3-chloro-l-phenyl

I.3.4.2.6. Compounds with Unusual Double Bonds 1,3-Dipolar cycloaddition of l-chloro-2-phenyl-2-trimetkylsilyl-l-phosphaethene with nitrile oxides, followed by elimination of Me SiCl, results in 3,5-diphenyl-l,4,2-oxaphosphazole 190 (356). Chromium, molybdenum, and tungsten pentacarbonyls of 3,5-diphenyl-).3-phosphinins react with nitrile oxides to give the corresponding 1,3-dipolar cycloadducts, at the P = C bond, see 191 (Ar = Ph, Mes) (357). 

The distinct dipolarophilic reactivity of the phosphaalkenes can be demonstrated, among others, with the l-chloro-2-phenyl-2-trimeth-ylsilyl-l-phosphaethene. It reacts at once with diazoalkanes even at room temperature in a [3 + 2] cycloaddition. The expected primary products of addition aromatize, spontaneously eliminating trimeth-ylchlorosilane, to the l//-l,2,4-diazaphospholes, showing the triply... 

The reaction of l-chloro-2-phenyl-2-trimethylsilylphosphaethene 1 with a-pyrones 2 yields the A3-phosphinines 4a-e. With cyclopenta-dienones 3 the phosphinines 4f,g are obtained [Eq. (30)]. [The reaction proceeds via the 2-phenyl-l-phosphaethine that is formed under these reaction conditions ([Pg.278]

Seyferth ef al." generated chlorocarbene from /i-butyllithium and methylene chloride in the presence of triphenylphosphine to produce triphenylphosphine chloromethyl-enc, which reacts with acetophenone to give a mixture of W.v- and rran.v-l-chloro-2-phenyl-l-prupene (2). 

Starting with 2-bromo-l-chloro-2-phenylacetaldehyde (4-toluene)sulfonylhydra-zone (2.288) (l-chloro-2-phenylethenyl)(4-toluenesulfonyl)diazene (2.289) was obtained with triethylamine in ether. A solution of the diazene in methylene chloride becomes greenish after addition of antimony pentachloride at -30°C. Above — 20°C N2 is evolved. At — 70°C, however, a red solution is formed. The latter develops N2 even at — 60 °C. The red solution corresponds to the l-chloro-2-phenyl-ethenediazonium ion 2.290 (2-111). The structure of 2-phenylethynediazonium ion (2.291) can be attributed to the compound in the greenish solution on the basis of the IR spectrum (C = C at 2150 and 2255 cm — N N at 2295 cm ) and of the following reactions with nucleophiles. 

Chloro-3-(2-phenyl-4E -l-benzopyran-4-yHdene)ethyHdene)-1-cyclohexen-l-yl)-2-phenyl-1-benzopyryHumperchlorate. 

Another example of the analogy between pyrazole and chlorine is provided by the alkaline cleavage of l-(2,4-dinitrophenyl)pyrazoles. As occurs with l-chloro-2,4-dinitrobenzene, the phenyl substituent bond is broken with concomitant formation of 2,4-dinitrophenol and chlorine or pyrazole anions, respectively (66AHC(6)347). Heterocyclization of iV-arylpyrazoles involving a nitrene has already been discussed (Section 4.04.2.1.8(i)). Another example, related to the Pschorr reaction, is the photochemical cyclization of (515) to (516) (80CJC1880). An unusual transfer of chlorine to the side-chain of a pyrazole derivative was observed when the amine (517 X = H, Y = NH2) was diazotized in hydrochloric acid and subsequently treated with copper powder (72TL3637). The product (517 X = Cl, Y = H) was isolated. 

BENZYL CHLOROMETHYL KETONE (2-Propanone, l-chloro-3-phenyl-)... 

As with the pyrroles, N-chloroamides have been widely employed in indole chlorination [66JOC2627 80H( 14)867 81JOC2054]. Chloroindolen-ines may be isolated under controlled conditions [80H( 14)867 81JOC2054], 2-Phenyl-, l-methyl-2-phenyl-and 3-methyl-2-phenyl-indoles were converted by 1-chloroisatin (NCI) into the 3-chloro derivatives... 

The synthesis of enantiomerically pure propargylic alcohols is possible using the same methodology 43b. Thus, addition of (—)-[(l-chloro-2-phenylethyl)sulfinyl]-4-methylbenzene (14) to propan-al led to a mixture of the diastereomers 15A/15B (d.r. 44 56) which are easily separated by column chromatography. After thermal elimination of the sulfinyl group the vinyl chlorides 16A/16B were obtained as a mixture of E- and Z-oleftns. Elimination of hydrogen chloride was carried out with three equivalents of butyllithium, leading to enantiomerically pure 1 -phenyl-1-pentyn-3-ol. 

Schmid and Heinola [J. Am. Chem. Soc., 90 (131), 1968] have studied the liquid phase reactions of 1-phenylpropyne (A) and 2,4-di-nitrobenzenesulfenyl chloride (B) in chloroform solution at 51° C. The primary products of the reaction are l-phenyl-t/ams-l-chloro-2-(2, 4 di-nitrophenylthio) propene (C) and 1-phenyl-tnms-2-chloro-l-(2, 4-dinitrophenylthio) propene (D). The reaction stoichiometry may be... 

Castro (1964) reported that iron(II) porphyrins in dilute aqueous solution was rapidly oxidized by DDT to form the corresponding iron(III) chloride complex (hematin) and DDE, respectively. Incubation of /5,//-DDT with hematin and ammonia gave p./Z-DDD, p./Z-DDE, bis(/5-chloro-phenyl)acetonitrile, l-chloro-2,2-bis(jD-chlorophenyl)ethylene, 4,4 -dichlorobenzophenone, and the methyl ester of bis (jo-chlorophenyl) acetic acid (Quirke et al., 1979). 

In all these reactions a by-product was obtained, i.e., 3-amino-3-phe-nylacrylonitrile (40) being formed in a relative small yield (6-10%) (Scheme 11.23). Moreover, it was also observed that the 2-chloro compound, when reacting at -33°C for a short period of time (3-4 min), gave a rather stable second product, i.e., 4-amino-l-cyano-2-phenyl-l-azabuta-diene (41). This compound could be isolated in about 50% yield when the reaction was carried out at -75°C. 

Fig. 2. Reactivity of aromatic diisocyanates 0.02 M with 2-ethyihexanol 0.4 M and diethylene glycol adipate polyester in benzene at 28°C. (A) l-Chloro-2,4-phenylene diisocyanate. (B) m-Phenylene diisocyanate. (C) p-Phenylene diisocyanate. (D) 4,4 -Methylene bis(phenyl isocyanate). (E) 2,4-Tolylene diisocyanate. (F) Tolylene diisocyanate (60%, 2,4-isomer, 40% 2,6-isomer). (G) 2,6-Tolylene diisocyanate. (H) 3,3 -Dimethyl-4,4 -biphenylene diisocyanate (0.002 M) in 0.04 M 2-ethylhexanol. (I) 4,4 -Methylene bis(2-methylphenyl isocyanate). (J) 3,3 -Dimethoxy-4,4 -biphenylene diisocyanate. (K) 2,2,5,5 -Tetramethyl-4,4 -biphenylene diisocyanate. (L) 80% 2,4- and 20% 2,6-isomer of tolylene diisocyanate with diethylene glycol adipate polyester (hydroxyl No. 57, acid No. 1.6, and average molecular weight 1900). Reprinted from M. E. Bailey, V. Kirss, and R. G. Spaunburgh, Ind. Eng. Chem. 48, 794 (1956). (Copyright 1956 by the American Chemical Society. Reprinted by permission of the copyright owner.)...

Nucleophilic displacement of 2-chloro-3-phenylquinoxaline with methylamine at 100°-150° and with sodium phenoxide in excess of phenol of 100° gives the expected 2-methylamino- and 2-phenoxy-3-phenylquinoxalines.155 2-Chloroquinoxaline and its 3-phenyl derivative undergo ring closure with aminoacetaldehyde dimethylacetal to an imidazo[l,2-a]quinoxaline.136 Nucleophilic substitution of 2-chloro-quinoxaline with hydroxide ion in water is accelerated by cationic micelles and retarded by anionic micelles. These results were correlated with reactions of l-chloro-2,4-dinitrobenzene, and the characteristics of their transition states were discussed.137... 

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