Styryl amine

Recently, Chen s group reported a deep blue OLED based on an asymmetric mono(styryl) amine derivative DB1 (192) as shown in Scheme 3.59. PL spectra of this deep blue dopant in toluene solution showed a peak emission of 438 nm, which is about 20 nm hypsochromic shift compared with DSA-amine symmetric dopant, due to the shorter chromophoric conjugated length of the mono(styryl) amine. OLED device based on this blue dopant achieved a very high efficiency of 5.4 cd/A, with CIE coordinates of (0.14, 0.13) [234]. 

SCHEME 3.59 An asymmetric mono(styryl) amine as a deep blue dopant material. 

We have previously reported results of the application of these procedures for the amination of poly(styryl)lithium (11). After an investigation of a variety of procedures, a 92% yield of poly(styryl)-amine was obtained using two equivalents of the amlnating reagent in a THF/Et20/hexane mixture of -78°C followed by slow warming to -15°C and quenching in methanol (eq. 2). 

A variety of procedures were utilized to analyze this reaction mixture and to characterize a,10-diaminopolystyrene. Thin layer chromatographic analysis using toluene as eluent exhibited three spots with Rf values of 0.85, 0.09, and 0.05 which corresponded to polystyrene, poly(styryl)amine and a,w-diaminopolystyrene (see Figure 1). Pure samples of each of these products were obtained by silica gel column Chromatography of the crude reaction mixture initially using toluene as eluent [for polystyrene and poly(styryl)amine] followed by a methanol/toluene mixture (5/100 v/v) for the diamine. Size-exclusion chromatography could not be used to characterize the diamine since no peak was observed for this material, apparently because of the complication of physical adsorption to the column packing material. Therefore, the dibenzoyl derivative (eq. 5) was prepared and used for most of the analytical characterizations. 

Natori et al. reported [81] the synthesis of a copolymer that consists of p-phenylene, p-phenylene vynelene, and styryl amine ... 

Epoxy, methacryloxy, vinyl, chloropropyl, amine, mercaptan, methyl, polyamlne, tri-isostearate, styryl-amine, tri-lauryl myristyl, glass resin... 

Pyridine, 4-methoxy-3-styryl-photoelectron spectroscopy, 2, 137 Pyridine, 2-methyI-alkylation, 2, 176 amination, 2, 233, 236 carboxylation, 2, 53 chlorination, 2, 201, 331 Claisen condensation, 2, 51 methiodide... 

Hydrolysis of an enamine yields a carbonyl compound and a secondary amine. Only a few rate constants are mentioned in the literature. The rate of hydrolysis of l-(jS-styryl)piperidine and l-(l-hexenyl)piperidine have been determined in 95% ethanol at 20°C 13). The values for the first-order rate constants are 4 x 10 sec and approximately 10 sec , respectively. Apart from steric effects the difference in rate may be interpreted in terms of resonance stabilization by the phenyl group on the vinyl amine structure, thus lowering the nucleophilic reactivity of the /3-carbon atom of that enamine. 

Allyl p-tolyl sulphoxide 535 reacts with sodium methoxide in methanol by initial prototropic isomerization and subsequent addition of methanol to give 536 (equation 333). Protic solvents are photochemically incorporated by the open chain olefinic bond of trans methyl )S-styryl sulphoxide 537 in a Markovnikov regiospecificity (equation 334). Mercaptanes and thiophenols add to vinyl sulphoxides in a similar manner (compare also Reference 604 and Section IV.B.3) to give fi-alkylthio(arylthio)ethyl sulphoxides 538 (equation 335). Addition of deuteriated thio-phenol (PhSD) to optically active p-tolyl vinyl sulphoxide is accompanied by a low asymmetric a-induction not exceeding 10% (equation 336) . Addition of amines to vinyl sulphoxides proceeds in the same way giving )S-aminoethyl sulphoxides in good to quantitative yields depending on the substituents at the vinyl moiety When optically active p-tolyl vinyl sulphoxides are used in this reaction, diastereoisomeric mixtures are always formed and asymmetric induction at the p- and a-carbon atoms is 80 20 (R = H, R = Me) and 1.8 1 (R = Me, R = H), respectively (equation 337) ... 

Amination (11) and solution carbonation (8) reactions were carried out as described previously. For solid-state carbonations, a benzene solution of poly(styryl)lithium was freeze-dried on the vacuum line followed by introduction of high-purity, gaseous carbon dioxide (Air Products, 99.99% pure). Analysis and characterization of polymeric amines (11) and carboxylic acids (8) were performed as described previously. Benzoyl derivatives of the aminated polystyrenes were prepared in toluene/pyridine (2/1. v/v) mixtures with benzoyl chloride (Aldrich, 99%). 

Methyl-3-phenylquinoxaline reacts with aryl aldehydes to form 2-styryl derivatives (124), but forcing conditions (reflux in oil bath for 12-15 hours) are necessary to overcome the steric effect of the 3-phenyl group.124 Direct N-amination of 2-phenylquinoxaline has been reported with O-mesitylsulfonylhydroxylamine. The reactive nitrogen is N-4, the least sterically hindered, and the product was characterized by conversion into the N-benzoylimine (125).132... 

Pyrimidin-4-amine, 5-nitro-2-styryl-reduction, 3, 88 Pyrimiidin-4-amine, 2-phenyl-hydrolysis, 3, 84 Pyrimidin-4-amine, 5-phenyl-synthesis, 3, 116 Pyrimidin-4-amine, triphenyl-synthesis, 3, 119... 

F. Dobler, on aromatio aldehydes F. Bidet, on primary amines, etc. G. Baume, and A. M. Wasilieff studied the system with methyl ether and ethyl alcohol with ammonia and C. A. Kraus and E. H. Zeitfuchs, equilibrium in liquid mixtures of ammonia and xylene. H. H. Schlubach and H. Miedel observed that ammonia or ammonium salts may act as a reducing agent on some organic compounds—phenyl-butylene, styryl methyl ketone, pyridine, and nitrobenzene, but not acetophenone, benzil, benzoin, and deoxybenzoin. A soln. of sodium in liquid ammonia is added gradually to a soln. of ammonium chloride in the same solvent in which the substance to be reduced is at least partly dissolved at —80° to —50°. If the compound under investigation is not sufficiently soluble in liquid ammonia, benzene or ether... 

Helary and Fontanille 1781 have studied the influence of the tertiary amine crown molecule tetramethyltetraazocyclotetradecane (TMTA) upon the propagation of poly(styryl)lithium in cyclohexane at 20 °C using a rapid calorimetric procedure. The complexing agent, employed at a [TMTA] [Li] ratio of unity, caused a shift of the absorption maximum from 326 to 345 nm, indicating an increase in interionic separation it was presumed that, under these conditions, there is no aggregation... 

On thermolysis, one cannot exclude the provisional disturbance of aromaticity by a reverse electronic process followed by an electrocyclic ring-closure to acylnaphthalene 225 as described for the reaction of 1-styryl-substituted 2-benzopyrylium salts 199 with secondary amines (Section III,C,4,a,iv). 

Methyl-8-formylBIPS (71, Z = O) was condensed with amines to give in 36-61% yields the 8-anils (Z = N-R) (R = benzyl and 4-X-phenyl, [X = acetyl, nitro, and methyl]), and with aldehydes to give in 62-76% yields the 8-styryl ketones (Z=CH-R ) (R = methyl, phenyl, and 2-hydroxyphenyl). The styryl ketones were shown by their NMR spectra to be the cis isomers. Of the anils, only the 4-nitrophenyl... 

Intramolecular addition of the secondary amine moiety to the styrene double bond in styryl kelobascs Ph—CH=CH—CO—CH2CH2—NH—Ar also produces piperidino derivatives. ... 

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