Reaction with phenyl lithium

Tetrachloroselenophene undergoes a ring-opening reaction on treatment with phenyllithium initiated by nucleophilic attack on selenium. Further reaction with phenyl-lithium results in the formation of diphenyl selenide (Scheme 11) (76CS(10)133). 

Telluraxanthene was converted to 9-lithiotelluraxanthene in a reaction with phenyl lithium. The lithiotelluraxanthene and carbon dioxide reacted to produced 9-carboxytelluraxanthene2. 

By reaction with phenyl lithium, mesembrine produced phenyl-mesembrinol (XVI) which was dehydrated with thionyl chloride to a mixture of two isomeric phenylmesembrenes (XVII). Methylation and Hofmann degradation of the mixture of methiodides afforded a uniform des-iV-methylphenylmesembrene (XVIII). Methylation of XVIII and Hofmann degradation of the resulting methiodide yielded, besides ethylene and trimethylamine, 3,4-dimethoxy-p-terphenyl (XIX). The isolation of 3,4-dimethoxy-p-terphenyl served to locate the position of the keto group. 

Additionally, Kobayashi and co-workers demonstrated the reaction of 125 with phenyl lithium, followed by treatment with different electrophiles results in 1,3,4-trisubstituted dihydroisoquinolines 126, as shown below <06BCJ1126>. 

Machiguchi, Nozoe and coworkers have very recently observed that in contrast to chemical reactivity of tropones, the tosylate of tropone oxime undergoes a facile ring-opening to 6-substituted (Z,Z,Z)-1,3,5-hexatriene nitriles on reaction with various nucleophiles305. For example, reaction of phenyl lithium results in the corresponding hexatriene carbonitrile (equation 183). 

Reactions with Carboxylic Acid Esters Alkyl nitrones can be metallized upon treatment with phenyl lithium in ether solution. The Li-derivatives react with carboxylic acid esters to give 3-oxo nitrones (305)- the analogs of 3-diketones and j3-keto esters (545). With the help of the 13C NMR method it has been found that 3-oxo nitrones (305) exist as an equilibrium mixture... 

Organic groups are bound to the silica surface after grinding silica in organic liquids (277). A more controlled substitution of surface silanol groups was reported by Wartmann and Deuel (194). Silica gel which had been treated with thionyl chloride was allowed to react with phenyl lithium. Silicon-phenyl bonds could be detected by infrared spectroscopy. The phenyl content of Aerosil treated in this way as estimated from carbon analysis corresponded to 85% of the silanol groups (188). However, it is not certain whether the reaction... 

Although phenyl-sodium and -potassium may be made from reactions between phenyl-lithium and the heavier metal alkoxides, the structures of the donor-free solid compounds are apparently still unknown. The dimeric adducts [NaPh.PMDTA]2 and [NaC6H4Ph.TMEDA]2 have been characterized1 and the structure of a solvent-free arylsodium [Na(C6H3Mes2-2,6)]2, 32 (Fig. 17), has been described.63 The sodium interacts with the ipso... 

In the first, Fe(CO)5 is converted into the carbonyl hydride anion by reductive decarboxylation following initial OH" attack on a carbonyl carbon (55). The carbonyl group is thus oxidized to carbonate in basic medium. The second reaction, (3) (56), is one of E. O. Fischer s celebrated carbene forming reactions (57). Phenyl lithium reacts with Cr(CO)6 leading to an anionic acyl complex. A subsequent alkylation step using Me30+ yields the methoxy-phenylcarbene complex Cr(CO)5(CPh(OMe)). 

The reaction of phenyl lithium with a dimethylnaphthalic ester or with 1,8-dibenzoylnaphthalene gives rise to 2,2,9-triphenyl-9-hydroxynaphtho[c[Pg.59]

Schreiber draws attention to the reaction of phenyl lithium with esters, e. g. 

Since much of our interest in alkenylphosphazenes is related to their incorporation into traditional vinyl polymers ( 5,6), we were pleased to observe facile copolymerization of N3P3F C(OC2H3)=CH2 with styrene. We also have prepared some mixed substituent derivatives. The reaction of phenyl lithium with... 

The reaction of diphenyl tellurium dichloride with phenyl lithium yielded tetraphenyl tellurium1. Bis[trifluoromethyl] tellurium dichloride and bis[trifluoromethyl] cadmium reacted to produce tetrakis[trifiuoromethyl tellurium2. 

Other types of leaving groups and of nucleophilic reagents also show greater reactivity at the 4-position 2,4-dichloropyrimidine with alcoholic potassium thiocyanate ° (to 304) and with chemical monodehalogenation (zinc and ammonia or ammonium chlor-ide), 2,4-(lH,3/f)-pyrimidinedithione with ammonia or amines to give 305, 2,4-(l/f,3 f)-pyrimidinedione thiona-tion o 8 o with phosphorus pentasulfide (of. 126 and 127), pyrimidine with phenyl lithium, and 2,4,6-trichloropyrimidine with several sulfanilamide anions. In the latter reaction, the absence of a... 

Orthometallation of substituted arenes has been re-viewed. The ortho-directing ability of substituents in ( ) -arene)Cr(CO)3 complexes decreases as F > CONHR > NHCOR > CH2NR2 OMe CH20Me. Heavier alkali metal arenes can be formed from the reaction of phenyl lithium with sodium or potassium aUcoxides. 

The original 1964 synthesis of a carbene complex was a classic in organome-tallic chemistry and generated the prototype of what are now known as Fischer carbene complexes. In this synthesis, W(CO)6 was allowed to react with phenyl-lithium in diethylether to form the anion [W(CO)5COC6H5]. Reaction of this ion with diazomethane (CH2N2) yielded the carbene complex shown below in equation 6.6. 

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