivalent weight and a viscosity of 80 140 mPa-s(=cP) at 70°C. PMDA products normally contain, in addition to the isomers and oligomers of MDA, small amounts of aniline, water, chlorides, and various alkylated amines. AH MDA products should be stored in sealed containers in a cool dry area. 

Primary ( ) amines e.g. alkyl amines [1—3] lipid amines [4] a, co-diamines [5, 6] polyamines [6] alkanol amines [7] subst. anilines [8] aminoglycoside antibiotics [9, 10] biogenic amines [11] hydrazines... 

The Zincke reaction is an overall amine exchange process that converts N- 2,A-dinitrophenyl)pyridinium salts (e.g, 1), known as Zincke salts, to iV-aryl or iV-alkyl pyridiniums 2 upon treatment with the appropriate aniline or alkyl amine. The Zincke salts are produced by reaction of pyridine or its derivatives with 2,4-dinitrochlorobenzene. This venerable reaction, first reported in 1904 and independently explored by Konig, proceeds via nucleophilic addition, ring opening, amine exchange, and electrocyclic reclosure, a sequence that also requires a series of proton transfers. By... 

Diethanolamine (DEA), 2,2 -iminodiethanol di( -ethyloxy)aniline. HN-(CH2CH2OH)2, MW = 105.1. Sp. gr. = 1.097. Flash point = 280 °F. Also used as an absorbent for acidic gases in petrochemical operations. Hygroscopic. Available as a 98.5+% alkyl amine commodity product from various international manufacturers, including Texaco Corporation. Commonly available through chemical distributors. 

It has been shown that the imidoyl chloride moiety of 2(lff)-pyrazinones can imdergo an easy addition/elimination reaction with alkyl amines [24], while reactions with anilines proceed under harsher conditions. Ullmann coupling [109-113] of 2(lff)-pyrazinones with substituted anilines could open the way to the libraries of physiologically active compounds useful in inhibiting HIV replication [7]. Polymer-bound pyrazinone was successfully... 

In the previous analysis for the second quadrant amines, there was evidence that the presence of an aromatic ring (BzAM) increased competition with the deactivating intermediate(s) and significantly the amount of DHQ obtained. The study was thus extended to other aromatic amines aniline (AN), 2-ethylaniline (2-ETAN), 3-ethylaniline (3-ETAN) and N-ethylaniline (N-ETAN). These amines are not classified in the literature analysis of amine properties (16), although aniline and pyridine were studied by statistical analysis of their solvent properties and classified in the same sector (16). By analogy, we hypothesize that these model aromatic amines should be classified in the second sector. Thus, they may aid in an understanding of the specific role of the aromatic ring and the effect of an alkyl substituent. 

With the exception of intramolecular amination reactions, all of the early aryl halide aminations were catalyzed by palladium complexes containing the sterically hindered P(o-tol)3. In papers published back-to-back in 1996, amination chemistry catalyzed by palladium complexes of DPPF and BINAP was reported.36,37 These catalysts allowed for the coupling of aryl bromides and iodides with primary alkyl amines, cyclic secondary amines, and anilines. 

Complexation of [Cp IrCl2]2 with iV-heterocyclic carbenes has led to complexes such as 25, developed by Peris and coworkers [107, 108], and 133, developed by Crabtree and coworkers [12]. Complex 24 is activated by the addition of silver triflate and is effective for the iV-alkylation of amines with alcohols and for the iV-alkylation of anilines with primary amines. Complex 25 has also been shown to couple benzyl alcohol 15 with a range of alcohols, including ethanol 134, to give ether products such as ether 135 (Scheme 31). Complex 133 was an active hydrogen transfer catalyst for the reduction of ketones and imines, using 2-propanol as the hydrogen source. It was also an effective catalyst for the iV-alkylation of amines... 

The phosphate method has not been synthetically useful for alkylation of anilines of low basicity such as -nitro- or p-trifluoroaniline. Only monoalkylation occurs in introducing branched-chain alkyl groups such as isopropyl. Use of this method for alkylation of aliphatic amines has not been reported. 

The Zincke reaction is an overall amine exchange process that converts N- 2,A-dinitrophenyl)pyridinium salts, known as Zincke salts, to A -aryl or A -alkyl pyridiniums upon treatment with the appropriate aniline or alkyl amine. 

Aromatic amines (anilines) may become activated in vivo to form reactive amines. These are nucleophiles and may attack DNA, forming covalent modifications. Aromatic nitro compounds can be metabolised to also form reactive amines. A-nitroso compounds result in the alkylation of oxygen sites in DNA bases (0-6 in guanine and 0-4 in thymidine) [8,10]. 

The N-alkylation of amines with alcohols [63] can also be carried out with Ir catalysts through a similar domino sequence reaction. In this case, the aldehyde/ketone resulting from oxidation is condensed with an amine to the corresponding imine, which is hydrogenated to the alkylated amine [63]. By way of example, the reaction of benzyl alcohol with aniline in toluene afforded benzylaniline in a 88% isolated yield by using catalytic amounts of [ lr(/z-Cl)Cp Cl 2]/K2C03. 

The increasing industrial demand for alkylated aromatic amines initiated research to develop heterogeneous catalytic process for the alkylation of aniline and alkyl anilines. 

The procedure has also been applied for the hydroxylation of aromatic amines. Aniline and its /V-alkyl-substimted derivatives show similar behavior under similar conditions to afford the meta-substi tuted aminophenols as the major hydroxylated product.627 Product formation was interpreted by the attack of protonated hydrogen peroxide on the anilinium ion protected by /V-protonation from oxidation or degradation. Indoles, indolines, and tetrahydroquinoline have also been successfully hydroxylated with H202 in HF-SbF5 with the hydroxyl group meta to the nitrogen function.559,628 Hydroxylation of tryptophane and tryptamine derivatives affords pretonine and serotonine derivatives in 42% and 38% yields, respectively.629... 

The use of alkenyl boronic acid derivatives 50, which are readily prepared via hydroboration or bromoboration of alkynes, affords the corresponding p,y-unsaturated amino acids (e.g. 52-57) in a geometrically pure form [34], A variety of amines 48, including primary and secondary amines, anilines, amino alcohols and hydroxylamines can effectively participate in this process, while the alkenyl boronic acid can contain alkyl, aryl or bromo-substituents. Although the alkenyl amino acid side chain is introduced through the boronic acid component, the use of more substituted a-keto acids 49 allows the simultaneous incorporation of an additional a-substituent (e.g. 57). 

The extent to which secondary and tertiary amines are formed by reductive alkylation is controlled to some degree by the steric bulk of the amine and the carbonyl compound. The more hindered the system, the higher the temperature and hydrogen pressure needed to affect the reaction. While the reductive alkylation of secondary aliphatic amines with formaldehyde takes place under mild conditions (Eqn.l9.52X N,N-dimethylaniline was prepared by reductive alkylation over palladium at 120°C and 15 atmospheres pressure (Eqn. 19.53). 153 54 Reductive alkylation of aniline with acetone over palladium gave a 67% yield of the monoalkylaniline at 100°C and 40 atmospheres pressure but secondary amine formation using the more sterically accessible ketones, 2-tetralone or 2-indanone, took place at room temperature and 4 atmospheres pressure (Eqn. 19.54). 55 Palladium was the preferred catalyst in these reactions since with platinum or rhodium ring hydrogenation was also observed. 54,155... 

Onaka and coworkers have reported highly selective V-monoalkylation of aniline and its derivatives over alkali cation exchanged X- and Y-type zeolites. The intrinsic pore structures of X and Y zeolites are assumed to be responsible for the high selectivity. Linde 3A zeolites cannot promote the alkylation of aniline because of their smaller pore structure (Scheme 3). Aniline derivatives having strong electron-withdrawing substituents, such as p-nitroaniline, which is otherwise hardly alkylated even in the presence of KOH, can be successfully alkylated in benzene. Celite coated with KF is also effective for the alkylation of amines. - ... 

---