Dialkylamino compounds

Cowley DJ, Peoples AH (1977) Rotational isomerism and dual luminescence in dipolar dialkylamino-compounds. J Chem Soc Chem Commun 352-353... 

Aminolysis of the corresponding halides is the preferred method for the synthesis of dialkylamino derivatives of boron,1 silicon,2 germanium,3 phosphorus,4 arsenic,5 and sulfur.6 (Dialkylamino) chlorosilanes are prepared stepwise by the reaction of silicon tetrachloride with dialkylamines. This method may be utilized equally well for the conversion of alkyl- or aryl-substituted halides [e.g., (CH3) SiCl4. ] or of oxide and sulfide halides (e.g., POCl3 or PSC13) to the corresponding dialkylamino compounds. 

Oxidation of 3-methoxy- or 3-phenoxy-1,2,4-triazines (228) with perbenzoic acid converted them into the appropriate 1-oxides (229) (71JOC787). Peracid treatment of 1,2,4-triazin-3-ones with an unsubstituted 5-position (84 R5 = H) gave l,2,4-triazine-3,5-diones (182) (69JHC403), while 5-substituted l,2,4-triazin-3-ones (84) afforded the appropriate 1-oxides (230) (66JOC3914). 3-Amino-l,2,4-triazines with an unsubstituted (86a) or a monosubstituted amino group (86b) were oxidized by peracids to give the 2-oxides (231), while the 3-dialkylamino compounds (86c) afforded the 1-oxides (232) (77JOC546). 

Bis-cationic metal-complex dyes are suitable for dyeing leather. Cationic monoazo dyes in which a trialkylammonium group is linked via a carboxamide group to the diazo component [116] and disazo dyes are known. The latter are prepared from dialkylamino compounds by quatemization with alkylene dibromides. They are suitable for dyeing paper [117],... 

First, intramolecular general base catalysis has been demonstrated for aliphatic and aromatic keto-carboxylates ([3]—151) (Bell and Fluendy, 1963 Harper and Bender, 1965 Bell et al., 1972 Bell and Covington, 1975), keto-dialkylamino compounds ([6] and [7]) (Coward and Bruice, 1969 Bell and Timimi, 1973) and for the anion of o-hydroxyacetophenone [8 (Bell et al.,... 

At the other extreme, the most stable derivatives of the B2X4 type appear to be the tetrakis(dialkylamino) compounds. Thus, tetrakis(dimethylamino)-diborane(4) is stable at its boiling point of 206° C 17). The compound decomposes at 300° C to form bis(dimethylamino)borane and involatile residues containing B—C bonds. It is reported that tetra(A -methylanilino)-borane(4) is pyrolyzed at 300° C by a different mechanism to yield N-methylaniline 18). 

In the case of jV,jV-dialkyl-5-phenyl-6f/-l, 3,4-thiadiazin-2-amines, the reaction stops at the stage of 1 as ring opening and formation of a carbodiimide moiety are not possible wnth the 2-(Ar,A -dialkylamino) compounds. 

Nucleophilic substitutions with alkoxides and secondary amines on halo-dialkylaminopyridazines were investigated. Alkoxides replace the 3-chlorine atom of 3,6-dichloro-4-dialkylaminopyridazines, whereas secondary amines attack the 4-chlorine.398 Both nucleophiles replace the 4-halogen atom of 3,4-dichloro-6-dialkylamino compounds and that at position 3 of 3,4-di-chloro-5-dialkylamino compounds. No selectivity was observed with the corresponding trichloro compounds.398... 

Acyloxy)dialkylboranes are best prepared from carboxylic acids with tri-alkylboranes.1,12-16 Other methods involve reactions of halodiorganobo-ranes with carboxylic acids17 or with acetic anhydride.18 Alternative syntheses from acetic anhydride using dialkyl(alkylthio)boranes or dialkylamino compounds have also been described.19... 

Triazapyrenes were aminated successfully into mono- and bis-dialkylamino compounds under mild conditions in aqueous solution with potassium hexacyanoferrateflll) as oxidant (Scheme 50) [157, 158],... 

A mixture of the substrate and 10% palladium-on-charcoal catalyst (1 1, w/w) in ethanol or aqueous ethanol is stirred in the presence of the requisite aldehyde (30— 400% excess) under hydrogen, at room temperature and at ordinary pressure, until either reduction ceases or slightly more than the theoretical amount of hydrogen is consumed (3—I6h). The mixture is then heated to boiling and filtered, the catalyst is washed with hot ethanol, and he combined filtrates are concentrated to dryness to give the dialkylamino compound with some residual aldehyde. 

Dialkylamino compounds such as 11 are formed from 2, 3 -di-0-mesyl-S -0-trityluridine on treatment with the secondary amine, reaction proceeding via the 2,2 -anhydronucleoside. The presence of the 3 -6)-me l group facilitates the caning of the anhydronucleoside by the amine, since the ampound lacldng this activation does not (q>en with dialkylamines. ... 

If such a dialkylamino compound is compared with luminol at pH 11, misleadingly low values will be obtained for the naphthalene derivative. The pH must also influence the ionisation of hydrogen peroxide which has a pK of about 11.0. 

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