Phenyllithium Research Articles

Ring contraction in the reaction of cationic (h 5-C 5H 5)Mo(CO) 2(schiff base chelate) complexes with methyl and phenyl lithium

The crystal structures of (C 5H 5)Mo(CO) 2(NHR)[C(NC 5H 4)R′] with R = −CH(CH 3)(C 6H 5), R′ = −CH 3(I) and R = −CH(CH 3) 2, R′ = −(C 6H 5)(II) have been determined from single crystal X-ray diffraction data. The first compound crystallizes in the monoclinic space group P2 1/a with a = 17.053(9), b = 11.185(5), c = 11.011(3) Å, β = 104.48(3)dg; the second crystallizes in the orthorhombic space group P2 12 12 1 with a = 8.477(3), b = 14.132(7), c = 16.670(8) Å. Both compounds are characterized by the existence of a three membered ring formed by a n 2-aminomethylene ligand bonded to the Mo through its C and N atoms. The coordination polyhedron around the Mo atom is a distorted square pyramid; the greatest deviation from the theoretical geometry being the N(1)MoC(8) angle for which values of 37.6(4) and 38.0(2)° were observed. The orientation of the pyridine ring is determined by the formation of a strong intramolecular hydrogen bond between its nitrogen and the N(1)H(6) hydrogen of the aminomethylene moiety.

Nucleophilic ring cleavage of mono-activated cyclopropanes via sodium and lithium phenyl selenolate

Nucleophilic ring cleavage of mono-activated cyclopropanes via sodium and lithium phenyl selenolate

Thiophile addition von phenyllithium an thioketen-S-oxide

Thiophile addition von phenyllithium an thioketen-S-oxide

Conjugate Addition of Lithium Dimethylcuprate, Lithium Diphenylcuprate and a Chiral Lithium Phenyl(aryl)cuprate Reagent to Methyl 3-(2-Furyl)acrylate.

Conjugate Addition of Lithium Dimethylcuprate, Lithium Diphenylcuprate and a Chiral Lithium Phenyl(aryl)cuprate Reagent to Methyl 3-(2-Furyl)acrylate.

Lithiation of the cycloalkeno [b] quinolines by phenyllithium

Lithiation of the cycloalkeno [b] quinolines by phenyllithium

ORGANOLANTHANIDES AND ORGANOACTINIDES. IV. TRICYCLOPENTADIENYLPHENYLURANIUM(IV)

Abstract Tricyclopentadienylphenyluranium(IV) has been synthesized from Cp3U–Cl and phenyl lithium in THF and contains a U(IV)–carbon σ bond. Infrared and 1H NMR spectra support the presence of a phenyl group bound to uranium; proton assignments for the compound were confirmed from the spectrum obtained for tricyclopentadienyl-p-tolyluranium(IV) and a contact mechanism postulated to explain the shift of the ortho and para protons relative to the meta.

Thiosteroids-XXXII: Preparation, reactions, proton magnetic resonance spectra, and dipole moments of 3-substituted 5α-cholestan-2α,5- anti-episulphoxides

Oxidation of 3-substituted 5α-cholestan-2α,5-episulphides ( 4a, 4b, 5, 6a, 6b, 10a, and 10b) with m-chloroperbenzoic acid afforded the corresponding anti-sulphoxides ( 7a, 7b, 8, 9a, 9b, 11a, and 11b, respectively). Sulphinyl configurations have been assigned from chemical evidence and established by dipole-moments and NMR spectroscopy, 3β-Bromo- anti-sulphoxide 11a with phenyl lithium was found to give cholesta-2,4-diene. A mechanism is discussed which involves the formation of 5-(S)-phenylsulphinyl-5α-cholest-2-ene as an incipient intermediate, followed by syn-elimination via a cyclic intramolecular mechanism. Anisotropie shielding effects and benzene-induced solvent shifts concerning the S → O bond introduced are discussed.

Bicyclo[2.1.1]hexan-5-one via the reaction of 2-chloronorbornene with phenyllithium

Bicyclo[2.1.1]hexan-5-one via the reaction of 2-chloronorbornene with phenyllithium

Coupling of phenyllithium with trans- and cis-1-chloro-2-butene

Coupling of phenyllithium with trans- and cis-1-chloro-2-butene

Sulfur crosslinks in polybutadiene vulcanizates

AbstractFor the first time the crosslink terminus structure of monosulfide crosslinks and the amount of that structure in an elastomer vulcanizate has been determined directly from a sample of the vulcanizate. By measuring the rate of swelling of vulcanizates, immersed in either methyl iodide or methyl bromide, the rate of crosslink cleavage was measured. Comparison of this cleavage rate with the cleavage rate of model monosulfide compounds permits a measure of the terminus structure of the monosulfide crosslinks. The fraction of each monosulfide structure was determined from the cleavage rate equation for the vulcanizate. The monosulfide crosslink terminus structure in a particular polybutadiene vulcanizate was saturated, having secondary carbon atoms on both sides of the sulfur atom, i.e., it was a saturated, tetrafunctional crosslink. Polysulfide crosslinks in 1,4‐polybutadiene vulcanizates are readily cleaved at room temperature by a solution of phenyl lithium in benzene. The number of polysulfide crosslinks was estimated from a measure of the volume swelling of the vulcanizate before and after treatment with phenyl lithium. This reagent does not cleave the monosulfide crosslinks in polybutadiene vulcanizates.

Carbon compounds of the transition metals. Part XII. Crystal and molecular structure of phenylmethoxycarbenepentacarbonylchromium

The compounds prepared by the nucleophilic addition of lithium phenyl or methyl to tungsten and chromium carbonyls are shown to have structures which are consistent with those expected for carbene complexes. Details of the crystal and molecular structure of the chromium complex are presented.

The syntheses of trimeric sulphanuric fluorides and certain of their derivatives

Trimeric sulphanuric fluorides have been synthesized successfully from α-sulphanuric chloride and potassium fluoride in acetonitrile, and the so-called “ cis” isomer has been isolated in a state of purity. This compound is more stable with respect to ring cleavage than the sulphanuric chlorides and undergoes a variety of substitution reactions. Reaction with phenyl lithium in diethyl ether in the corresponding mole ratios yields the mono- and diphenyl derivatives, whereas reaction with benzene in the presence of anhydrous aluminum chloride yields the triphenyl derivative in two isomeric forms. Several secondary amines form disubstituted products, each in two isomeric forms. The infra-red spectra of all of these compounds have been determined and evaluated.

Reactions of Halopyrenes with Phenyllithium in Ether.

Reactions of Halopyrenes with Phenyllithium in Ether.

The synthesis of 1:2, 3:4, 5:6, 7:8, 9:10, 11:12-hexabenzocoronene

The acid (1) was condensed with phthalic anhydride to the dicarboxylic acid (II). One sided cyclization yielded the acid (III) which was reduced to (IV). A second cyclization gave the pentacene derivative (V) which was oxidized to the diquinone (VI). Compound VI reacted with phenyl lithium to form the tetraol (VII) which was condensed to hexabenzocoronene (VIII) by heating with copper powder.

The Reaction between Acenaphthenequinone and Phenyllithium

The Reaction between Acenaphthenequinone and Phenyllithium

Additions of Phenyllithium to cis- and trans-Dibenzoylstyrenes1,2

Additions of Phenyllithium to cis- and trans-Dibenzoylstyrenes^1,2

ALIPHATIC CHEMISTRY OF FLUORENE: PART VIII. BENZYL 9-FLUORENYL SULPHOXIDE AND SOME 9-FLUORENYL SULPHIDES

Allyl 9-fluorenyl sulphide, benzyl 9-fluorenyl sulphide, and di-9-fluorenyl sulphide are stable to boiling ethereal phenyl lithium, in marked contrast to the corresponding ethers. Benzyl 9-fluorenyl sulphoxide has been prepared and shown to be more weakly acidic than 9-fluorenyl sulphones.

Communications- The Action of Phenyllithium on Bromomethyl- and Iodomethyltriphenylphosphonium Halides

Communications- The Action of Phenyllithium on Bromomethyl- and Iodomethyltriphenylphosphonium Halides

The Reaction of Carbon Monoxide with Phenyl Lithium

フェニルリチウムと一酸化炭素との反応圧力常圧,反応温度 -10°C および反応時間 40 分の条件下で行なった。その反応生成物のうち,一酸化炭素が関与しているものとしてベンズアルデヒド,ベンズヒドロール・トリフェニルメタン,ベンゾフユノン,ベンゾイン,ジフェニルベンゾイルメタン,p-オキシトリフェニル酢酸および安息香酸が単離されたほか・一酸化炭素の関与しない生成物としてフェノール,ジフェニルおよびメチルフェニルカルビノールがえられた。反応は有機マグネシウムハロゲン化物の場合と同様に一酸化炭素とフェニルリチウムとの間に配位錯化合物を形成して進むものと考えられる。

Metallation of 2,4-Lutidine and 2,4,6-Collidine with Phenyllithium

Metallation of 2,4-Lutidine and 2,4,6-Collidine with Phenyllithium