Multiple-walled carbon nanotubes were functionalized by cycloaddition of dichlorocarbene.The chemical modification was performed by using chloroform and sodium hydroxide.Various phase transfer catalysts were used to i...Multiple-walled carbon nanotubes were functionalized by cycloaddition of dichlorocarbene.The chemical modification was performed by using chloroform and sodium hydroxide.Various phase transfer catalysts were used to increase the efficiency of the reaction.Benzyltriethylammonium chloride used as phase transfer catalyst could highly enhance the effect of functionalization.Elemental analysis was used to evaluate the degree of functionalization.Characterization was performed using scanning electron microscopy（SEM）and transmission electron microscopy（TEM）.Fourier transform infrared spectroscopy（FTIR）and energy-dispersive X-ray spectroscopy（EDS）were used to confirm the resulting material.展开更多
Understanding the chemistry of BNNT is a crucial step toward their ultimate practical use. A comparative study of Reactions A （ASWCNT （5,5） and CCl2） and B （ASWBNNT （5,5） and CCl2） have been performed by using...Understanding the chemistry of BNNT is a crucial step toward their ultimate practical use. A comparative study of Reactions A （ASWCNT （5,5） and CCl2） and B （ASWBNNT （5,5） and CCl2） have been performed by using ONIOM （B3LYP/6-31G＊： AM1） method in Gaussian03 program package. The results show that （1） the two reactions are both exothermic; （2） the mechanism of Reaction B is a two-step mechanism; （3） the difference in energy barriers suggests that the reaction of CCl2 with BNNT is easier than with CNT; （4） in reaction B, CCl2 prefers to attack the boron atom of BNNT first.展开更多
In Me2SO, an X-philic reaction took place between α-cyanobenzyl carbanion and CCl4. The intermediate dichlorocarbene was trapped by the primary product dicyanostilbene to give the alkene-carbene adduct, 1, 1-dichloro...In Me2SO, an X-philic reaction took place between α-cyanobenzyl carbanion and CCl4. The intermediate dichlorocarbene was trapped by the primary product dicyanostilbene to give the alkene-carbene adduct, 1, 1-dichloro - 2, 3 -dicyano -2, 3 -diphenylcyclopropane.展开更多
The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro- carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ, pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substit...The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro- carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ, pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substituted-cyclopropanes Ⅺ and 2H-1,4-benzothiazin-2-ones Ⅻ.The structures of these products were confirmed by the analytical and spectral data.Compound Ⅷ and Ⅸ are two new ring systems.展开更多
The reaction mechanism between CC12 and armchair single-walled carbon nanotubes （ASWCNTs） （3,3） and （4,4） has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CC12 adding to AS...The reaction mechanism between CC12 and armchair single-walled carbon nanotubes （ASWCNTs） （3,3） and （4,4） has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CC12 adding to ASWCNT （3,3） and （4,4） are computed and compared. The lower barrier of CC12 forms cycloaddition isomer on （3,3） maybe because the strain energy of （3,3） is larger than that of （4,4）. Our theoretical results are consistent with the experimental results.展开更多
The insertion of dichlorocarbene generated from chloroform by Phase Transfer Catalysis(PTC)into carbon-boron bond of dialkylborate anions 3,obtained by method A and B,resulted in the formation of the inter- mediates 5...The insertion of dichlorocarbene generated from chloroform by Phase Transfer Catalysis(PTC)into carbon-boron bond of dialkylborate anions 3,obtained by method A and B,resulted in the formation of the inter- mediates 5,which were oxidized with alkaline hydrogen peroxide to give the corresponding dialkylketones in 36-77.9% yields.展开更多
Three kinds of products have been separated from the reaction mixtures of 1,2-dihydro-2, 4-disubstituted-1,5-benzodiazepine with: CCI_2.Besides the addition products of: CCI_2 to C=N.the inserted products of: CCI_2 to...Three kinds of products have been separated from the reaction mixtures of 1,2-dihydro-2, 4-disubstituted-1,5-benzodiazepine with: CCI_2.Besides the addition products of: CCI_2 to C=N.the inserted products of: CCI_2 to N-H and C-H single bonds were obtained, too.展开更多
The reactions of tri-2-benzofuranylborane or aminoethyl di-2-thienylborinate and 2-thienylphenylborinate with dichlorocarbene generated in situ from chloroform under phase transfer conditions were explored as a new ro...The reactions of tri-2-benzofuranylborane or aminoethyl di-2-thienylborinate and 2-thienylphenylborinate with dichlorocarbene generated in situ from chloroform under phase transfer conditions were explored as a new route for the preparation of heteroaromatic ketones. It was found that a good yield of the ketones can be obtained by solid-liquid system.展开更多
Reaction of 2,3-dihydro-1H-l,5-benzodiazepines with dichlorocarbene generated in situ using benzyltriethylammonium chloride (TEBA) as a phase transfer catalyst in chloroform-aqueous sodium hydroxide mixture gave mainl...Reaction of 2,3-dihydro-1H-l,5-benzodiazepines with dichlorocarbene generated in situ using benzyltriethylammonium chloride (TEBA) as a phase transfer catalyst in chloroform-aqueous sodium hydroxide mixture gave mainly 1,2-cycloadducts, as and trans-la,3-disubstituted-1, 1-dichloro-1a,2,3,4-tetrahydro-1H-azirino[l,2-a][l,5]benzodiazepines (2,3), and formylated 1,2-cycloadducts, trans-la,3-disubstituted-l, 1-dichloro-4-formyl-1a,2,3,4-tetrahydro-lH-azirino[l,2-a][l,5]benzodiazepines (4). The stereo-structures of cycloadducts and the mechanism are also discussed.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.20576142and50772133)the Doctor's Scientific Re-search and Innovation Foundation of Central South University of China(No.134376211).
文摘Multiple-walled carbon nanotubes were functionalized by cycloaddition of dichlorocarbene.The chemical modification was performed by using chloroform and sodium hydroxide.Various phase transfer catalysts were used to increase the efficiency of the reaction.Benzyltriethylammonium chloride used as phase transfer catalyst could highly enhance the effect of functionalization.Elemental analysis was used to evaluate the degree of functionalization.Characterization was performed using scanning electron microscopy（SEM）and transmission electron microscopy（TEM）.Fourier transform infrared spectroscopy（FTIR）and energy-dispersive X-ray spectroscopy（EDS）were used to confirm the resulting material.
基金supported by the National Natural Science Foundation of China (No 20303010, 20273034 and 20673063)NKStar HPC Program The authors appreciate the assistance provided by Professor Zun-Sheng Cai
文摘Understanding the chemistry of BNNT is a crucial step toward their ultimate practical use. A comparative study of Reactions A （ASWCNT （5,5） and CCl2） and B （ASWBNNT （5,5） and CCl2） have been performed by using ONIOM （B3LYP/6-31G＊： AM1） method in Gaussian03 program package. The results show that （1） the two reactions are both exothermic; （2） the mechanism of Reaction B is a two-step mechanism; （3） the difference in energy barriers suggests that the reaction of CCl2 with BNNT is easier than with CNT; （4） in reaction B, CCl2 prefers to attack the boron atom of BNNT first.
文摘In Me2SO, an X-philic reaction took place between α-cyanobenzyl carbanion and CCl4. The intermediate dichlorocarbene was trapped by the primary product dicyanostilbene to give the alkene-carbene adduct, 1, 1-dichloro - 2, 3 -dicyano -2, 3 -diphenylcyclopropane.
文摘The reaction of two series of 2,3-dihydro-1,5-henzothiazepines Ⅰ with dichloro- carbene,gave azirino[2,1-d][1,5]benzothiazepines Ⅷ,azirino[2,1-e][1,6]benzothiazocines Ⅸ, pyrrolo[2,1-b][1,3]benzothiazoles Ⅹ,substituted-cyclopropanes Ⅺ and 2H-1,4-benzothiazin-2-ones Ⅻ.The structures of these products were confirmed by the analytical and spectral data.Compound Ⅷ and Ⅸ are two new ring systems.
基金This work was supported by the National Natural Science Foundation of China (No. 20303010), NKStar HPC Program and the Science Foundation of Nankai University
文摘The reaction mechanism between CC12 and armchair single-walled carbon nanotubes （ASWCNTs） （3,3） and （4,4） has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CC12 adding to ASWCNT （3,3） and （4,4） are computed and compared. The lower barrier of CC12 forms cycloaddition isomer on （3,3） maybe because the strain energy of （3,3） is larger than that of （4,4）. Our theoretical results are consistent with the experimental results.
文摘The insertion of dichlorocarbene generated from chloroform by Phase Transfer Catalysis(PTC)into carbon-boron bond of dialkylborate anions 3,obtained by method A and B,resulted in the formation of the inter- mediates 5,which were oxidized with alkaline hydrogen peroxide to give the corresponding dialkylketones in 36-77.9% yields.
文摘Three kinds of products have been separated from the reaction mixtures of 1,2-dihydro-2, 4-disubstituted-1,5-benzodiazepine with: CCI_2.Besides the addition products of: CCI_2 to C=N.the inserted products of: CCI_2 to N-H and C-H single bonds were obtained, too.
文摘The reactions of tri-2-benzofuranylborane or aminoethyl di-2-thienylborinate and 2-thienylphenylborinate with dichlorocarbene generated in situ from chloroform under phase transfer conditions were explored as a new route for the preparation of heteroaromatic ketones. It was found that a good yield of the ketones can be obtained by solid-liquid system.
文摘Reaction of 2,3-dihydro-1H-l,5-benzodiazepines with dichlorocarbene generated in situ using benzyltriethylammonium chloride (TEBA) as a phase transfer catalyst in chloroform-aqueous sodium hydroxide mixture gave mainly 1,2-cycloadducts, as and trans-la,3-disubstituted-1, 1-dichloro-1a,2,3,4-tetrahydro-1H-azirino[l,2-a][l,5]benzodiazepines (2,3), and formylated 1,2-cycloadducts, trans-la,3-disubstituted-l, 1-dichloro-4-formyl-1a,2,3,4-tetrahydro-lH-azirino[l,2-a][l,5]benzodiazepines (4). The stereo-structures of cycloadducts and the mechanism are also discussed.
