Tertiary amines, derivatives preparation

In other investigations by the author [2,3] additional positive resists compositions were prepared containing either imidazole, (11), or tertiary amine derivatives, (III), respectively, and then blended with the select copolymer, (IV), as illustrated. 

Preparative Methods the title reagent is prepared by the treatment of (IR, 25)-(—)-norephedrine with 1,4-dibromo-butane and NaHCOs in toluene. This approach can be modified to form a wide variety of cyclic and acyclic tertiary amine derivatives. The enantiomeric reagent has also been formed from (+)-norephedrine. 

Feng and Wilson (243) prepared some tertiary amines derived from ephedrine the quaternary ammonium halides of ephedrine have been described by Feng (244). 

The workhorse amphoteric surfactants are the alkyl- and alkylamidopropyl betaines, containing C8-C18 linear chain distributions that are derived from coconut or palm kernel oil, or ethylene-based alpha olefins. The alkyl betaines are prepared from ADMA feedstocks that are typically derived from alpha olefins and dimethyl amine throngh hydrohalogenation and alkylation reaction steps. The alkylamidopropyl betaines are based on tertiary amines derived from whole triglycerides or their fractionated derivative fatty acids or methyl esters reacted with DMAPA. 

Isoindoles and isoindolines have been prepared from tertiary amines derived from 2-chlorobenzylamine, via aryne intermediates. ... 

The present invention relates to novel tertiary amines derived from bisphenols, diepoxides and aromatic secondary amines, to a process for their preparation and to their use as hardening accelerators for ethylenically unsaturated cold hardenable acrylic and polyester resins. 

Secondary and tertiary amines are not generally prepared in the laboratory. On the technical scale methylaniline is prepared by heating a mixture of aniline hydrochloride (55 parts) and methyl alcohol (16 parts) at 120° in an autoclave. For dimethylaniline, aniline and methyl alcohol are mixed in the proportion of 80 78, 8 parts of concentrated sulphuric acid are added and the mixture heated in an autoclave at 230-235° and a pressure of 25-30 atmospheres. Ethyl- and diethyl-anihne are prepared similarly. One method of isolating pure methyl- or ethyl-aniline from the commercial product consists in converting it into the Y-nitroso derivative with nitrous acid, followed by reduction of the nitroso compound with tin and hydrochloric acid ... 

Hinsberg procedure for the separation of primary, secondary and tertiary amines is given under (viii) above, and this method may be used. The following experimental details may, however, be found useful for the preparation of derivatives of primary and secondary amines. 

A number of less hindered monoalkylboranes is available by indirect methods, eg, by treatment of a thexylborane—amine complex with an olefin (69), the reduction of monohalogenoboranes or esters of boronic acids with metal hydrides (70—72), the redistribution of dialkylboranes with borane (64) or the displacement of an alkene from a dialkylborane by the addition of a tertiary amine (73). To avoid redistribution, monoalkylboranes are best used /V situ or freshly prepared. However, they can be stored as monoalkylborohydrides or complexes with tertiary amines. The free monoalkylboranes can be hberated from these derivatives when required (69,74—76). Methylborane, a remarkably unhindered monoalkylborane, exhibits extraordinary hydroboration characteristics. It hydroborates hindered and even unhindered olefins to give sequentially alkylmethyl- and dialkylmethylboranes (77—80). 

This reaction can also be utili2ed to prepare functionali2ed initiators by reaction of butyUithium with a substituted 1,1-diphenylethylene derivative. For example, polymers end functionali2ed with primary amine, tertiary amine, phenol, and bis(phenol) groups have been prepared in essentiaUy quantitative yield by using the reaction of butyUithium with the corresponding substituted (or protected) 1,1-diphenylethylene (87). 

Acetoiicetyliition Reactions. The best known and commercially most important reaction of diketene is the aceto acetylation of nucleophiles to give derivatives of acetoacetic acid (Fig. 2) (1,5,6). A wide variety of substances with acidic hydrogens can be acetoacetylated. This includes alcohols, amines, phenols, thiols, carboxyHc acids, amides, ureas, thioureas, urethanes, and sulfonamides. Where more than one functional group is present, ring closure often follows aceto acetylation, giving access to a variety of heterocycHc compounds. These reactions often require catalysts in the form of tertiary amines, acids, and mercury salts. Acetoacetate esters and acetoacetamides are the most important industrial intermediates prepared from diketene. 

Cationic Starches. The two general categories of commercial cationic starches are tertiary and quaternary aminoalkyl ethers. Tertiary aminoalkyl ethers are prepared by treating an alkaline starch dispersion with a tertiary amine containing a P-halogenated alkyl, 3-chloto-2-hydtoxyptopyl radical, or a 2,3-epoxypropyl group. Under these reaction conditions, starch ethers are formed that contain tertiary amine free bases. Treatment with acid easily produces the cationic form. Amines used in this reaction include 2-dimethylaminoethyl chloride, 2-diethylaminoethyl chloride, and A/-(2,3-epoxypropyl) diethylamine. Commercial preparation of low DS derivatives employ reaction times of 6—12 h at 40—45°C for complete reaction. The final product is filtered, washed, and dried. 

The reaction between epoxides and ammonia is a general and useful method for the preparation of P-hydroxyamines. " Ammonia gives largely the primary amine, but also some secondary and tertiary amines. The useful solvents, the ethanolamines, are prepared by this reaction. For another way of accomplishing this conversion, see 10-54. The reaction can be catalyzed with Yb(OTf)3 and in the presence of a-BINOL is l,l -bi-2-naphthol derivative gives amino alcohols with high asymmetric induction. A variation used Yb(OTf)3 at lOkbar or at ambient pressure. Lithium triflate can also be used. Primary and secondary amines give, respectively, secondary and tertiary amines, for example. 

Suitable reagents for derivatizing specific functional groups are summarized in Table 8.21. Many of the reactions and reagents are the familiar ones used in qualitative analysis for the characterization of organic compounds by physical means. Alcohols are converted to esters by reaction with an acid chloride in the presence of a base catalyst (e.g., pyridine, tertiary amine, etc). If the alcohol is to be recovered after the separation, then a derivative which is fairly easy to hydrolyze, such as p-nltrophenylcarbonate, is convenient. If the sample contains labile groups, phenylurethane derivatives can be prepared under very mild reaction conditions. Alcohols in aqueous solution can be derivatized with 3,5-dinitrobenzoyl chloride. 

The nitrogen atom in quinolizidine derivatives behaves as a tertiary amine and hence it can undergo quaternization by reaction with alkyl halides. For instance, berberine derivative 101 was transformed into 102 by treatment with 3-iodopropanol followed by anion exchange. Compound 102 was then transformed into intermediate 103, which was employed as a precursor for the the preparation of bis-ammonium salt 104 (Scheme 10). This compound showed ultrashort curare-like activity in rhesus monkeys <2001JOC3495>. 

Enantioselective Diels-Alder reactions proceed smoothly in the presence of a chiral Sc catalyst, prepared in situ from Sc(OTf)3, R)- I )-l,l -bi-2-napluhol [(R)-BINOL], and a tertiary amine in dichloromethane.58 The catalyst is also effective in Diels-Alder reactions of an acrylic acid derivative with dienes (Scheme 14). 

Figure 1.8 Derivatives of amines can be prepared from acylating or alkylating agents to give amide, secondary amine, or tertiary amine bonds.

The above sequence mimics the proposed biosynthesis of Ervatamia alkaloids and in this context Thai and Mansuy (190) set out to determine whether an enzyme preparation would be able to promote the same transformation. By incubation of dregamine hydrochloride with a suspension of liver microsomes from a rat pretreated with phenobarbital (as a good inducer of P-450 cytochromes) in the presence of NADPH and 02, 20-epiervatamine (45) was formed together with the major metabolite Nl -demethyldregamine. It is well known that microsomal reaction on tertiary amines results in Af-oxide formation or N-deal-kylation. Thus it is likely that 45 was derived either from a rearrangement of dregamine JV4-oxide, catalyzed by the iron cytochrome P-450 or from one-electron oxidation of 30. 

In the case of quaternary derivatives made from the non-planar aliphatic amines 7.64, 7.65 and 7.66, steric strains further destabilise the C-N+ bond so that reaction with cellulose occurs under alkaline conditions at 30 °C, whereas temperatures of about 40-50 °C are required for the pyridinium derivatives 7.67. The quaternisation approach appeared to offer the opportunity to prepare dyes yielding reactivity levels intermediate between those of aminochloro- and dichlorotriazine dyes without loss of the desirable stability of the dye-fibre bond to acidic conditions that is characteristic of aminohalotriazine dyes. Unfortunately, this ideal was not attainable because of the objectionable odours of the tertiary amines liberated by the fixation reaction and the sensitivity of the reactivity behaviour of the quaternised derivatives to the nature of the chromogen attached to the triazine ring, making it difficult to select compatible combinations of dyes. 

A second method of activating the acid for esterification (see Section 7.6) is as the mixed anhydride. The mixed-anhydride reaction had been employed decades ago for preparing activated esters. However, it was never adopted because of its unreliability and the modest yields obtained. The method was fine-tuned (Figure 7.12), after reliable information on the properties of mixed anhydrides was acquired (see Section 2.8). Tertiary amine is required for esterification of the mixed anhydride to occur. The method is generally applicable, except for derivatives of asparagine, glutamine, and serine with unprotected side chains. The base also prevents decomposition that occurs when the activated derivative is a Boc-amino acid (see... 

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