跳躍二烯烴提氫反應的機理研究
發(fā)布時間：2018-10-11 12:12
【摘要】：研究目的跳躍二烯烴的兩個雙鍵是孤立二烯烴中距離最短的,其雙鍵之間亞甲基上的碳氫鍵的鍵能低具有很高的反應活性,因而備受關注,本文通過不同類型的氫受體與跳躍二烯烴反應力求深入研究提氫反應的反應機制,研究氫供體構(gòu)型、氫受體類型以及取代基對反應熱力學屬性與動力學參數(shù)的影響,進一步研究結(jié)構(gòu)與反應之間的關系,揭示原子轉(zhuǎn)移反應的本質(zhì)。研究方法本文采用量子化學中密度泛函理論(DFT)的B3LYP泛函在6-31g(d)基組和6-311++g(d,p)基組上優(yōu)化反應物與產(chǎn)物的結(jié)構(gòu),得到相應的能量,用M062X泛函在6-311++g(d,p)基組上計算激發(fā)態(tài)的相關能量,采用Ki SThel P程序計算反應速率常數(shù)和隧穿因子,利用Multiwfn程序得到基態(tài)到激發(fā)態(tài)的電子密度差圖和基態(tài)到相應激發(fā)態(tài)的躍遷密度矩陣圖。以氫轉(zhuǎn)移反應作為研究對象,對比線性過渡態(tài)(TS)與非線性TS的差別,探討氫供體的剛性與柔性對提氫反應的影響,根據(jù)激發(fā)態(tài)硫雜蒽酮類(TXs)光引發(fā)劑(PI)與亞油酸甲酯(MLO)和油酸甲酯(MO)的反應,研究光活性三線態(tài)物質(zhì)引發(fā)的提氫反應的具體機理。通過對不同類型的提氫反應的研究加深對氫原子轉(zhuǎn)移反應機理的理解。通過實時紅外法研究硫醇-烯烴聚合動力學,選擇油酸蔗糖酯(O-170)、1,10-癸二硫醇(DDT)與1173或二苯甲酮(BP)這兩個體系,研究不同濃度的組分、不同PI、不同光照時間、不同光照強度和不同單體對轉(zhuǎn)化率的影響。實驗結(jié)果由2,5-庚二烯(HD)與苯甲酰自由基(BR)類型氫受體反應為模型,根據(jù)Boltzmann分布和裂解能計算結(jié)果判斷2,5-庚二烯的最穩(wěn)定構(gòu)型為HD(Boltzmann分布所占百分比為85.04%,BDE為68.7kcal/mol)。BR常來源于裂解型PI的光解,如1173,184,2959等,其中2959的鍵裂解能最低(61.3kcal/mol),三甲基苯甲酰自由基(TMBR)常來源于含磷裂解型PI的光解,如TPO,TPO-L和BAPO等,其中BAPO的C-P鍵裂解能最低(59.6kcal/mol)。BR與氫供體反應TS夾角在誤差范圍內(nèi)可視為擬線性TS,三甲基BR與氫供體反應TS夾角為非線性。根據(jù)內(nèi)稟反應坐標(IRC)得到從反應物復合物到鞍點的活化能、形變能和相互作用能隨反應進程的關系圖,結(jié)果顯示隨著反應進程的推進,活化能和形變能逐漸升高,而相互作用能則逐漸下降。非線性TS反應的活化能和形變能高于擬線性TS反應。根據(jù)鍵能鍵級(BEBO)理論,得到擬線性TS反應裂鍵指數(shù)比非線性TS小,根據(jù)Evans-Polanyi關系,得到擬線性TS反應Polanyi因子比非線性TS大。這些數(shù)據(jù)表明:非線性TS構(gòu)型與反應物復合物更接近,為似反應物型,而擬線性TS構(gòu)型與產(chǎn)物復合物更接近,為產(chǎn)物型。Ki SThel P程序計算結(jié)果顯示,自由基誘發(fā)的提氫反應隧穿因子較大(3.5-4.0),而光活性三線態(tài)硫雜蒽酮類誘導的提氫反應隧穿因子較小(1.1-1.8),接近于自由基加成反應(1.1)。擬線性TS反應速率常數(shù)比非線性TS大3-4個數(shù)量級。根據(jù)M062X泛函在6-311++g(d,p)基組上計算光活性三線態(tài)氫受體(TXs)的垂直激發(fā)能、絕熱激發(fā)能和重組能,結(jié)果表明,三線態(tài)的垂直激發(fā)能與絕熱激發(fā)能小于單線態(tài)的垂直激發(fā)能與絕熱激發(fā)能,而三線態(tài)的重組能則大于單線態(tài),由此證實,三線態(tài)的反應活性遠遠大于基態(tài)。由Multiwfn程序得到躍遷密度矩陣圖和電子密度差圖,結(jié)果顯示TXs從基態(tài)到激發(fā)態(tài),主要是羰基上的電子激發(fā),反應位點以羰基基團為主。三線態(tài)與基態(tài)的鍵角鍵長發(fā)生了改變,推測是由于電子結(jié)構(gòu)重新排布的結(jié)果。TXs分別與MO和MLO反應,與MLO反應的活化能較小,反應速率常數(shù)較大。所有TS角均在線性誤差范圍內(nèi),均為擬線性TS。與自由基誘發(fā)的提氫反應相比,光活性三線態(tài)物質(zhì)誘發(fā)的提氫反應的相互作用能較大,是活化能的重要組成部分。1173裂解產(chǎn)生的BR與DDT反應的活化能大于BP與DDT反應的活化能。實時紅外研究結(jié)果表明,轉(zhuǎn)化率和反應速率受反應物種類、反應物濃度、光照強度、光照時間等的影響。O-170、DDT與1173或BP三體系中,O-170、DDT、1173/BP摩爾比為反應摩爾比2:2:4時,1173體系轉(zhuǎn)化率與反應速率均達到最大,若1173過量或不足,則反應速率與轉(zhuǎn)化率均下降,但BP過量時,轉(zhuǎn)化率與反應速率繼續(xù)升高;若DDT不足,轉(zhuǎn)化率隨DDT濃度下降而下降,DDT的濃度對轉(zhuǎn)化率和反應速率的影響,BP體系比1173體系更明顯;若O-170不足反應摩爾比時,轉(zhuǎn)化率反而下降,O-170的濃度對轉(zhuǎn)化率和反應速率的影響,BP體系比1173體系更明顯;相同配比時1173體系的轉(zhuǎn)化率大于BP體系的轉(zhuǎn)化率。結(jié)論由變形能相互作用能模型和BEBO理論得知,非線性TS反應的活化能和變形能比擬線性TS反應大,非線性TS出現(xiàn)比擬線性TS推遲出現(xiàn),此外,由于變形受限,反應物的剛性與柔性會影響TS出現(xiàn)的早晚。TXs PI的電子激發(fā)主要集中在兩個苯環(huán)間的羰基上,單線態(tài)激發(fā)能高于三線態(tài),三線態(tài)重組能較大,由于電子結(jié)構(gòu)的改變,最優(yōu)三線態(tài)幾何構(gòu)型與基態(tài)時相比發(fā)生了改變,使三線態(tài)羰基奪取氫原子的能力增強。三線態(tài)TXs PI與跳躍二烯間的亞甲基氫反應時TS的出現(xiàn)比與普通雙鍵?位的亞甲基的反應更早,活化能更低,反應速率更快,光活性三線態(tài)誘導的提氫反應,TS基本都呈線性。光照時間越長,轉(zhuǎn)化率越高;光照強度越大,反應速率越快;BP難溶于O-170和DDT混合物中,故O-170、DDT與1173配方優(yōu)于O-170、DDT與BP配方。
[Abstract]:The two double bonds of the jump diolefins are the shortest in isolated diolefins, and the bond energy of the carbon hydrogen bonds between the double bonds of the two double bonds is low and has very high reaction activity, The effects of hydrogen donor configuration, hydrogen acceptor type and substituent on reaction thermodynamic properties and kinetic parameters were studied by different types of hydrogen acceptors and hopping diolefin reactions, and the relationship between structure and reaction was further studied. The essence of atom transfer reactions is revealed. In this paper, the structure of reactants and products is optimized in 6-31g (d) group and 6-311 ++ g (d, p) groups by using the B3LYP functional theory of quantum chemistry intermediate density functional theory (DFT). The electron density difference map of the ground state to the excited state and the transition density matrix of the ground state to the corresponding excited state are obtained by using the Ki SThel P program. Based on the difference between the linear transition state (TS) and the non-linear TS, the influence of the rigidity and flexibility of the hydrogen donor on the hydrogen-stripping reaction was discussed. The specific mechanism of hydrogen-stripping reaction initiated by optically active triplet state substance was studied according to the reaction of the excited state sulfur heteropolyketone (TXs) photoinitiator (PI) with methyl linoleate (MLO) and methyl oleate (MO). The understanding of hydrogen atom transfer reaction mechanism is deepened through the study of different types of hydrogen stripping reactions. By studying the polymerization kinetics of thiol-olefins by real-time infrared method, the two systems of sucrose ester (O-170), 1, 10-dithiodithiol (SO) and 1173 or benzophenone (BP) were selected to study the components of different concentrations, different PI and different illumination time. Effects of different light intensity and different monomer on conversion rate. The experimental results were determined by the reaction of 2,5-heptalene (HD) with the benzene-free radical (BR) type hydrogen acceptor, and the stable configuration of 2,5-heptalene was determined according to Boltzmann distribution and pyrolysis energy. The most stable configuration of the 2,5-heptalene was HD (85. 04% for Boltzmann distribution and 68. 7mol/ mol for BDE). BR often comes from photolysis of lysing PI, such as 1173, 184, 2959, etc., where 2959 bond cleavage can be the lowest (61. 3mol/ mol), and trimethylbenzene free radical (TMBR) is often derived from photolysis of phosphorus-containing cleavage type PI, such as TPO, TPO-L and BAPO, etc. The cleavage energy of the C-P bond of BAPO can be the lowest (59. 6mol/ mol). The included angle of the reaction TS of BR and hydrogen donor can be regarded as quasi-linear TS in the error range, and the included angle between trimethylBR and hydrogen donor is non-linear. According to the intrinsic reaction coordinate (IRC), the activation energy, deformation energy and interaction energy from the reactant complex to the saddle point are obtained. The results show that the activation energy and deformation can be gradually increased with the advancing of the reaction process, and the interaction energy gradually decreases. The activation energy and deformation of the nonlinear TS reaction can be higher than that of the quasi-linear TS. According to the key-energy-key-level (BEBO) theory, the quasi-linear TS reaction crack bond index is smaller than that of the non-linear TS, and the proposed linear TS reaction Polanyi factor is larger than the non-linear TS according to the Langmuir-Polanyi relation. These data indicate that the non-linear TS configuration is closer to the reactant complex and is of a quasi-reactant type, while the proposed linear TS configuration is closer to the product complex as a product type. The results of the Ki-SThel P program show that the radical-induced hydrogen-stripping reaction tunnel wear factor is large (3,5-4.0), while the photoreactive triplet sulfur heteropolyketide-induced hydrogen-stripping reaction tunnel wear factor is smaller (1,1-1.8), close to the free radical addition reaction (1,1). The quasi-linear TS reaction rate constant is 3-4 orders of magnitude larger than the non-linear TS. The vertical excitation energy, adiabatic excitation energy and recombination energy of photoreactive triplet hydrogen receptors (TXs) were calculated on 6-311 ++ g (d, p) groups according to the M062X functional group. The results show that the vertical excitation energy and adiabatic excitation energy of triplet states can be less than the vertical excitation energy and adiabatic excitation energy of singlet state. The recombination energy of triplet state is larger than singlet state, thus confirming that the reaction activity of triplet state is far greater than the ground state. The transition density matrix diagram and the electron density difference map are obtained by the Multiwfn program. The results show that the TXs is excited from the ground state to the excited state, mainly the electron excitation on the electron beam, and the reaction site is mainly composed of the chromophore group. The bond length of the three-wire state and the ground state has changed, presumably due to the re-arrangement of the electronic structure. TXs were reacted with MO and MLO respectively, and the activation energy of the reaction with MLO was small and the reaction rate constant was large. All TS angles are within the linear error range and are quasi-linear TS. Compared with free radical-induced hydrogen-stripping, the interaction energy of the hydrogen-assisted reaction induced by the photoactive triplet state substance can be larger, which is an important part of the activation energy. The activation energy of the BR and the hydrogen cyanide reaction generated by the pyrolysis of 1173 is greater than the activation energy of the BP and the hydrogen cyanide reaction. The results of real-time infrared studies show that the conversion rate and reaction rate are influenced by reactant species, reactant concentration, illumination intensity, illumination time, etc. When the molar ratio of O-170, 1173, and 1173/ BP was 2: 2: 4, the conversion rate and reaction rate of 1173 system reached the maximum. If 1173 excess or insufficient, the reaction rate and conversion rate were all decreased, but when BP was over, the conversion rate and reaction rate continued to increase. If the reaction rate was insufficient, Compared with 1173 system, the conversion rate and the reaction rate decreased, the conversion rate decreased, and the concentration of O-170 was more obvious than 1173 system. The conversion rate of 1173 system was higher than that of BP system at the same ratio. The results show that the activation energy and deformation of the non-linear TS reaction can be compared with the linear TS due to the interaction energy model of the deformation energy and the BEBO theory, and the non-linear TS is compared with the linear TS. In addition, due to the limited deformation, the rigidity and flexibility of the reactant affect the occurrence of TS. The electron excitation of TXs PI is mainly focused on the triplet state between the two benzene rings, the excitation energy of singlet state can be higher than triplet state, the recombination energy of triplet state can be larger, because of the change of the electronic structure, the optimal three-wire state geometry is changed compared with the ground state, The ability to capture hydrogen atoms in triplet states is enhanced. The ratio of the presence of TS to the normal double bond at the time of the methylene-hydrogen reaction between the three-wire TXs PI and the hopping diene? The reaction of methylene in position is earlier, the activation energy is lower, the reaction rate is faster, the photoactivity triplet state induced hydrogen stripping reaction, TS is basically linear. The longer the illumination time, the higher the conversion rate, the higher the illumination intensity, the faster the reaction rate, the higher the BP difficult to dissolve in the O-170 and the water-soluble mixture, so the O-170, the BSF and 1173 formulations are better than the O-170, the Nafion and the BP formula.
【學位授予單位】：廣州醫(yī)科大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.25
本文編號：2264147
[Abstract]:The two double bonds of the jump diolefins are the shortest in isolated diolefins, and the bond energy of the carbon hydrogen bonds between the double bonds of the two double bonds is low and has very high reaction activity, The effects of hydrogen donor configuration, hydrogen acceptor type and substituent on reaction thermodynamic properties and kinetic parameters were studied by different types of hydrogen acceptors and hopping diolefin reactions, and the relationship between structure and reaction was further studied. The essence of atom transfer reactions is revealed. In this paper, the structure of reactants and products is optimized in 6-31g (d) group and 6-311 ++ g (d, p) groups by using the B3LYP functional theory of quantum chemistry intermediate density functional theory (DFT). The electron density difference map of the ground state to the excited state and the transition density matrix of the ground state to the corresponding excited state are obtained by using the Ki SThel P program. Based on the difference between the linear transition state (TS) and the non-linear TS, the influence of the rigidity and flexibility of the hydrogen donor on the hydrogen-stripping reaction was discussed. The specific mechanism of hydrogen-stripping reaction initiated by optically active triplet state substance was studied according to the reaction of the excited state sulfur heteropolyketone (TXs) photoinitiator (PI) with methyl linoleate (MLO) and methyl oleate (MO). The understanding of hydrogen atom transfer reaction mechanism is deepened through the study of different types of hydrogen stripping reactions. By studying the polymerization kinetics of thiol-olefins by real-time infrared method, the two systems of sucrose ester (O-170), 1, 10-dithiodithiol (SO) and 1173 or benzophenone (BP) were selected to study the components of different concentrations, different PI and different illumination time. Effects of different light intensity and different monomer on conversion rate. The experimental results were determined by the reaction of 2,5-heptalene (HD) with the benzene-free radical (BR) type hydrogen acceptor, and the stable configuration of 2,5-heptalene was determined according to Boltzmann distribution and pyrolysis energy. The most stable configuration of the 2,5-heptalene was HD (85. 04% for Boltzmann distribution and 68. 7mol/ mol for BDE). BR often comes from photolysis of lysing PI, such as 1173, 184, 2959, etc., where 2959 bond cleavage can be the lowest (61. 3mol/ mol), and trimethylbenzene free radical (TMBR) is often derived from photolysis of phosphorus-containing cleavage type PI, such as TPO, TPO-L and BAPO, etc. The cleavage energy of the C-P bond of BAPO can be the lowest (59. 6mol/ mol). The included angle of the reaction TS of BR and hydrogen donor can be regarded as quasi-linear TS in the error range, and the included angle between trimethylBR and hydrogen donor is non-linear. According to the intrinsic reaction coordinate (IRC), the activation energy, deformation energy and interaction energy from the reactant complex to the saddle point are obtained. The results show that the activation energy and deformation can be gradually increased with the advancing of the reaction process, and the interaction energy gradually decreases. The activation energy and deformation of the nonlinear TS reaction can be higher than that of the quasi-linear TS. According to the key-energy-key-level (BEBO) theory, the quasi-linear TS reaction crack bond index is smaller than that of the non-linear TS, and the proposed linear TS reaction Polanyi factor is larger than the non-linear TS according to the Langmuir-Polanyi relation. These data indicate that the non-linear TS configuration is closer to the reactant complex and is of a quasi-reactant type, while the proposed linear TS configuration is closer to the product complex as a product type. The results of the Ki-SThel P program show that the radical-induced hydrogen-stripping reaction tunnel wear factor is large (3,5-4.0), while the photoreactive triplet sulfur heteropolyketide-induced hydrogen-stripping reaction tunnel wear factor is smaller (1,1-1.8), close to the free radical addition reaction (1,1). The quasi-linear TS reaction rate constant is 3-4 orders of magnitude larger than the non-linear TS. The vertical excitation energy, adiabatic excitation energy and recombination energy of photoreactive triplet hydrogen receptors (TXs) were calculated on 6-311 ++ g (d, p) groups according to the M062X functional group. The results show that the vertical excitation energy and adiabatic excitation energy of triplet states can be less than the vertical excitation energy and adiabatic excitation energy of singlet state. The recombination energy of triplet state is larger than singlet state, thus confirming that the reaction activity of triplet state is far greater than the ground state. The transition density matrix diagram and the electron density difference map are obtained by the Multiwfn program. The results show that the TXs is excited from the ground state to the excited state, mainly the electron excitation on the electron beam, and the reaction site is mainly composed of the chromophore group. The bond length of the three-wire state and the ground state has changed, presumably due to the re-arrangement of the electronic structure. TXs were reacted with MO and MLO respectively, and the activation energy of the reaction with MLO was small and the reaction rate constant was large. All TS angles are within the linear error range and are quasi-linear TS. Compared with free radical-induced hydrogen-stripping, the interaction energy of the hydrogen-assisted reaction induced by the photoactive triplet state substance can be larger, which is an important part of the activation energy. The activation energy of the BR and the hydrogen cyanide reaction generated by the pyrolysis of 1173 is greater than the activation energy of the BP and the hydrogen cyanide reaction. The results of real-time infrared studies show that the conversion rate and reaction rate are influenced by reactant species, reactant concentration, illumination intensity, illumination time, etc. When the molar ratio of O-170, 1173, and 1173/ BP was 2: 2: 4, the conversion rate and reaction rate of 1173 system reached the maximum. If 1173 excess or insufficient, the reaction rate and conversion rate were all decreased, but when BP was over, the conversion rate and reaction rate continued to increase. If the reaction rate was insufficient, Compared with 1173 system, the conversion rate and the reaction rate decreased, the conversion rate decreased, and the concentration of O-170 was more obvious than 1173 system. The conversion rate of 1173 system was higher than that of BP system at the same ratio. The results show that the activation energy and deformation of the non-linear TS reaction can be compared with the linear TS due to the interaction energy model of the deformation energy and the BEBO theory, and the non-linear TS is compared with the linear TS. In addition, due to the limited deformation, the rigidity and flexibility of the reactant affect the occurrence of TS. The electron excitation of TXs PI is mainly focused on the triplet state between the two benzene rings, the excitation energy of singlet state can be higher than triplet state, the recombination energy of triplet state can be larger, because of the change of the electronic structure, the optimal three-wire state geometry is changed compared with the ground state, The ability to capture hydrogen atoms in triplet states is enhanced. The ratio of the presence of TS to the normal double bond at the time of the methylene-hydrogen reaction between the three-wire TXs PI and the hopping diene? The reaction of methylene in position is earlier, the activation energy is lower, the reaction rate is faster, the photoactivity triplet state induced hydrogen stripping reaction, TS is basically linear. The longer the illumination time, the higher the conversion rate, the higher the illumination intensity, the faster the reaction rate, the higher the BP difficult to dissolve in the O-170 and the water-soluble mixture, so the O-170, the BSF and 1173 formulations are better than the O-170, the Nafion and the BP formula.
【學位授予單位】：廣州醫(yī)科大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.25
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