Amines products

Anyway, there have been two very hot topics in chemistry lately clay microwaves. Both have been shown to do remarkable things in preparative organic chemistry. And this article Strike has [58], has combined both to produce some stunning reductive ami-nations of ketones to final amine products. The procedure involves mixing naked ketone, the amine, some clay and some NaBH4 in a beaker and zapping it in the microwave for only a couple of minutes. That s it. The general procedure is as follows ... 

The acid-base reactions that occur after the amide bond is broken make the overall hydrolysis irreversible m both cases The amine product is protonated m acid the car boxylic acid is deprotonated m base... 

Although this reaction is useful for preparing a ammo acids (Table 22 3 fifth entry) it IS not a general method for the synthesis of amines Its major limitation is that the expected primary amine product is itself a nucleophile and competes with ammonia for the alkyl halide... 

Bromination. 1-Bromoalkanes are produced commercially by the anti-Markovnikow free-radical addition of HBr to a-olefins. These are further reacted with dimethyl amine to produce alkyldimethyl amines, which ultimately are converted to amine products for household cleaning and personal care. 

The acid and amine products of equations 3, 4, and 5 condense to form new amide end groups (eq. 6). 

Fig. 1. Amine distribution general behavior. Converted alcohol to amine product as the ammonia to alcohol ratio increases.

Company and plant location Amine products Capacity, t/yr Method... 

Cycloahphatic amine production economics are dominated by raw material charges and process equipment capital costs. Acetone (isophorone), adiponitnle, aniline, and MDA are all large-volume specification organic intermediates bordering on commodity chemicals. They are each cost-effective precursors. 

Fatty amine products are normally shipped in 55-gal (208 L), lined and unlined, steel dmms or in tank cars or tank tmcks for bulk shipments. High melting amines can be flaked and shipped in cardboard cartons or paper bags. The amines are corrosive to skin and eyes. Protective splash goggles and gloves should be worn when handling these materials. 

To analy2e fatty amines, both wet and instmmental methods of analysis are used. Wet methods routinely used are total amine value (ASTM Method D2073) combining weight or neutralization equivalent primary, secondary, and tertiary amine content (ASTM Method D2083) moisture, Kad-Fischer (ASTM Method D2072) and iodine value, measure of unsaturation (ASTM Method D2075). These provide important information on physical and chemical characteristics of the amine products used in various appHcation areas (8,76,81). In addition to the ASTM methods available, the American Oil Chemists Society has developed methods of analysis for fatty amines (82). 

Fat Tertiary Amines, Product Bulletin, CG-180R(288), Ethyl Corporation, Baton Rouge, La., Feb. 1988. 

Kemamine Patty Amines, Product Bulletin AMN 901 /Ml, Humko Sheffield Chemical, Memphis, Term., 1978. 

Transition-state stabilization in chymotrypsin also involves the side chains of the substrate. The side chain of the departing amine product forms stronger interactions with the enzyme upon formation of the tetrahedral intermediate. When the tetrahedral intermediate breaks down (Figure 16.24d and e), steric repulsion between the product amine group and the carbonyl group of the acyl-enzyme intermediate leads to departure of the amine product. 

A search has not been made for products of displacement of halogen from the benzo-ring in polyhalo compounds, but it is clear that the major mono-substitution occurs in the azine ring. For example, 2,6- and 2,7-dichloroquinoxalines give 70-80% of the 2-amination product with )S-diethylaminoethylamine (150°, 2 hr) or y-(l-piperidyl)-propylamine (220°, 2 hr). 2,3,6-Trichloroquinoxaline gives with... 

Boilers and steam systems Steel steam lines can be inhibited by the use of a volatile amine-based inhibitor such as ammonia, morpholine or cyclohexylamine introduced with the feedwater. It passes through the boiler and into the steam system, where it neutralizes the acidic conditions in pipework. The inhibitor is chemically consumed and lost by physical means. Film-forming inhibitors such as heterocyclic amines and alkyl sulphonates must be present at levels sufficient to cover the entire steel surface, otherwise localized corrosion will occur on the bare steel. Inhibitor selection must take into account the presence of other materials in the system. Some amine products cause corrosion of copper. If copper is present and at risk of corrosion it can be inhibited by the addition of benzotriazole or tolutriazole at a level appropriate to the system (see also Section 53.3.2). 

Another alternative for preparing a primary amine from an alkyl halide is the Gabriel amine synthesis, which uses a phthalimide alkylation. An imide (—CONHCO—) is similar to a /3-keto ester in that the acidic N-H hydrogen is flanked by two carbonyl groups. Thus, imides are deprotonated by such bases as KOH, and the resultant anions are readily alkylated in a reaction similar to the acetoacetic ester synthesis (Section 22.7). Basic hydrolysis of the N-alkylated imide then yields a primary amine product. The imide hydrolysis step is analogous to the hydrolysis of an amide (Section 21.7). 

The imine is reduced by NaBH4 or F /Ni to yield the amine product. 

Neutralizing capacity is not the only measure of a required amine feed rate. Once all acidic characteristics have been neutralized, amine basicity becomes the important issue because this raises the pH above the neutralization point, to a more stable and sustainable level. Consequently, in practice we are concerned with the level of amine necessary to raise the condensate pH to a noncorrosive level. This practical amine requirement is difficult to obtain from theoretical calculations because it must take account of the amine volatility, DR, and the boiler system amine recycling factor (as well as temperature). As noted earlier, the basicity of an amine has little or no relationship to its volatility or DR, so that reliable field results are probably a more important guide in assessing the suitability of an amine product than suppliers tables. 

Chloro-7-nitroquinoxaline (103, Q = Cl, R = H) gave a separable mixture of 6-nitro-3-piperidinoquinoxaline [103, Q = N(CH2)2, R = H] (product of amino-lysis) and 6-nitro-2,3-dipiperidinoquinoxaline [103, Q = R = N(CH2)s] (product of an additional amination) [excess HN(CH2)5, Et20, 20°C, <4h the amination product was least in an inert atmosphere and most in an oxygen atmosphere, inferrring an addition-oxidation mechanism]. 

The inertia of (TMS)3SiH toward azides allows this functionality to be used as a radical acceptor. An example is given in Reaction (52) where the amine product was tosylated before work-up. 

The much more reactive 2,3-dihydro-l,4-phthalazine 248, on reaction with five equivalents of benzylamine, HMDS 2, and (NH4)2S04 for 24 h at 160°C, furnishes the bis-aminated product 249 in 87% yield [27] (Scheme 4.26). 

Likewise, l-[4-methylbenzyl]-4,7-dihydroxy-l,2,3-triazolo[4,5-d]pyridazine 275 reacts with phenylhydrazine, HMDS 2, and (NH4)2S04 to give the monoamino product 276 in 60% yield [83]. Reaction of l-benzyl-3-n.-butyl-4-hydroxy-l,2,3-triazo-lo[4,5-d]-pyrimidine 277 for 8 h at 120°C with cyclopentylamine, HMDS 2, and (NH4)2S04 affords the aminated product 278 in 49% yield [84] (Scheme 4.33). 

Iron phthalocyanine is an efficient catalyst for intermolecular amination of saturated C-H bonds. With 1 mol% iron phthalocyanine and 1.5 equiv. PhlNTs, amination of benzylic, tertiary, and ally lie C-H bond have been achieved in good yields (Scheme 31). With cyclohexene as substrate, the allylic C-H bond amination product was obtained in 75% yield, and the aziridination product was found in minor amount (17% yield) [79]. 

With some secondary amines, especially morpholine, the reaction leads to a mixture of the oxidative amination product and of the hydroamination product, both corresponding to an anh-Markovnikov addition (Eq. 4.39) [166]. 

In all the above reactions, secondary amines give good yields of butenyl compounds, whereas with primary amines products of high molecular weight, i.e. containing more than 2 butadiene units per mol of amine, are also formed. The latter have been shown to be aldimine derivatives containing three C4 units [203]. 

A modification of the previous formulation uses amine products containing preferably only tertiary amino groups [1845]. These amines have favorable... 

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