The application of microwave irradiation in organic synthesis develope very fast, since 1969, the first time the microwave irradiation technology used in organic reactions by American scientist Vanderhoff. The characteristic of microwave irradiation is that it can heating reaction substrates in a very short time, this heating method can make these reactions which can not proceed on conventional heating processes taking place. Microwave technology has a wide application prospect in all branches of chemistry, biotechnology and environmental protection.Benzimidazole moiety displays a broad spectrum of biological activities including antiviral, antifungicide, anti-inflammatory effects, some benzimidazole compounds have found applications in diverse therapeutic areas for hypertension and ulcer. As an active center functional group of some enzymes, benzimidazole scaffold takes part in many signficant biochemical processes and paly an important role in biological activities. 1,2,4-triazolo[3,4-b]-1′,3′,4′-thiadiazine, thiosemicarbazide, 1,3,4-thiadiazole heterocyclic compounds also exhibits high biological activities, such as anti-inflammatory, analgesic, antibacterial, inhibit microorganism, antiviral and regulation of plant growth.In order to realize combination of multiform active ingredients, we designed and have synthesized a series of novel thiadiazine, thiosemicarbazide and 1,3,4-thiadiazole derivatives which containing benzimidazole compounds in order to enhance their biological activities. It extended the research field of such compounds and provided abundant leading compounds for later selecting work of effective drugs.This thesis consists of two major parts:The first part is about literature review. The progress in application and synthesis of benzoimidazole, thiadiazine, thiosemicarbazide, thiadiazole derivatives and the principle of microwave irradiation and it’s application in organic reactions were systematic exposition.The second part is about experimental content. Major work as follows:1. A series of novel 1,2,4-triazolo[3,4-b]- 1′,3′,4′-thiadiazine derivatives were synthesized by the reaction of 3-(2-substituted benzoimidazole-1-methylene)-4-amino-5-mercapto-1,2, 4-triazole withα-bromoacetophenones under microwave irradiation and heating. Comparison of the conventional refluxing method and microwave irradiation accelerate means, discussed for the results; 2. A series of novel 1-(2-trifluoromethylbenzimidazol-1-acetyl)-4-aroylthiosemicarbazide were synthesized by the reaction of 1-(2-trifluoromethylbenzimidazole-1-yl)acetyl hydrazine with aroylisothiocyanate under microwave irradiation and heating.The preliminary biological activity of the target compounds have been tested;3. 1-(2-trifluoromethylbenzimidazol-1-acetyl)-4-aroylthiosemicarbazide were synthesized under microwave irradiation. Then compounds were cyclized in acetic acid to afford a series of novel 2-aroylamino-5-(2-trifluoromethylbenzimidazol-1-ylmethyl)-1,3,4-thiadi- azole in excellent yields under microwave irradiation. Comparison of the conventional refluxing method and microwave irradiation accelerate means, discussed for the results.The innovations of the paper are based on the follow:1. 3-(2-methyl benzoimidazole-1-methylene)-6-aryl-7H-1′,2′,4′-triazolo[3,4-b]-1″,3″,4″- thiadiazine and 3-(2-trifluoromethyl benzoimidazole-1-methylene)-6-aryl-7H-1′,2′,4′ -triazolo[3,4-b]-1″,3″,4″-thiadiazine were synthesized unreported in the literatures under microwave irradiation. The conditions of microwave irradiation were discussed;2. A series of novel 1-(2-trifluoromethylbenzimidazol-1-acetyl)-4-aroylthio-semicarbazide were synthesized under microwave irradiation. The preliminary biological activity of the target compounds have been tested, the result show that compound 2a have some anti-HIV-1 reverse transcriptase activity;3. Ten 2-aroylamino-5-(2-trifluoromethyl-benzimidazol-1-ylmethyl)-1,3,4-thiadiazole were synthesized under microwave irradiation, ten precursor compounds were synthesized under microwave irradiation too. After two steps of the microwave irradiation, high purity products were obtained.

Diglycerides always called DAG for short,produced by glycerol and two fatty acid,is savageness component in edible oils,and the inter-production in metabolize by oils,concluded in GRAS,safety,nutrition,fit for processing,easiness for body and so on virtue,attribute to functional additive,applied for food,cosmetic,and medica,also attribute to single type food class emulsification,and have no difference between edible oils in edible sense,colour、taste.There are few DAG in savageness plants,so it is important to prepare DAG by oils.This paper study on preparation technology of DAG mainly,from Purification of linoleic acid from corn Oil with urea adduction fractionation,prepare CLA material to emphases on prepare DAG by esterification mathod,Purificate production by molecule distillation,discussed influence of centrifugation on purification of linoleic acid from corn oil with urea adduction fractionation,and synthesize DAG by Immobilized lipase Lipozyme TL IM.This article has done below the research and obtains the conclusion:ONE、Saponification and decompose to prepare linoleic mixture by corn oils,Purification high content linoleic with urea adduction fractionation,change structure of linoleic by alkali,the best parameter made certain in this experiment.In this conditions,the temperature is 15℃,centrifugation speed is 3000r/min,centrifugation time is10min,the linoleic content of from fatty acid mixture improved from 55.61%to 66.26%by centrifugation,compared with mixed fatty acids before centrifugation,content of linoleic acid is increased 12.29%,content of linoleic acid achieved 93.99%,in urea adduction fractionation experiment,the best parameter were fatty acid/urea/ethanol is 1:1.5:3,fractionation temperature is 15℃,time is 12 hour more suitable,effect of dissolving urea by different concentration of ethanol from 80%～100%on linoleic acid was researched,the results indicate that:The difference between iodine value and recovery of linoleic acid is not remarkable,so recycle ethanol may used again.As index of efficience of transformation,confirm the best parameter by single factor experiment and orthogonal experiment,get results:reaction temperature 170℃,time 4h,alkali to fatty acid 0.4,solvent to alkali 3 or 4.Validation experiment was done by the best parameter, efficience of transformation is 95%.We get the exact result of conjugated linoleic acid content by GC method,the c9,t11 and t10,c12 structure of conjugated linoleic acid are 40.011%and 42.192%.Scaning the all spectrums of production of preparation by UV and FT-IR,compared with the standards,the analysis results indicated:conjugated linoleic acid is the preparation production.TWO、As the process of producting 1,3-Conjugated linoleic acid Diglycerides,added glycerol adsorbption material can avoid phenomenon of enzyme grouped,convenient for mixing,reaction equality,enzyme can be cycled,the material of glycerol adsorbption more appropriate for AL302,in this condition that:mol ratio of fatty and glycerol is 2:1,content of enzyme added is 15%bottom material,temperature is 70℃,time is 6 h,quality ratio silica gel to glycerol is 1:1,glycerol adsorbption material added may delay using times of enzyme, esterification rate may improve 20%,silca gel added may extend enzyme repeat times;the regressin equation was get by single factor experiment and orthogonal experiment before DPS soft processing.Y=71.38714+2.35701XJ₁+0.70723X₂+0.97932X₃-0.62125X₁X₂-0.64375X₁X₃ -5.12326X₁²-1.39327X₂² -0.62076X₃²The best combination of esterification rate is X₁=0.1827,X₂=0.1023,X₃=0.6554,namely ,the best precept of producting 1,3-Conjugated linoleic acid Diglycerides is:mol ratio of fatty and glycerol is 2.11%,content of enzyme added is 15.30%,weight ratio of glycerol adsorbption material and glycerol is 1.20%,reaction temperature is 70℃,reaction time is 10h,the esterification rate is 71.96%in this condition,acid value of mixture is 58.4,monoglycerol content is 26.4%,diglycerides content is 42.5%,triglycerides content is 9.4%,fatty acid content is 21.7%.Three、Two classes process molecule distillation technology were made use of purifying 1,3-Conjugated linoleic acid diglycerides,confirm the purification technics of molecule distillation:feed temperature is 70～80℃,feed speed is 0.4～0.51./h,first class process temperature is 130℃～140℃,two class process temperature is 210℃～220℃,distillion pressure is 0.1Pa,speed is 280～320 r/min,in this condition the effect is better,after two class process molecule distillation,and separate by TLC,monoglycerol content is 2.4%,diglycerides content is 77.4%,triglycerides content is 17.2%,fatty acid content is 3.0%.

Solvent puping is available way that can separate fiber,lignin,sugars, and other components from raw materials to achieve cleaner production,.Ethanol and methanol as the representative of the lower aliphatic alcohol (boiling point less than 100℃) is the most common organic solvents of solvent pulping, due to these lower aliphatic alcohol solvent with a low boiling point, highly volatile and flammable properties, high pressure caused easily during ethanol pulping, high security requirements is needed for the process of pulping equipment and operation, otherwise the solvent recovery is very difficult. For this reason, 1,4 -butanediol is chose as solvent of pulping for this study, and explore the process and mechanism during HBS(1,4 – butanediol) pulping of bagasse , Research including: process conditions optimization of pulping and pulp washing , cooking reaction course, kinetics of deligniflcation and carbohydrate degradation. The results are as following:1、The HBS (1,4 – butanediol) pulping without acid catalyst showed that the temperature had greatest effect on cooking. The result of bagasse HBS pulping show that the appropriate conditions for the preparation of lignin and pulp: 1,4 – butanediol solvent concentration of 60 %, cooking temperature of 190℃, time at temperature of 90 min, liquid ratio of 1:6.2、The objectives of rearch were to investigate the effect of catalysts on HBS pulping,the results showed that: Catalyst (formic acid, acetic acid, citric acid) used in HBS pulping were able to increase the removal of lignin ,and reduce cooking temperatures and cooking time during HBS pulping, among them citric acid had the best obvious effects on the delignification ,however catalyst used in HBS pulping decrease the physical strength of the paper. The infrared analysis of the lignin showed that acid catalyst had little effect on the structure of lignin.3、HBS pulp washing research shows that the stage and solvent content of washing had greatest effect on pulp washing . After two stages of 1,4 -butanediol washing most of lignin adsorbed on the fiber surface were removed. SEM analysis of fiber surface showed that: the traditional washing used water in room temperature was not efficent for HBS pulp washing ,two stages of 1,4 -butanediol washing were able to remove lignin adsorbed on the fiber surface. Finally ,we can achieve the 1,4 – butanediol pulp washing appropriate conditions : washing solvent content greater than 60%, time at temperatue of 30 min, temperature of 80℃, liquid ratio of 1:6, washing stages of 2.4、Study of HBS cooking couse without catalyst show that pH of pulping system had great effect on delignification and carbohydrate degradation, reaction rate is fast at the previous stage and become slowly at later stage . The kinetics analysis of the cooking process showed that the delignification reaction follow two pseudo first-order kinetics,bulk and final phases., and the activation energy was 98.6 kJ/mol and 152.3kJ/mol ,respectively; The carbohydrate degradation of cooking process are all in the pseudo fist order ,the bulk an the residual phases activation energy were 117.4kJ/mol and 125.9kJ /mol, respectively.This paper study on the factor of cooking and washing duiring HBS pulping ,and optimize the appropriate conditions for the preparation of lignin and pulp ,and show reaction rules of physical chemistry, in order to provide the basic data for cleaner production of pulp and paper making and resource utilization of agricultural and forestry waste materials.

Metal such as Al,Zn,Mg and Ti Schiff-base complexes have been reported to be effective catalyst for the ring-opening polymerization of lactones and show great potential for application. However, little rare earth Schiff-base complexes used as catalysts for the polymerization have been reported. By far, only a few catalysts （such as tin（Ⅱ） ethylhexanoate） have been used to prepare poly（1,4-dioxan-2-one） （PPDO） with either low reaction rate and low activity or low monomer conversion and low molecular weight. In this thesis, the rare earth lanthanum Schiff-base complexes synthesized from the Schiff-base and anhydrous lanthanum chlorides were used for the homopolymerization of 1,4-dioxan-2-one（PDO） and copolymerization of PDO with e-CL. The process of polymerization and structure of polymer were explored for developing a new approach to synthesize PPDO and providing theoretical foundation for application of biodegradable materials.Lanthanum tris（N-phenylethyl-3,5-di-t-butylsalicylaldiminato）s[La（OPEBS）₃] was an effective initiator for polymerization of PDO, it was found to be more active than Lanthanum tris（2,6-di-methylphenolate）La（ODMP）₃ under conditions tested. So La（OPEBS）₃ was chosen as single initiator for the synthesis of poly（1,4-dioxan-2-one）: The results show that temperature influences the monomer conversion slightly, but the molecular weight of PPDO greatly. The higher temperature is, the lower molecular weight is. The monomer conversion （91.5%） with relatively high molecular weight of PPDO（Mv≈5.99×10⁴） can be obtained in mild reaction conditions for 24h. In ¹HNMR spectrum, three characteristic peaks of PPDO were observed:δ=4.45ppm, （-OCH₂COO-,s）,δ=4.00ppm（-OCH₂CH₂OCO-, t）,δ=4.62ppm （-OCH₂CH₂OCO-,t）. The obvious difference between PPDO and PDO was observed in the IR spectrum. The XRD of PPDO showed that the characteristic diffraction peaks （2θ） were at 20-25°The TG-DSC of PPDO （Mv=6.87×10⁴） was detected, thermal degradation of PPDO occurred above 150℃and reached a loss of weight of 100% at 175℃.The copolymerization of PDO withε-CL by lanthanum complexes have been studied. It was proved that the copolymer could be prepared by copolymerization of PDO with e-CL initiated by La（OPEBS）₃, but La（OMDP）₃ and lanthanum Borohydride Complex La（BH₄）₃（THF）₃ nearly no activity. It was found that the feed ratio of monomers influenced the copolymerization greatly. When the feed ratio ofε-CL is more than 0.5, only polymers of PPDO or PCL can be obtained. The copolymer can be prepared when the f_CL is less than 0.5, polymerization temperature is at 50℃, polymerization time is in 24h and the molar ratio of monomer to initiator is 200. The copolymer was extracted by toluene and characterized by ¹H-NMR, both the characteristic peaks of PCL chain and PPDO chain were found in the spectrum:δ=2.32ppmδ=1.64ppm,δ=1.35ppm,δ=4.09ppm of PCL andδ=4.15ppm,δ=3.77ppm,δ=4.33ppm of PPDO.

1.1,4-Bis(4-Phenoxybenzoyl)benzene was synthesized by nucleophilic and electrophilic substitution: (1)1,4-bis(4-chlorobenzoyl)benzene was obtained from chlorobenzene and terephthaloyl chloride (TPC). Then, the resulting compound p-EKKE was synthesized by 1,4-Bis(4-chlorobenzoyl)benzene with Natrium phenate, taking N-methyl-2-pyrrolidone (NMP) as solvent. (2) p-EKKE was synthesized by Friedel-Crafts acylation of terephthaloyl chloride (TPC) and excessive diphenylether (DPE) in 1,2-dichloroethane with aluminium trichloride (AlCl3) as catalyst. Its structure was characterized by FT-IR, 1H NMR, Micromelting point apparatus, WAXD, SEM and DSC etc. The results show that the compound was anticipated and has high purity. EKKE has the same crystalline diffraction characterization as PEKK which is the unqiue crystallinaion habits of PEKK.2.Poly(Aryl Ether Ketone Ketone)s have excellent thermal stability, resistance to corrosion, creep and other properties, considered as outstanding engineering thermo- plastics. It is very difficult to investigate their micro-structure and properties, for their high melting points and poor solubility in common organic solvents. One of efficient strategies studied the compositions and crystal properties of the macromolecule, attributed to comparing the model compounds which are similar to their segment. In this paper, a series of high molecular weight of alternative and random Poly(Aryl Ether Ketone Ketone) copolymers were prepared by low-temperature solution poly-condensation, with 1,4-Bis(4-Phenoxybenzoyl)benzene (p-EKKE), 1,3-Bis(4- Phenoxybenzoyl)benzene (m-EKKE), diphenyl ether (DPE) and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC) respectively. The inherent viscosities (ηinh) of resulting copolymers were in the range of 0.63~1.08 dL/g. The chemical structure of p-EKKE, m-EKKE and PEKKs were confirmed by FT-IR. Thermal properties of copolymers obtained by DSC and TG, DSC results indicated that the melt temperature (Tm) and the glass transition temperature (Tg) decreased with increasing of the amount of meso- phenylene substituted in the main chain. TG results show that copolymers had excellent thermo-oxidative stability, and their thermally stable were above 530℃, which affected slightly by the amount of meso- phenylene substituted in the main chain. The alternative copolymer a-PEKK has better order and higher crystallinity than random copolymers. WAXD show that copolymer a-PEKK and the model compound has the same crystallization diffraction spectra, which belong to rhombic system. While the morphology of copolymer i-PEKK and the corresponding model compound attribute to needle crystals, and their type of crystallization belong to anorthic system. i-PEKK is difficult to crystallize again in the course of melting, and it converts into amorphous.3.Poly(aryl ether ketone ketone ether ketone ketone/ether sulfone ether ketone ketone) (PEKKEKK/ESEKK) copolymers of high molecular weight were synthesized by low temperature solution polycondensation of 1,4-bis(4-chlorobenzoyl)-benzene (p-EKKE), 4,4′-diphenoxydiphenylsulfone (DPODPS) and terephthaloyl chloride (TPC) in a catalyst/solvent of AlCl3/ClCH2CH2Cl/DMAc. The copolymers characterized by FT-IR, DSC, TG and WAXD. The results show that copolymers exhibited excellent thermal stability. With increasing the content of DPODPS in the copolymer the glass transition temperature (Tg) of the copolymer improved greatly, while Tm and the degree of crystallinity decreased. When the ratio of DPODPS/p-EKKE is above 70 to 30, copolymers turn into amorphous.4.The alternative polymer a-PEKK which is changed to amorphism by quenching, crystallized by solvant, fusion and elongation at above melting temperature treatment. The crystal morphology of alternative copolymers was examed by DSC and WAXD. The results show that the sample of S3 is crystallized completely treated in dichloroacetic acid about forty-eight hours. Prolonged the time has not been effected to the crystallination. WAXD results showed two crystal types co-exist, but typeⅡdominated in the crystalline. Provided that the thermal treatment of the induced crystallization sample is done at ambient conditions, typeⅡconverted into the most stable crystal typeⅠ. The sample of S4 induced crystallization by fusion in the same temperature only exist crystal typeⅠ. The density of crystalline was affected by the speed of cooling down in DSC. There is no cold crystallization peak in DSC curve by fusion wire drawing orientation treatment. While the sample of S5 processed at fusion temperature for two hours, there is a cold crystallization peak in DSC curve. This strategy indicated that crystal has two types of crystallization. The ratio of crystallinity typeⅠand typeⅡis determined by the the ratio of ketone to ether in the macromolecular chain, wire drawing temperature, the ratio of drawing.

1.1,4-Bis(4-Phenoxybenzoyl)benzene was synthesized by nucleophilic and electrophilic substitution: (1)1,4-bis(4-chlorobenzoyl)benzene was obtained from chlorobenzene and terephthaloyl chloride (TPC). Then, the resulting compound p-EKKE was synthesized by 1,4-Bis(4-chlorobenzoyl)benzene with Natrium phenate, taking N-methyl-2-pyrrolidone (NMP) as solvent. (2) p-EKKE was synthesized by Friedel-Crafts acylation of terephthaloyl chloride (TPC) and excessive diphenylether (DPE) in 1,2-dichloroethane with aluminium trichloride (AlCl3) as catalyst. Its structure was characterized by FT-IR, 1H NMR, Micromelting point apparatus, WAXD, SEM and DSC etc. The results show that the compound was anticipated and has high purity. EKKE has the same crystalline diffraction characterization as PEKK which is the unqiue crystallinaion habits of PEKK.2.Poly(Aryl Ether Ketone Ketone)s have excellent thermal stability, resistance to corrosion, creep and other properties, considered as outstanding engineering thermo- plastics. It is very difficult to investigate their micro-structure and properties, for their high melting points and poor solubility in common organic solvents. One of efficient strategies studied the compositions and crystal properties of the macromolecule, attributed to comparing the model compounds which are similar to their segment. In this paper, a series of high molecular weight of alternative and random Poly(Aryl Ether Ketone Ketone) copolymers were prepared by low-temperature solution poly-condensation, with 1,4-Bis(4-Phenoxybenzoyl)benzene (p-EKKE), 1,3-Bis(4- Phenoxybenzoyl)benzene (m-EKKE), diphenyl ether (DPE) and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC) respectively. The inherent viscosities (ηinh) of resulting copolymers were in the range of 0.63~1.08 dL/g. The chemical structure of p-EKKE, m-EKKE and PEKKs were confirmed by FT-IR. Thermal properties of copolymers obtained by DSC and TG, DSC results indicated that the melt temperature (Tm) and the glass transition temperature (Tg) decreased with increasing of the amount of meso- phenylene substituted in the main chain. TG results show that copolymers had excellent thermo-oxidative stability, and their thermally stable were above 530℃, which affected slightly by the amount of meso- phenylene substituted in the main chain. The alternative copolymer a-PEKK has better order and higher crystallinity than random copolymers. WAXD show that copolymer a-PEKK and the model compound has the same crystallization diffraction spectra, which belong to rhombic system. While the morphology of copolymer i-PEKK and the corresponding model compound attribute to needle crystals, and their type of crystallization belong to anorthic system. i-PEKK is difficult to crystallize again in the course of melting, and it converts into amorphous.3.Poly(aryl ether ketone ketone ether ketone ketone/ether sulfone ether ketone ketone) (PEKKEKK/ESEKK) copolymers of high molecular weight were synthesized by low temperature solution polycondensation of 1,4-bis(4-chlorobenzoyl)-benzene (p-EKKE), 4,4′-diphenoxydiphenylsulfone (DPODPS) and terephthaloyl chloride (TPC) in a catalyst/solvent of AlCl3/ClCH2CH2Cl/DMAc. The copolymers characterized by FT-IR, DSC, TG and WAXD. The results show that copolymers exhibited excellent thermal stability. With increasing the content of DPODPS in the copolymer the glass transition temperature (Tg) of the copolymer improved greatly, while Tm and the degree of crystallinity decreased. When the ratio of DPODPS/p-EKKE is above 70 to 30, copolymers turn into amorphous.4.The alternative polymer a-PEKK which is changed to amorphism by quenching, crystallized by solvant, fusion and elongation at above melting temperature treatment. The crystal morphology of alternative copolymers was examed by DSC and WAXD. The results show that the sample of S3 is crystallized completely treated in dichloroacetic acid about forty-eight hours. Prolonged the time has not been effected to the crystallination. WAXD results showed two crystal types co-exist, but typeⅡdominated in the crystalline. Provided that the thermal treatment of the induced crystallization sample is done at ambient conditions, typeⅡconverted into the most stable crystal typeⅠ. The sample of S4 induced crystallization by fusion in the same temperature only exist crystal typeⅠ. The density of crystalline was affected by the speed of cooling down in DSC. There is no cold crystallization peak in DSC curve by fusion wire drawing orientation treatment. While the sample of S5 processed at fusion temperature for two hours, there is a cold crystallization peak in DSC curve. This strategy indicated that crystal has two types of crystallization. The ratio of crystallinity typeⅠand typeⅡis determined by the the ratio of ketone to ether in the macromolecular chain, wire drawing temperature, the ratio of drawing.

The research work in the thesis is based on the novel ligands containing nitrogen. Ten novel complexes were synthesed by using aniline or its derevative 2, 6- diisopropylaniline as starting materials via the reaction to cyanoamines free-fromα-hrdrogen. The major contents include the syhtheses and structural studies of novel 1, 3-diazaallyl metal complexes and 1,3,5-triazapentadienyl complexes. All the complexes here were chatacterized by ¹H-NMR, ¹³C NMR, elemental analysis and single crystal X-ray diffraction.Chapter one introduces in detail the background and the significance of the research. The following four parts were included: introduction; development, structural features and synthesis of 1, 3, 5-triazapentadienyl complexes; brief introduction and synthetic method of guanidinates; the applications and outlooks of guanidinates.Chapter two discusses the synthesis and structures of the novel 1,3,5-triazapentadienyl complexes 1a and 1b （Scheme 1） from the reaction of ligand PhN（Li）SiMe₃ （L¹）with carbonatriles free-fromα-hrdrogen at the ratio of 1:1. Their structures were chracterised by ¹H-NMR, ¹³C NMR, elemental analysis and single crystal X-ray diffraction. The steric effects of the substitutes in the carbonitrile on the structures were investigated. A lanthanide 1,3,5-triazapentadienyl complex was prepared for the first time.Chapter three discusses the synthesis and structures of a series of novel 2,4-disubstituted-1,3,5-triazapentadienyl complexes prepared via the reactions of the ligand （Dipp）N（Li）SiMe₃ （Dipp = 2,6- ⁱPr₂-C₆H₃） （L²） with carbonatriles free-from a-hrdrogen at the ratio of 1:2（including Mn, Fe, Co, Ni, Cu complexes, Scheme 2 and Scheme 3）. The structures of 2a-2g were characterized by ¹H-NMR, ¹³C NMR, elemental analysis and single crystal X-ray diffraction. The influences of the central metal on the structures were studied.Chapter four involves a new method for 3,5-Disubstituted-1,2,4- triazole complex. This kind of compounds can be easily prepared via the reaction of PhN（Li）SiMe₃ （L¹）with carbonatriles free-fromα-hrdrogen at the ratio of 1:2, using CuCl)2 as catalyst. This method is simple and environmentally friendly. The proposed pathway for the formation of the complex is underway.Scheme 1 Reagents and conditions: i Me₂CN, Et₂O, ca. -78℃; ii YCl₃, THF/Hex, ca. -78℃; iii Bu^tCN, Et₂O, ca. -78℃; iv Me₂CN, Et₂O, ca. -78℃; TMEDAScheme 2 Reagents and conditions: i 2Me₂CN, Et₂O, ca. -78℃; ii MnCl₂, Et₂O, ca. -78℃; iii FeCl₂, Et₂O, ca. -78℃; iv CoCl₂, Et₂O, ca. -78℃; v NiCl₂ . 6H₂O, Et₂O, ca. -78℃. Scheme 3 Reagents and conditions: i 2Me₂CN, Et₂O, ca. -78℃; ii H₂O, r.t., ca. 25℃; iii CuCl/PPh₃, Et₂O, ca. -78℃; CH₂Cl₂（in N₂）; iv CuCl, Et₂O, ca. -78℃; CH₂Cl₂（in air）.Scheme 4 Reagents and conditions: i 2Me₂CN, Et₂O, ca. -78℃; ii CuCl₂, Et₂O, ca. -78℃.

1,3-propanediol is acknowledged as one of six new petrochemical products currently in the world. Its main function is as an important monomer to synthesize a new type of polyester,polyether,polyurethane. 1,3-Propanediol is produced by two ways:chemical synthesis and microbial conversion. Producing 1,3-propanediol by microbial fermentation have many obvious advantages and become the focuses of research.Klebsiella sp. was used as the original strain for further research. A high 1,3-Propanediol-producing strain was obtained by UV and (0.5mg/mL)NTG-ultrasound (200W, 50kHz, 20min) inducing mutagenesis. In batch fermentation of mutant,the production of 1,3- propanediol was increased to 23.31 g/L (by 36.72%). The mutant strain showed genetic stability after 10 generations. The by-product, acetate, was increased, and ethanol was decreased, respectively. The amount of enzyme was not found changed significantly, but the activity of GDHt rises by 21% and the activity of PDOR also rise in a certain extent.The fermentation condition for Klebsiella sp. mutant producing 1,3-propanediol was preliminary optimized by single factor experiment. Different concentration of glycerol, yeast extract, KH2PO4 and other factors influencing the glycerol conversing to 1,3-propanediol was studied respectively. A further study on the fermentation medium composition was by orthogonal test. The optimum medium for mutant was as follows: glycerol 60g/L, yeast extract 6g/L, KH2PO4 3g/L、MgSO4·7H2O 1g/L. In flask fermentation, the production of 1,3- propanediol was increased to 27.03 g/L(by 9.92%).Effects on 1,3-propanediol production of Klebsiella sp. mutant by addition of reductant(VC, GSH, Cys, DTT)were studied.The yield of 1,3-propanediol can reach 29.77 g/L, 29.32 g/L, 29.87 g/L by adding 0.35 mmol/L DTT, 0.35 mmol/L Cys, 0.45mmol/L GSH singlely. They were all exceeded the value of control(27.01 g/L). The yield of 1,3-propanediol is 30.01 g/L(rise by 11.11%)by adding 0.25 mmol/L VC. Studying on the concentration variation of side products by adding VC, the results showed that the final concention of acetic acid, ethanol is increased by 3.77%, 3.35% accordingly. Experimental results also showed that addition of VC had an inhibitory effect on cell growth, but increased 1,3-propanediol production per cell considerably.Effects on 1,3-propanediol production of Klebsiella sp. by addition of ATP were studied. The result showed that addition of ATP had an inhibitory effect on cell growth. Adding 0.04 g/L ATP had a remarkable inhibitory effect on cell growth, the value of OD600 decreased by 26.5%. The yield of 1,3-propanediol is 30.05 g/L(rise by 11.26%)by adding 0.06 g/L ATP. Addition of ATP increased 1,3-propanediol production per cell and the conversion of side product acetate.Comparing to the control, the yield of acetic acid rised by 8.7% by adding 0.06 g/L ATP. Adding 0.06 g/L ATP to flasks at different fermentation stage(0h、4h、18h), the highest yield of 1,3-propanediol is 30.13 g/L(by 11.26%) by adding 0.06 g/L ATP at 4h. The value of 1,3-PD/OD is maximum (rise by 25.84%)by adding 0.06 g/L ATP at 0h, respectively.

Piperidones and its derivatives have been widely utilized in the production of medicines, pesticides, fine-chemicals because of their pharmaceutical importance.N-Ethyl-4-piperidone was chosen as the target molecule in our work. The synthetic route of N-Ethyl-4-piperidones has been systematically investigated.N-Ethyl-4-piperidone was prepared by double Michael addition reaction, followed subsequently by Dieckmann cyclocondensation catalyzed by sodium methoxide by employing ethylamine and methylacrylate as starting materials.The total yield of N-Ethyl-4-piperidone was about 14 %, due to its thermal and chemical instability during normal purification process.The intermediate, 1,5-Dichloropentan-3-one, was prepared by using classic Friedel-Crafts acylation, in which ethylene gas and 3-chloropropionyl chloride used as starting materials and aluminium chloride used as catalyst. The total yield was>90 %, and the level of purity was about 75 %, determined by Gas Chromatography. The purified 1,5-Dichloropentan-3-one reacted with the primary amine, aniline and ethylamine respectively, giving the target piperidones with a yield ranging from 40-50%.Based on atomic economic principia, we tried to synthesize N-Ethyl-4-piperidone by employing Double-Mannich reaction under various reaction conditions. The reaction was investigated systematically by changing solvents and activators. Although a satisfied yield has not obtained in our study, it sheds some light on improving and optimizing the reaction conditions in the future.

Several series of 1,2,3-triazoles containing heterocyclic and naphthalimides compounds were designed and synthesized and their spectra properties,DNA intercalative,antitumor and DNA photo-damaging activities were evaluated.A series of 1,2,3-triazoles fused 1,8-naphthalimide derivatives with electron-deficiency characteristics were designed and synthesized.Their spectra properties,DNA intercalative, DNA photo-damaging and antitumor activities were evaluated.The scatchard binding constant between CT DNA with K1 was monitored by fluorescence spectroscopy technique. The result showed that K1 could effectively intercalate into the CT DNA and the scatchard binding constant reached 10⁵ M^-1.Titration CD spectra of CT DNA by K2 illustrated that the mode of K2 interacted with DNA changed from intercalation to aggregation with the concentration of K2 increased.It also revealed that the CT DNA unwound upon K2 intercalation,followed by which the tertiary structure of CT DNA underwent a transition from B-form to A-like conformation.DNA photo-damaging assay showed that these compounds could effectively cleave supercoiled DNA.The antitumor activities test of these compounds exhibited efficient activities against U251,A549 and MOLT-4 cell lines.A series of 6-1,2,3-triazol-1,8-naphthalimide derivatives were designed and synthesized via “Click Chemistry”.Their spectra properties,DNA intercalative,DNA photo-damaging and antitumor activities were evaluated.Titration CD spectra of CT DNA by V2 illustrated that the mode of V2 interacted with DNA changed from intercalation to aggregation with the concentration of V2 increased.It also revealed that the CT DNA unwound upon V2 intercalation,followed by which the tertiary structure of CT DNA underwent a transition from B-form to A-like conformation.DNA photo-damaging assay showed that these compounds could effectively cleave supercoiled DNA.The inhibitory test against A549 and MOLT-4 cell lines in vitro of V2 showed that this compound exhibited high antitumor activities,IC₅₀ of compound V2 against A549 cell reached 0.426μM.A series of 5-1,2,3-triazol-1,8-naphthalimide derivatives were designed and synthesized via “Click Chemistry”.Their spectra properties,DNA intercalative,DNA photo-damaging and antitumor activities were evaluated.The scatchard binding constant between CT DNA with F1 was monitored by fluorescence spectroscopy technique.The result showed that F1 could effectively intercalate into the calf thymus DNA and the scatchard binding constant reached 10⁵ M^-1.DNA photo-damaging assay showed that these compounds could effectively cleave supercoiled DNA.The inhibitory test against A549 and MOLT-4 cell lines in vitro of I2 and F2 showed that the compounds exhibited high antitumor activities,especially IC₅₀ of compound F2 against A549 cell reached 0.333μM.These two compound also exhibited high selectivity against A549 and MOLT-4 cell lines.