4- dimethylaminophenyl

IODINE AND IODINE COMPOUNDS] (Vol 14) 17b-Hydroxy-llb-(4-dimethylaminophenyl-l)-17a-(prop-l-ynyl)-estra-4,9-diene-3-one... 

Lissamine Green B l-[bis-(4,4 -dimethylaminophenyl)methyl]-2-hydroxynapbthalene-3,6-disulfonic acid sodium salt. Acid Green 50 [3087-16-9] M 576.6, m >200°(dec). Cl... 

Ring closure of 2-chloro-l-phenethylpyridinium ion (247) (prepared in situ) to l,2-dihydro-3,4-benzoquinolizium ion involves intramolecular nucleophilic displacement of the chloro group by the phenyl 77-electrons. A related intermolecular reaction involving a more activated pyridine ring and more nucleophilic 7r-electrons is the formation of 4-( -dimethylaminophenyl)pyridine (and benzaldehyde) from dimethylaniline and 1-benzoylpyridinium chloride (cf. Section III,B,4,c). 

Methyl-6-aminobenzoselenazole when treated with 3-penten-2-one gave by a simple Doebner-Miller type reaction the 2,7,8-trimethylselenazoloquinoline 43 in 18.6% yield, that is the angular product and not the linearly annelated one was formed. Its structure was confirmed by the coupling constant in proton NMR (71JHC693). Selenazoloquinoline 43 can be converted via the 6-methylpyridium salt in the reaction with 4-dimethylaminobenzaldehyde to 2,6-dimethyl-7,9-bis(l-(4-dimethylaminophenyl)-2-ethenyl)selenazolo[5,4-/]quinolinium iodide 44 (Ar = 4-dimethylaminophenyl). This dye exhibited two absorption maxima between 500 and 600 nm (72MI2). 

Considering the fact that 3,3-bis(4-dimethylaminophenyl)phthalide (1), commonly known as Malachite Green lactone, was reported1 well over 100 years ago, it is somewhat surprising to realize that the analogous 6-dimethylaminophthalide [Crystal Violet lactone (CVL)] (2) was not described until 1945,2 and that the vast majority of references cited herein are considerably more recent. 

A different approach for the modification of the basic Malachite Green lactone structure has been the replacement of one 4-dimethylaminophenyl group by electron-rich heterocycles. The most thoroughly investigated heterocycle has been the 3-indolyl residue, which may be introduced by two different routes as shown in Scheme 7. 

Experimental Procedure19 for 3-[a-(4-dimethylaminophenyl)benzyl]indole (45). To a solution of 4-A(A7-dimethylaminobenzhydrol (0.45 g, 2 mmol) in MeOH (25 ml) under reflux, was added a solution of indole and concentrated hydrochloric acid (0.8 ml) in water (25 ml). The mixture was heated under reflux for 90 min, followed by the addition of KOH solution (5%, 30ml). After the reaction was allowed to cool, the product was isolated by filtration (0.63 g, 97%). 

Experimental Procedure19 for 4-bis(4-dimethylaminophenyl)methyl-2,6 dimethoxyphenol (55a). A mixture of syringaldehyde (5.46 g, 30 mmol, A.A-dimethylaniline (7.26 g, 60 mmol), urea (2.7 g), and concentrated sulfur ic acid (4.41 g) in isopropanol (100ml) was heated at 90°C under a nitrogen atmosphere for 24h. The reaction was cooled to room temperature and 40ml of water added followed by 50% NaOH until alkaline. The mixture was filtered and the residue washed with 200ml of cold water. The solid was recrystallized from ethanol and yielded 12.0g (97%), mp 136-138°C. 

A different approach to design a self-calibrating dye was proposed [70], in which a viscosity-sensitive molecular rotor (2-cyano-3-(4-dimethylaminophenyl) prop-2-enoic acid) was covalently linked to a reference dye, 7-methoxycoumarin-3-carboxylic acid, which exhibited no viscosity sensitivity (40, Fig. 13). A ratiometric measurement, that is, rotor emission relative to reference emission, was shown to be widely independent of dye concentration [70]. However, the design of such a ratiometric dye poses some challenges because of resonance energy transfer from... 

Zr compounds are also useful as Lewis acids for oxidation and reduction reactions. Cp2ZrH2 or Cp2Zr(0 Pr)2 catalyze the Meerwein-Ponndorf-Verley-type reduction and Oppenauer-type oxidation simultaneously in the presence of an allylic alcohol and benzaldehyde (Scheme 40).170 Zr(C)1 Bu)4 in the presence of excess l-(4-dimethylaminophenyl) ethanol is also an effective catalyst for the Meerwein-Ponndorf-Verley-type reduction.1 1 Similarly, Zr(0R)4 catalyze Oppenauer-type oxidation from benzylic alcohols to aldehydes or ketones in the presence of hydroperoxide.172,173... 

The previous extension of solvent mixtures involved solvent interfaces. This organic-water interfacial technique has been successfully extended to the synthesis of phenylacetic and phenylenediacetic acids based on the use of surface-active palla-dium-(4-dimethylaminophenyl)diphenylphosphine complex in conjunction with dode-cyl sodium sulfate to effect the carbonylation of benzyl chloride and dichloro-p-xylene in a toluene-aqueous sodium hydroxide mixture. The product yields at 60°C and 1 atm are essentially quantitative based on the substrate conversions, although carbon monoxide also undergoes a slow hydrolysis reaction along with the carbonylation reactions. The side reaction produces formic acid and is catalyzed by aqueous base but not by palladium. The phosphine ligand is stable to the carbonylation reactions and the palladium can be recovered quantitatively as a compact emulsion between the organic and aqueous phases after the reaction, but the catalytic activity of the recovered palladium is about a third of its initial activity due to product inhibition (Zhong et al., 1996). 

Reaction of 2-[(m-diethylaminophenyl)amino]pyridine (277) and 4,4 -bis(dimethylamino)benzophenone in boiling phosphoryl chloride for 3.5 h yielded 3-diethylamino-ll, 1 l-bis(4-dimethylaminophenyl)-ll//-pyrido[2,l-b]quinazoline (278) (88HCA33). 

The compound bis-(4,4 -dimethylaminophenyl)-sulfone (DMAPS) and related compounds show multiple fluorescences in polar solvents due to excited state charge transfer (Rettig and Chandross [144]). Su and Simon [84,85] have examined the intramolecular electron transfer reaction in DMAPS, in alcohol solution over the temperature range from — 50°C to + 30°C. They observe that the decay of the local excited state is nonexponential and significantly faster than the longitudinal relaxation time of the solvent. In addition, they observed that the emission spectrum of the TICT state... 

Antiprogestins, such as RU-486 (lift-hydroxy-11/3 (4 dimethylamino phenyl-1 )-17ry-(prop-l-ynyl)-estra-4.9-diene-3-one) (33) and ZK98299 1 l/J-(4-dimethylaminophenyl)-17a-hydroxy-17/j-(3-hydroxypropyl-13a-methyl-4,9-gonadien-3-one) represent a new class of drags for fertility regulation. Also, these drugs have potential applications in the treatment of uterine cancer. 

Even in such molecules with large ground state dipole moment, we observed the production of non-centrosymmetric crystal structures exhibiting SHG by introduction of asymmetric amino acid derivatives into the cyclobutenedione. (-)4-(4,-dimethylaminophenyl)-3-(2l-hydroxypropylamino) cyclobutene-1,2-dione (DAD) (3), (+)4-(4 -di-... 

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