Alkylations aminoalkylation

The addition of compounds of type 3 to C=N double bond systems leads to O-alkyl(aminoalkyl) O-silylphosphonates 9. Monoalkyl esters of aminoalkyl phosphonous acids 10 are formed in excellent yield by solvolysis of 9 [3]. 

Recently, the power of solid-phase synthesis and combinatorial chemistry was employed for the synthesis of several libraries of structurally modified DFO analogs 139 (R -R = alkyl, cycloalkyl, aryl), in addition to nonamide analogs 140 (m, n, p = 1, 3, 5), C-terminal modified nonamide analogs 141 (R = alkyl, aryl, aminoalkyl, m, n, p = 1, 3, 5, a=0, 1), as well as reverse-amide analogs 142 (R -R = alkyl, aminoalkyl, car-... 

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. 

Quaternary ammonium alkyl ethers are prepared similarly an alkaline starch is reacted with a quaternary ammonium salt containing a 3-chloto-2-hydtoxyptopyl or 2,3-epoxyptopyl radical. Alternatively, such derivatives can be prepared by simple quaternization of tertiary aminoalkyl ethers by reaction with methyl iodide. Sulfonium (107) and phosphonium (108) starch salts have also been prepared and investigated. Further work has explained the synthesis of diethyl aminoethyl starch (109) as well as the production of cationic starches from the reaction of alkaline starch with... 

V-Aminoalkylation of 5/f-dibenzo[4/][l,3]diazcpin-6(7//)-ones 17 is accomplished by successive treatment with sodium amide and a (dialkylamino)alkyl chloride. Selected examples are given yields were not reported.179 ... 

In this section alkylation, Michael additions, hydroxyalkylation (reaction with carbonyl compounds), aminoalkylation, acylation and some other reactions of a-sulphinyl carbanions will be discussed. 

Diastereoselective alkylation of lactams derived from 7 -(-)-phenylglycinol is an efficient method for the preparation of various substituted piperidines <961(52)7719, 961(52)7727, 961L(37)849>. Ihe asymmetric s mthesis of a series of 2-(l-aminoalkyl)piperidines using (-)-2-cyano-6-phenyloxazolopiperidine has been described <96JOC(61)6700>. 

Table 6.23 AMINOALKYL INDOLES - N- ALKYL CHAIN SUBSTITUENTS [181]...

The addition of a-aminoalkyl cuprates to 2,3-alkadienoates leads to 3-(amino-alkyl)-3-( )-alkenoates 490 with high stereoselectivity [223]. 

Lactones and lactams have also be prepared by the carbonylation of 2-(co-hydroxy-alkyl)- and 2-(co-aminoalkyl)bromobenzenes [29] (see Section 8.3). 

An examination of some of the factors influencing the chemical and enzymatic hydrolysis of nicotinic acid esters was undertaken [45-48]. Twenty-five esters of nicotinic acid were prepared whose pro-moiety was a simple alkyl (unbranched, sec-, or /er/-alkyl), a chloroalkyl, a hydroxyalkyl, an alkoxyalkyl, a carbamoylmethyl, an aminoalkyl, a cycloalkyl, an arylalkyl, or an aryl group (Table 8.5). 

The alkylation with alcohols and amines can lead to alkyl derivatives or a-hydroxy and a-aminoalkyl derivatives according to the nature of the heteroaromatic base and the reaction conditions. The intermediate products in both cases are, however, the a-hydroxy and a-aminoalkyl dihydro derivatives, which can be aromatized by disproportionation or oxidation, while the loss of water or ammonia leads to the alkyl derivatives (Scheme 7). 

---