Alkylative amination

Review Comprehensive Organic Synthesis, Eds. B. M. Trost and I. Fleming, Pergamon, Oxford (1991), Vol 1, Part 1.12, p 355 

Harada, The Chemistry of the Carbon-Nitrogen Double Bond, Ed. S. Patai, Interscience, New York (1970) 

Houben-Weyl, Methods of Organic Chemistry, 4th ed, Vol E21b, G. Thieme, Stuttgart (1995), 

RLi (R = alkyl, aryl, vinylic), sparteine or bis(oxazolines) (chiral) 

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The examples in the preceding section, of the flotation of lead and copper ores by xanthates, was one in which chemical forces predominated in the adsorption of the collector. Flotation processes have been applied to a number of other minerals that are either ionic in type, such as potassium chloride, or are insoluble oxides such as quartz and iron oxide, or ink pigments [needed to be removed in waste paper processing [92]]. In the case of quartz, surfactants such as alkyl amines are used, and the situation is complicated by micelle formation (see next section), which can also occur in the adsorbed layer [93, 94]. 

Once amines that also cany heteroatoms were included in the study, a dataset of 80 proton affinities was obtained. For those alkyl amines the inductive effect as quantified by residual electronegativity had also to be taken into account, A simple... 

Figure 7-7. Equations for the calculation of proton affinities (PA) of simple alkyl amines and of heteroatom-substituted alkyl amines.

Semipermanent hair color products are formulated at an alkaline pH, usually between 8.5 and 10. At this pH the cuticle of the hair lifts away from the hair a Httie, allowing for easier penetration of dye. An alkyl amine buffered with an organic acid normally is used to obtain the desired pH. The formulations contain a mixture of solvents and surfactants to solubilize the dyes and a thickening agent is added so that the product stays on the hair without mnning or dripping. A 20—30 min appHcation time is normal for this type of product. A representative formula for a semipermanent dye product is given in Table 7. 

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). 

Wetting times of /V,/V-dimethy1-/ -alkyl amine oxides as a function of the alkyl chain length show a minimum with dimethyl dodecyl amine oxide (Table 3). Foam generation of dimethyl-/ -alkylamine oxides solutions show a maximum when the alkyl group contains 14 carbons. 

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. 

Ethoxylation of alkyl amine ethoxylates is an economical route to obtain the variety of properties required by numerous and sometimes smaH-volume industrial uses of cationic surfactants. Commercial amine ethoxylates shown in Tables 27 and 28 are derived from linear alkyl amines, ahphatic /-alkyl amines, and rosin (dehydroabietyl) amines. Despite the variety of chemical stmctures, the amine ethoxylates tend to have similar properties. In general, they are yellow or amber Hquids or yellowish low melting soHds. Specific gravity at room temperature ranges from 0.9 to 1.15, and they are soluble in acidic media. Higher ethoxylation promotes solubiUty in neutral and alkaline media. The lower ethoxylates form insoluble salts with fatty acids and other anionic surfactants. Salts of higher ethoxylates are soluble, however. Oil solubiUty decreases with increasing ethylene oxide content but many ethoxylates with a fairly even hydrophilic—hydrophobic balance show appreciable oil solubiUty and are used as solutes in the oil phase. 

For extraction of uranium from sulfate leach Hquors, alkyl phosphoric acids, alkyl phosphates, and secondary and tertiary alkyl amines are used in an inert diluent such as kerosene. The formation of a third phase is suppressed by addition of modifiers such as long-chain alcohols or neutral phosphate esters. Such compounds also increase the solubihty of the amine salt in the diluent and improve phase separation. 

For solvent extraction of pentavalent vanadium as a decavanadate anion, the leach solution is acidified to ca pH 3 by addition of sulfuric acid. Vanadium is extracted in about four countercurrent mixer—settler stages by a 3—5 wt % solution of a tertiary alkyl amine in kerosene. The organic solvent is stripped by a soda-ash or ammonium hydroxide solution, and addition of ammoniacal salts to the rich vanadium strip Hquor yields ammonium metavanadate. A small part of the metavanadate is marketed in that form and some is decomposed at a carefully controlled low temperature to make air-dried or fine granular pentoxide, but most is converted to fused pentoxide by thermal decomposition at ca 450°C, melting at 900°C, then chilling and flaking. 

Commercial Antioxidants Table 4 includes the main classes of antioxidants sold in the United States and the suppHer s suggested apphcations. Some of these are mixtures rather than single substrates. This is especially tme of alkylated amines and alkylated phenols. The extent of alkylation and the olefins used for alkylation can vary among manufacturers. Table 4 is not a complete listing of available antioxidants in the United States. 

Verapamil. Verapamil hydrochloride is a pbenyl alkyl amine and is considered the prototype of the Class I calcium channel blockers. Verapamil is also a potent inhibitor of coronary artery spasm and is useful in Prinzmetal s angina and in unstable angina at rest. Verapamil produces negative chronotropic and inotropic effects. These two actions reduce myocardial oxygen consumption and probably account for the effectiveness of verapamil in chronic stable effort angina (98,99). Moreover, verapamil is an effective antihypertensive agent. 

A variant of the H2/NH2 chemical exchange process uses alkyl amines in place of ammonia. Hydrogen exchange catalyzed by NH2 is generaHy faster using alkyl amines than ammonia, and a dual-temperature flow sheet for a H2/CH2NH2 process has been developed (69). 

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. 

Amines or amides Alkyl amines (iindecyloctyl and diamyl methyl amine) polyamides (acyl derivatives of piperazine) Boiler foam sewage foam fermentation dye baths... 

BAYLIS - HILLMAN Vinyl alkylation Amine catalyzed converelon of acrylates to a-(hydroxyalkyl) acrylates or of vinyl ketones to a-(hydroxyalkyO vinyl ketones. 

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. 

One of the best leaving groups is molecular nitrogen in alkyl diazonium ions. Diazonium ions are generated by nitrosation of primaiy amines. The diazonium ions generated from alkyl amines are veiy unstable and immediately decompose with loss of nitrogen. 

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... 

Air Products Chemicals Alkyl Amines Chemicals (India) Ashland Chemical Atofina (France)... 

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