Multifunctional organolithium initiator was prepared in cyclohexane solvent. The process started with adding the cyclohexane solution of butadiene to naphthalene-lithium in batches to produce butadiene oligomer dilith...Multifunctional organolithium initiator was prepared in cyclohexane solvent. The process started with adding the cyclohexane solution of butadiene to naphthalene-lithium in batches to produce butadiene oligomer dilithium with 4-8 butadiene repeating units. In the first feeding, the maximum loading of cyclohexane and the minimum concentration of butadiene cyclohexane solution must be controlled under Vcyclohexane 〈 1.33 VTHF and p 〉 40.6cN. Then, SnCl4 was added and eventually the multifunctional organolithium initiator containing Sn atom was synthesized through coupling reaction. Experiment results showed that adding the cyclohexane solution in batches was effective in overcoming some difficulties, such as insolubility of naphthalene-lithium in cyclohexane, low efficiency of naphthalene-lithium in initiating butadiene. In practice, benzene can be replaced by cyclohexane completely, which can not only reduce environmental pollution from benzene, but also overcome the difficulty of solvent recovery caused by similar boiling point between benzene and cyclohexane. Prepared with multifunctional organolithium containing Sn atom as initiator, the star-shaped solution polymerized styrene-butadiene rubber （star S-SBR） with better vulcanization performances, lower rolling resistance and higher wet-skid resistance was obtained.展开更多
Owing to their inexpensive and environmentally friendly properties,iron-based catalysts have been actively investigated for new organic reactions.In this account,we summarized our recent results on iron-catalyzed cros...Owing to their inexpensive and environmentally friendly properties,iron-based catalysts have been actively investigated for new organic reactions.In this account,we summarized our recent results on iron-catalyzed cross-coupling reactions and homo-coupling reactions.With iron-based catalysts,we constructed diverse carbon-carbon bonds,i.e.,C(sp^2)-C(sp^3),C(sp^3)-C(sp^3),C(sp^3)-C(sp^2)and C(sp^2)-C(sp^2)bonds.In order to demonstrate the usefulness of our iron protocol,we also carried out these reactions on gram-scale reactions,leading to good yields.展开更多
The conjugate addition reactions of four organolithium reagents to 2,3,4,5-tetraphenylcyclopentadienone （tetracyclone） were investigated to reveal the reactivity of organolithium reagents to tetracyclone. The result...The conjugate addition reactions of four organolithium reagents to 2,3,4,5-tetraphenylcyclopentadienone （tetracyclone） were investigated to reveal the reactivity of organolithium reagents to tetracyclone. The results show that 1,2-addition products 2,3,4,5-tetraphenyl-1-（2-thienyl）-2,4-cyclopentadien-l-ol（1）, 1-n-butyl-2,3,4,5-tetraphenyl- 2,4-cyclopentadien-l-ol（2） and 1,2,3,4,5-pentaphenyl-2,4-cyclopentadien-1-ol（3） were synthesized in excellent yields while tetracyclone reacted with 2-thienyllithium, n-butyllithium and phenyllithium, respectively. Interestingly, three 1,2-, 1,4- and 1,6-addition isomers 1-tert-butyl-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-ol（4）, 4-tert-butyl-2,3,4,5- tetraphenyl-2-cyclopenten-1-one（5） and 2-tert-butyl-2,3,4,5-tetraphenyl-3-cyclopenten-1-one（6）, were simultaneously obtained by the conjugate addition reaction of tert-butyllithium with larger steric hindrance to tetracyclone. Compounds 1-6 were characterized by ^1H and ^13C NMR spectra, Fourier transform infrared（FTIR） spectra and mass spectra（MS）. The crystal and molecular structures of compounds 1, 2 and isomers 5, 6 were determined by X-ray single crystal diffraction technique. The results imply that the steric hindrance of tert-butyllithium probably play a key role in controlling the conjugate addition reaction. The conjugate addition mechanism of organolithium reagents to tetracyclone was proposed.展开更多
The imine salt was formed initially by the addition of an organolithium compound to the aromatic nitricle.This type of reaction usually leads to cyclic products,such as triazines.We discussed the mechanism of organoli...The imine salt was formed initially by the addition of an organolithium compound to the aromatic nitricle.This type of reaction usually leads to cyclic products,such as triazines.We discussed the mechanism of organolithium compounds catalyzed trimerization of nitriles and study the catalystic charateristics.Using this new method,the yield of triazines was improved.展开更多
The addition of substituents at the 6,13-position improved the solubility and stability of pentacene, making it possible to use the derivatives in spin coating of organic field-effect transistors(OFETs). Three pentace...The addition of substituents at the 6,13-position improved the solubility and stability of pentacene, making it possible to use the derivatives in spin coating of organic field-effect transistors(OFETs). Three pentacene derivatives, 6,13-bis(m-tolyl)pentacene(MP), 6,13-bis(4-butylphenyl)pentacene(BP), and 6,13-bis((4-butylphenyl)ethynyl)pentacene(BPEP) were synthesized, and their properties were investigated. 6,13-Pentacenequinone and organolithium were used in the preparation of 6,13-dihydropentacene at 0 ℃, and pentacene derivatives were synthesized with SnCl_2/HCl as reducing agent, to reduce 6,13-dihydropentacene at room temperature. The structure of the derivatives was characterized using NMR. The thermal stability, photochemical properties, and electronic structure of the three compounds were investigated using TGA, cyclic voltammetry, and UV–Vis. BPEP was also characterized using X-ray diffraction and atom force microscopy. BPEP was used to fabricate an OFET device using spin coating. The device showed a mobility of 0.07 cm^2 V s^(-1) at V_(th) =-10 V and I_(ON)/I _(OFF) = 10~2.展开更多
Some organogermanium oligomers with different side groups were synthesized via ligand substitution polymerization from I, l-dioxane complex of germanium dichloride with different organolithium compounds. The oligomers...Some organogermanium oligomers with different side groups were synthesized via ligand substitution polymerization from I, l-dioxane complex of germanium dichloride with different organolithium compounds. The oligomers were isolated through either precipitation from methanol or extraction using toluene with a yield of no less than 50%. The weight average molecular weight (M-w) of the oligomers is ranging from 1.4 x 10(3) to 5.9 x 10(3) depending on the type and alkyl length of the organolithium compounds used.展开更多
A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molec...A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molecular weight, polydispersity index, microstructure and unit composition of the miktoarm star copolymers were characterized with GPC and 1H-NMR. Performances of the miktoarm star styrene-butadiene rubbers were investigated in comparison with those of the blend rubbers such as the tin-coupled star-shaped random copolymers of styrene-butadiene rubber（S-SBR）/natural rubber （NR） blend rubber and S-SBR/Cis-1, 4-polybutadiene rubber （Cis-BR） blend rubber.展开更多
基金supported by the "Tenth Five" National Scientific and Technological Projects (No.2004BA310A41 )
文摘Multifunctional organolithium initiator was prepared in cyclohexane solvent. The process started with adding the cyclohexane solution of butadiene to naphthalene-lithium in batches to produce butadiene oligomer dilithium with 4-8 butadiene repeating units. In the first feeding, the maximum loading of cyclohexane and the minimum concentration of butadiene cyclohexane solution must be controlled under Vcyclohexane 〈 1.33 VTHF and p 〉 40.6cN. Then, SnCl4 was added and eventually the multifunctional organolithium initiator containing Sn atom was synthesized through coupling reaction. Experiment results showed that adding the cyclohexane solution in batches was effective in overcoming some difficulties, such as insolubility of naphthalene-lithium in cyclohexane, low efficiency of naphthalene-lithium in initiating butadiene. In practice, benzene can be replaced by cyclohexane completely, which can not only reduce environmental pollution from benzene, but also overcome the difficulty of solvent recovery caused by similar boiling point between benzene and cyclohexane. Prepared with multifunctional organolithium containing Sn atom as initiator, the star-shaped solution polymerized styrene-butadiene rubber （star S-SBR） with better vulcanization performances, lower rolling resistance and higher wet-skid resistance was obtained.
基金financed by National Natural Science Foundation of China (Nos. 21672181, 21272199)GRF/RGC (Nos. 403012, CUHK14309216, CUHK14303815)+1 种基金grant to the State Key Laboratory of Synthetic Chemistry from the Innovation and Technology Commission, The Chinese Academy of Sciences-Croucher Foundation Funding Scheme for Joint LaboratoriesDirect Grant (No. 4053325) from The Chinese University of Hong Kong
文摘Owing to their inexpensive and environmentally friendly properties,iron-based catalysts have been actively investigated for new organic reactions.In this account,we summarized our recent results on iron-catalyzed cross-coupling reactions and homo-coupling reactions.With iron-based catalysts,we constructed diverse carbon-carbon bonds,i.e.,C(sp^2)-C(sp^3),C(sp^3)-C(sp^3),C(sp^3)-C(sp^2)and C(sp^2)-C(sp^2)bonds.In order to demonstrate the usefulness of our iron protocol,we also carried out these reactions on gram-scale reactions,leading to good yields.
基金Supported by the National Natural Science Foundation of China（Nos.21266019, 21062011） and the Inner Mongolia Auto- nomous Region Higher Scientific Research Project, China（No.NJZY14060）.
文摘The conjugate addition reactions of four organolithium reagents to 2,3,4,5-tetraphenylcyclopentadienone （tetracyclone） were investigated to reveal the reactivity of organolithium reagents to tetracyclone. The results show that 1,2-addition products 2,3,4,5-tetraphenyl-1-（2-thienyl）-2,4-cyclopentadien-l-ol（1）, 1-n-butyl-2,3,4,5-tetraphenyl- 2,4-cyclopentadien-l-ol（2） and 1,2,3,4,5-pentaphenyl-2,4-cyclopentadien-1-ol（3） were synthesized in excellent yields while tetracyclone reacted with 2-thienyllithium, n-butyllithium and phenyllithium, respectively. Interestingly, three 1,2-, 1,4- and 1,6-addition isomers 1-tert-butyl-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-ol（4）, 4-tert-butyl-2,3,4,5- tetraphenyl-2-cyclopenten-1-one（5） and 2-tert-butyl-2,3,4,5-tetraphenyl-3-cyclopenten-1-one（6）, were simultaneously obtained by the conjugate addition reaction of tert-butyllithium with larger steric hindrance to tetracyclone. Compounds 1-6 were characterized by ^1H and ^13C NMR spectra, Fourier transform infrared（FTIR） spectra and mass spectra（MS）. The crystal and molecular structures of compounds 1, 2 and isomers 5, 6 were determined by X-ray single crystal diffraction technique. The results imply that the steric hindrance of tert-butyllithium probably play a key role in controlling the conjugate addition reaction. The conjugate addition mechanism of organolithium reagents to tetracyclone was proposed.
文摘The imine salt was formed initially by the addition of an organolithium compound to the aromatic nitricle.This type of reaction usually leads to cyclic products,such as triazines.We discussed the mechanism of organolithium compounds catalyzed trimerization of nitriles and study the catalystic charateristics.Using this new method,the yield of triazines was improved.
基金supported by the National Natural Science Foundation of China (No. 21102099)
文摘The addition of substituents at the 6,13-position improved the solubility and stability of pentacene, making it possible to use the derivatives in spin coating of organic field-effect transistors(OFETs). Three pentacene derivatives, 6,13-bis(m-tolyl)pentacene(MP), 6,13-bis(4-butylphenyl)pentacene(BP), and 6,13-bis((4-butylphenyl)ethynyl)pentacene(BPEP) were synthesized, and their properties were investigated. 6,13-Pentacenequinone and organolithium were used in the preparation of 6,13-dihydropentacene at 0 ℃, and pentacene derivatives were synthesized with SnCl_2/HCl as reducing agent, to reduce 6,13-dihydropentacene at room temperature. The structure of the derivatives was characterized using NMR. The thermal stability, photochemical properties, and electronic structure of the three compounds were investigated using TGA, cyclic voltammetry, and UV–Vis. BPEP was also characterized using X-ray diffraction and atom force microscopy. BPEP was used to fabricate an OFET device using spin coating. The device showed a mobility of 0.07 cm^2 V s^(-1) at V_(th) =-10 V and I_(ON)/I _(OFF) = 10~2.
基金This project of 29504030 was supported by the National Natural Science Foundation of China
文摘Some organogermanium oligomers with different side groups were synthesized via ligand substitution polymerization from I, l-dioxane complex of germanium dichloride with different organolithium compounds. The oligomers were isolated through either precipitation from methanol or extraction using toluene with a yield of no less than 50%. The weight average molecular weight (M-w) of the oligomers is ranging from 1.4 x 10(3) to 5.9 x 10(3) depending on the type and alkyl length of the organolithium compounds used.
基金Supported by the National Natural Science Foundation of China(50573005)
文摘A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molecular weight, polydispersity index, microstructure and unit composition of the miktoarm star copolymers were characterized with GPC and 1H-NMR. Performances of the miktoarm star styrene-butadiene rubbers were investigated in comparison with those of the blend rubbers such as the tin-coupled star-shaped random copolymers of styrene-butadiene rubber（S-SBR）/natural rubber （NR） blend rubber and S-SBR/Cis-1, 4-polybutadiene rubber （Cis-BR） blend rubber.
