AW-dimethylaniline

The formation of /7-nitro-AW-dimethylaniline (in addition to the expected p-nitrophenyl ether) in the reaction of nitrophenate ion with the alkoxyphosphonium salts (158) indicates the intermediacy of the relatively stable interconverting phos-phoranes (159). Loss of dimethylamide ion gives the salt (160), which subsequently undergoes SurAr reactions.142... 

C relaxation studies on AW-dimethylaniline adsorbed on Si02 gel and octadecylsilanized Si02 gel provided information on mechanisms of molecular motion of these adsorbed species.130... 

Within the area of SET-promoted di-7t-methane reactions, recent studies have shown that irradiation of 1-aza-1,4-dienes, such as 32, and the 1,4-diene 34, using AW-dimethylaniline (DMA) as electron-donor sensitizer, leads to production of the corresponding cyclopropane derivatives 33 and 35 resulting from 1-ADPM and DPM rearrangements, respectively, in reactions that take place via radical-anion intermediates (Sch. 11) [25]. 

Another instance is the benzylation of AW-dimethylanilines and derivatives upon irradiation of benzyl cyanides, which cleave via the radical anion formed by electron transfer [212]. Yet another path for the benzylation of (hetero)aromatics is the SRN1 reaction, as shown by the smooth photoassisted reaction of the enolate from ethyl phenylacetate with 2-bromopyridine (77% yield) [213]. 

Selective reduction (UAIH4, THF, at — 70°C) of 3,4-dicarbomethoxy-quinoline at low temperatures unexpectedly affords 3-formyl-4-carbometh-oxyquinoline. 2- and 4-Substituted aminoquinolines have been obtained by heating quinolones with a mixture of amine hydrochloride, phosphorus pentoxide, and AW-dimethylaniline at 250°C. In a related reaction,... 

The photosensitized dealkylation of 8a-hydroxyalkylpurines (203) on irradiation ( > 290 nm) leads to regeneration of the original purines (204) in yields of up to 100%.m Sensitizers used include carbazole and AW-dimethylaniline, and a mechanism involving electron transfer from the sensitizer to the purine has been proposed. 

Chlorocar nyl o-(diphenylphosphino)-AW-dimethylaniline iridium(i) Ir, sp 1.794(7), square planar... 

The products were sampled on-line every 15 min and analyzed by GLC by using a colutim (2mx3nun) of 10% Carbowax 20M/2% KOH on Chromosorb W-AW 80/100. The alkylated anilines were identified (HR-MS, VG AutoSpec) as being mainly N-methyl (NMA) and N,N-dimethylaniline (NNDMA) and minor amounts of N,N-dimethyltoluidines (NNDMT, p- > 0-). The conversions reported here are on a methanol free aniline basis and selectivities are expressed as the ratio of moles of a given product to the sum of moles produced (mol%). 

AW-Diethylamine-anthracene1780 and the model system AW-dimethyl-4-[3-(9-anthryl)propyl]aniline1735 have been used in an investigation of the dynamics of inter- and intra-molecular charge-transfer interactions on the picosecond timescale. In hexane solutions, it has been determined that electron transfer occurs very rapidly (10 ps) when the free anthracene (A) and dimethylaniline (DMA) are separated by 8 A or less. In the model compound, with the A and DMA separated by only ca. 4 A, it takes 900 ps to form the charge-transfer... 

AW-Diethyl-2,6-dimethylaniline (154), a highly hindered tertiary amine, has been considered. This is illustrated by the decomposition o iV-nitrosoacet-anilide (169) and benzenediazonium acetate by two competing routes to give converted into (154) in four steps. 

The reaction between benzene and AQV-dimethylaniline N -oxide in the presence of CF3SO3H gives mainly (64—76%) 4-(AW-dimethylamino)biphenyl, probably via protonation on oxygen and loss of water to the JVN-dimethyl-immonium-benzenium ion. ° Treatment of ferrocene with 2-carboxy-4,6-diphenylpyrylium perchlorate yields the 2-ferrocenylpyrylium salt with decar-boxylation. ° ... 

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