Aminoalkylations

Aminoalkylation of N-[pyridyl-(2)]thiazolyl-(2)-amine yields the C-5-substituted compound (208) (Scheme 131) (132. 382. 383). 

Complex cyclic compounds may be named by adding the suffix -amine or the prefix amino- (or aminoalkyl-) to the name of the parent compound. Thus three names are permissible for... 

Phosphoric acid, monoalkyl phosphates, and phosphonic acids, but not dialkyl phosphates (107), can be aminoalkylated on the oxygen (108—110). 

The reaction of thioethers with ethyleneimine in the presence of acid yields sulfonium compounds. The reaction is reversible under alkaline conditions (125). Compounds in which double-bonded sulfur can exist in tautomerism with a form having a free SH group, such as thiourea (126,127), thiocarboxyhc acids (128), and thiophosphates (129), react to give aminoaLkylated products. The P-aminoethyl thiocarboxylate rearranges to give the amide. 

Reaction with Selenium Nucleophiles. The reactions of selenium nucleophiles are similar to those of the sulfur nucleophiles selenophosphates can be aminoaLkylated (135). A dihydroselenazine has been obtained by reaction of diethyl ketone, elementary selenium, and ethyleneimine (136). 

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... 

Benzo[b]thiophene-3-acetic acid, aminoalkyl-synthesis, 4, 879... 

When reacted with dimethyl acetylenedicarboxylate, the amines produced ben-zotriazolylaminobutendioates 188 accompanied by A-benzotriazolyl substituted 2-pyridones only in the case of 5-amino-2-methyl-2//-benzotriazole, the triazolo-9,10-dihydrobenzo[d]azepine and an unusual cyclization product, triazolo-2-oxindole (convertible into 2-methyltriazolo[4,5-/]carbostyril-9-carboxylate) were formed. The quinolones 189 were aromatized to chloroesters 190 these in turn were hydrolyzed to chloroacids 191 and decarboxylated to 9-chlorotriazolo[4, 5-/]quinolines 192 (Scheme 58) (93H259). The chlorine atom could be replaced with 17 various secondary amines to give the corresponding 9-aminoalkyl(aryl) derivatives 193, some of which exhibit both cell selectivity and tumor growth inhibition activity at concentrations between 10 and 10 " M (95FA47). 

Thus, deprotonation of the aminium radical from a secondary or primary amine will at last form an amino radical instead of an aminoalkyl radical and a CH2CH2CN radical. This amino radical will then serve as one of the active species for the initiation of polymerization. 

Acid-catalyzed aminomethylations of 5W-dibenz[/>,/]azepine (5) in ethanolic solution with formaldehyde and a secondary amine yield the 2-(aminoalkyl) derivatives, e.g. 6.186 If acetic acid is used as the solvent, however, then 2,8-bis(aminoaIkylatiou), e.g. formation of 7, results. 

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 ... 

Most other hydrophilic monomers inclined to radical polymerization (methacrylamide, methacrylic acid, N-vinylpyrrolidone, aminoalkyl and hydroxyalkyl methacrylates) do not form hydrogels with high swellability in water. 

Jervis used porous silica coated with chemisorbed polyacrylhydrazide for immobilization of adenosine monophosphate (AMP) [117]. After periodate oxidation of its ribose residue the ligand was coupled to the carrier and used for isolation of lactate dehydrogenase from rabbit muscle. The specific capacity was 2 mg of protein/g adsorbent with a ligand content of 10 pmol/g, whereas recovery of enzymatic activity after elution was 85%. Hipwell et al. [118] found that for effective binding of lactate dehydrogenases on AMP-o-aminoalkyl-Sepharose the spacer arm length required at least 4 methylene links. Apparently, a macromolecule of polyacrylhydrazide acts itself like an extended spacer arm and thus allow AMP to bind the enzyme. 

Photoredox systems involving carbonyl compounds and amines are used in many applications. Carbonyl compounds employed include benzophenone and derivatives, a-diketones [e.g. benzil, cainphoroquinone (85),2W 291 9,10-phenanthrene quinone], and xanthone and coumarin derivatives. The amines are tertiary and must have a-hydrogens [e.g. N,A7-dimethylani 1 ine, Michler s ketone (86)]. The radicals formed are an a-aminoalkyl radical and a ketyl radical. 

The reaction between the photoexcited carbonyl compound and an amine occurs with substantially greater facility than that with most other hydrogen donors. The rate constants for triplet quenching by amines show little dependence on the amine a-C-H bond strength. However, the ability of the amine to release an electron is important.- - This is in keeping with a mechanism of radical generation which involves initial electron (or charge) transfer from the amine to the photoexcited carbonyl compound. Loss of a proton from the resultant complex (exciplex) results in an a-aminoalkyl radical which initiates polymerization. The... 

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