Dimethyl- -amine

We chose benzyli dene acetone (4.39, Scheme 4.11) as a model dienophile for our studies. The uncatalysed Diels-Alder reaction of this compound with cyclopentadiene is slow, justifying a catalytic approach. Reaction of 4.39 with paraformaldehyde and dimethyl amine under acidic conditions in an aqueous ethanol solution, following a literature procedure, produced the HCl salt of 4.42 (Scheme 4.11). The dienophile was liberated in situ by adding one equivalent of base. 

Under appropriate conditions 2-amino-4-alkylthiazoles are alkylated in the 5-position 2-acetylamino-4-methylthiazole reacts with dimethyl-amine and formaldehyde to afford the corresponding Mannich base (113) (372). 2-Amino-4-methyl-thiazole is alkylated in the 5-position by heat-... 

Fig. 37. Resist images obtained with a cross-linking monocomponent TSI resist (PHOST polymer), cross-linked by photo-oxidation using light at 193-nm wavelength. After exposure, the film was treated with a vapor of dimethyl silyl dimethyl amine and then plasma developed using O2—RIE (122).

Until 1990 the EPA maintained a Hst of chemicals suitable for potable water treatment ia the United States. Siace then the entire question of certification and standards has been turned over to a group of organi2ations headed by the National Sanitation Eoundation, which has issued voluntary standards. As of January 1992, standards had been issued for most of the principal inorganic products, but only for two polymers, poly(DADMAC) and Epi-DMA (epichl orohydrin dimethyl amine) polymers (78). Certifications for commercial products meeting specified standards are issued by the National Sanitation Eoundation, Underwriter Laboratories, and Risk Eocus/Versar (79). 

Fuactioaalizatioa is completed by aminating the chloromethylated copolymer with either primary or secoadary amines. Dimethyl amine [124 0-3] (6) is geaerally preferred, especially ia the syathesis of the macroporous anion exchangers. 

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. 

FiaaHy, a-olefias find their way iato the surfactant and disiafectant market through conversion, first to alkyl dimethyl amine, then to benzyl chloride quats (BAUMAC) and amine oxides. The former are used broadly as disiafectants, often ia combination with cleaning products. The latter is a direct active ia consumer and iadustrial cleaning products. 

Bisphenol A diglycidyl ether [1675-54-3] reacts readily with methacrylic acid [71-49-4] in the presence of benzyl dimethyl amine catalyst to produce bisphenol epoxy dimethacrylate resins known commercially as vinyl esters. The resins display beneficial tensile properties that provide enhanced stmctural performance, especially in filament-wound glass-reinforced composites. The resins can be modified extensively to alter properties by extending the diepoxide with bisphenol A, phenol novolak, or carboxyl-terrninated mbbers. 

Linear alpha-olefins are the source of the largest volume of ahphatic amine oxides. The olefin reacts with hydrogen bromide in the presence of peroxide catalyst, to yield primary alkyl bromide, which then reacts with dimethylamine to yield the corresponding alkyl dimethyl amine. Fatty alcohols and fatty acids are also used to produce amine oxides (Fig. 1). 

AHphatic amine oxides such as alkyl dimethyl amine oxides and aLkylbis(2-hydroxylethyl)amiae oxides range from practically nontoxic to slightly toxic (79). Reported LD qS range from 1.77 g/kg to 6.50 g/kg. The commercial concentrated products are primary skin and eye irritants. At concentrations of 2%, these products may be considered as nonirritating to the skin or eye. 

Dimethyl amine borane [74-94-2] important as a reducing agent in electroless plating (qv) (8), can be synthesized as shown in equation 2 (9). 

Nearly all uses and appHcations of benzyl chloride are related to reactions of the active haUde substituent. More than two-thirds of benzyl chloride produced is used in the manufacture of benzyl butyl-phthalate, a plasticizer used extensively in vinyl flooring and other flexible poly(vinyl chloride) uses such as food packaging. Other significant uses are the manufacture of benzyl alcohol [100-51-6] and of benzyl chloride-derived quaternary ammonium compounds, each of which consumes more than 10% of the benzyl chloride produced. Smaller volume uses include the manufacture of benzyl cyanide [140-29-4], benzyl esters such as benzyl acetate [140-11-4], butyrate, cinnamate, and saUcylate, benzylamine [100-46-9], and benzyl dimethyl amine [103-83-8], and -benzylphenol [101-53-1]. In the dye industry benzyl chloride is used as an intermediate in the manufacture of triphenylmethane dyes (qv). First generation derivatives of benzyl chloride are processed further to pharmaceutical, perfume, and flavor products. 

Substituted methyl- or dimethyl amines are prepared by treating the appropriate primary or secondary amine with formaldehyde in the presence of hydrogenation catalysts (22,23). 

An important extension of these reactions is the Mannich reaction, in which aminomethyl-ation is achieved by the combination of formaldehyde, a secondary amine and acetic acid (Scheme 24). The intermediate immonium ion generated from formaldehyde, dimethyl-amine and acetic acid is not sufficiently reactive to aminomethylate furan, but it will form substitution products with alkylfurans. The Mannich reaction appears to be still more limited in its application to thiophene chemistry, although 2-aminomethylthiophene has been prepared by reaction of thiophene with formaldehyde and ammonium chloride. The use of A,iV-dimethyf (methylene) ammonium chloride (Me2N=CH2 CF) has been recommended for the iV,iV-dimethylaminomethylation of thiophenes (83S73). 

N-(Thexyl dimethylsilyl)dimethylamine (N-[2,3-dimethyl-2-butyl]dimethylsilyl dimethyl-amine) [81484-86-8] M 187.4, b 156-160°/720mm. Dissolve in hexane, filter, evaporate and distil. Colourless oil extremely sensitive to humidity. It is best to store small quatities in sealed ampoules after distillation. For estimation of purity crush an ampoule in excess O.IN HCl and titrate the excess acid with O.IM NaOH using methyl red as indicator. [Helv Chim Acta 67 2128 1984.]... 

An indole protected by a Mannich reaction with formaldehyde and dimethyl-amine is stable to lithiation. The protective group is removed with NaBH4 (EtOH, THE, reflux). The related piperidine analogue has been used similarly for the protection of a triazole. ... 

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