42808-98-0

Upstream product

• 17376-04-4 2-phenethyl iodide 
• 103-63-9 1-phenyl-2-bromoethane 
• 956-73-0 bis-β-phenylethylmercury 
• 13865-49-1 [2-(phenylsulfanyl)ethyl]benzene 

Downstream Products

• 77970-99-1 (Z)-2-Methyl-6-phenyl-hex-2-en-1-ol 
• 77971-03-0 (E)-2-Methyl-6-phenyl-hex-2-en-1-ol 
• 122445-08-3 trans-2,5-diphenylcyclopentanol 
• 1083-56-3 1,4-diphenylbutane 
• 1520-44-1 1,3-diphenylbutane 
• 54410-69-4 1-Phenyl-3-methylpentane 
• 122445-14-1 (3-cyclohexylbutyl)benzene 
• 122445-15-2 (3,4,4-Trimethyl-pentyl)-benzene 
• 104-51-8 1-butylbenzene 
• 122445-11-8 (3-methylnonyl)benzene 
• 122623-19-2 7-phenethyl-4,6-androstadiene-3,17-dione 
• 110966-42-2 (Z)-2-methyl-6-phenylhex-2-enenitrile 
• 110966-41-1 (E)-2-methyl-6-phenylhex-2-enenitrile 
• 146560-44-3 (4S,5R)-1-Acetyl-5-isopropoxy-4-phenethyl-pyrrolidin-2-one 

Relevant academic research and scientific papers

Reductive lithiation of alkyl phenyl sulfides in diethyl ether. A ready access to α,α-dialkylbenzyllithiums

Diethyl ether is a convenient solvent for the conversion of benzylic phenyl sulfides to the corresponding organolithiums by an uncatalyzed reductive metalation, while catalysis by naphthalene is required to achieve the same reaction for alkyl phenyl sulfides. The addition of magnesium 2-ethoxyethoxide to solutions of unstable alkyllithiums prepared in this way provides storable reagents.

(Phenylalkyl)palladium complexes containing β-hydrogen atoms: Synthesis and characterization of [PdR2(dppe)], [PdR(SPh)(dppe)] (R = CH2CH2Ph, CH2CH2CH2Ph, CH2CHMePh), and [Pd(CH2CH2CH2Ph)X(dppe)] (X = I, Br, Cl)

Reactions of HgR2 (R = CH2CH2Ph, 1a; CH2CH2CH2Ph, 1b; CH2CHMePh, 1c) (prepared from HgCl2 and the requisite Grignard compounds) with lithium in toluene afforded (phenylalkyl)lithium compounds LiR (2a-c) in yields of between 64 and 81%. At -30 °C, they react with [PdCl2(dppe)] [dppe = 1,2-bis(diphenylphosphanyl)ethane] yielding bis(phenylalkyl)palladium(II) complexes [PdR2(dppe)] (3a-c) which were isolated (Tdec = 159 °C, 3a; 80 °C, 3b; 145 °C, 3c) and fully characterized by 1H, 13C, and 31P NMR spectroscopy. Single-crystal X-ray diffraction of [Pd(CH2CH2Ph)2(dppe)] (3a) showed that the palladium atom is square-planar coordinated by two 2-phenylethyl ligands and the dppe ligand. The two CH2CH2Ph ligands exhibite nearly a fully staggered conformation. Overall, a good approximation for the complex is that it has C2 symmetry with the C2 axis defined by the Pd atom and the midpoint of the central C-C bond of the dppe ligand. Bis(phenylalkyl)palladium complexes 3a and 3b reacted with PhSH in a 1:1 ratio yielding [PdR(SPh)(dppe)] (R = CH2CH2Ph, 5a; CH2CH2CH2Ph, 5b), whereas in the case of complex 3c, besides [Pd(CH2CHMePh)(SPh)(dppe)] (5c), a considerable amount of [Pd(SPh)2(dppe)] (6a) was formed. Reactions of 3b with the less acidic alkanethiols iPrSH and tBuSH resulted in the formation of [Pd(CH2CH2CH2Ph)(SR′)(dppe)] (R′ = iPr, 5d; tBu, 5e) along with smaller amounts of [Pd(SR′)2(dppe)] (6) and [Pd(dppe)2] (7). Furthermore, complex 3b was found to react in THF with disulfides R′SSR′ (R· = Ph, Bz, Me), yielding [Pd(CH2CH2CH2Ph)(SR′)(dppe)] (R′ = Ph, 5b; Bz, 5f, Me, 5g) with small amounts (3-13%) of [Pd(SR′)2(dppe)] (6) as side products. The corresponding reaction with MeSe-SeMe afforded [Pd(CH2CH2CH2Ph)(SeMe)(dppe)] (8a) and 3% of [Pd(SeMe)2(dppe)] (9a) and [Pd(dppe)2] (7). Reactions of complex 5b with MeI and H2C=CHCH2Br in tetrahydrofuran and with neat H2C=CHCH2Cl readily proceeded at -30 °C to give halo(3-phenylpropyl)palladium complexes [Pd(CH2CH2CH2Ph)X(dppe)] (X = I, 10a; Br, 10b; Cl, 10c). They were isolated as pale yellow powdery/microcrystalline substances and fully characterized by 13C and 31P NMR spectroscopy. Solutions of complexes 10 in THF decompose rapidly above -30 °C. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

Carbanion Rearrangements by Intramolecular 1,ω Proton Shifts, III. The Reaction of 2-, 3-, 4-, and 5-Phenylalkyllithium Compounds

Upon addition of THF to a solution of 4-phenylbutyllithium (2) in diethyl ether a rapid intramolecular 1,4 proton shift takes place with the formation of 1-phenylbutyllithium (5).Similarly, although somewhat more slowly, 5-phenylpentyllithium (82) rearranges to 1-phenylpentyllithium (83) via 1,5 proton transfer.The corresponding rearrangements by 1,2 or 1,3 hydrogen shifts, however, starting with 2-phenylethyllithium (1) and 3-phenylpropyllithium (54), respectively, were not detected.With 3-phenylpropyllithium (54) a slow intramolecular 1,5 transfer an ortho proton is observed instead, yielding o-propylphenyllithium (100).The corresponding 1,6 shift with 4-phenylbutyllithium (2) was also detected in a minor amount in addition to the 1,4 proton shift already mentioned.There is no indication, however, for a 1,4 transfer of an ortho proton in 2-phenylethyllithium (1).The reaction products in this case can be exclusively explained by intermolecular transmetallation reactions.All ω-phenylalkyllithium compounds under investigation show interesting side and secondary reactions being rather different in deuterated solvents and in deuteriumfree solvents, respectively, due to the isotope effects.The analysis of the products is accomplished by 1H-NMR spectroscopy and, after derivatization, with the help of a GC-MS-combination.Stereoelectronic reasons are made responsible for the failure of the intramolecular 1,2 and 1,3 proton shift in these systems.