Post about "synthesis"

One-Pot Reaction of 3,3-Dimethyl-1-(1,2,4-Triazole-1-YL)-2-Butanone with Secondary Amines and Aldehydes

The feasibility of one-pot three-component reaction of 3, 3- dimethyl-1-(1, 2, 4-triazole -1-yl)-2-butanone was studied and the best reaction conditions, including cayalists, solvent and tempreture were considered. A series of new compounds were synthesized under the best condition which was obtained by the previous works. The structures of these compounds were confirmed by IR, 1H NMR, and theirs melting points were determined. In order to study the relationship between structure and effect of these compounds, the antimicrobial activity to pathogens and bacteria were considered. The main results are as follows:The Mannich type reaction of 3, 3- dimethyl-1-(1, 2,4-triazole-1-yl)-2-butanone, secondary amines and aldehydes reacted in aqueous media is feasible, and its best condition was 35℃in water .Under this condition, 13 conpounds including 6 new compounds were synthesized using 3, 3- dimethyl-1-(1, 2,4-triazole-1-yl)-2-butanone, secondary amines and aldehydes, and their structures were determined by IR and 1H NMR.The results inhibiting pathogenic fungi showed that the inhibitory rate of compounds c, e to Fusarium solani a were66.67%和78.33% at the concentration of 100mg/L; that of f to Fusarium graminearum was 69.23%; c, to Fusarium Cotton-wilt was78.33%. Compound f showed a promoting functions to Fusariumgraminearum.

Research on Synthetical Technology and Reaction Mechanism of Curing Agents of Amide

The curing agents ofβ-hydroxyalkylamides are widely used in polyesters which contain carboxyl and anhydride groups because of their non toxicity,high efficiency,economy and ecology.Firstly,this paper focused on synthesis and technology of N,N,N’,N’-tetra (β-hydroxyethyl)adipamide based on single factor experiments,orthogonal experiments and choice of auxiliaries under ratio of stoichiometric coefficient.The yield reached 90.7%with melting point meeting requirement.Moreover,two-step synthesis and gradient temperaturereducing synthesis were studied.By-product was identified by ~1HNMR in order to explore reaction mechanism.Secondly,N,N-bis(β-hydroxyethyl)benzoylamide was synthesized first by aminolysis of methyl benzoate with diethanolamine using a method of preparing N,N,N’,N’-tetra (β-hydroxyethyl)adipamide.Synthetical technology was studied with help of GC and optimal reaction condition was obtained.Under this condition,yield was about 87.8%.Liquid- liquid continuous extractor which was designed in person was used to separate target product.Thirdly,yellowing of N,N,N’,N’-tetra(β-hydroxyethyl)adipamide limits its application. In this paper,synthesis of N,N,N’,N’-tetra(acryloxyethyl)adipamide(Ⅰ)and N,N,N’,N’-tetra (epoxy propyloxyethyl)adipamide(Ⅱ)as its derivatives were explored to expand its new use. Methods of “acrylic acid”,”methyl acrylate” and “acryloyl chloride” were tried to synthesize I.Results revealed that method of acryloyl chloride had low reaction temperature and degree of polymerization which gave high yield compared to methods of acrylic acid and methyl acrylate.Two-step method under catalyst of acid and one-step method under catalyst of base were studied to prepareⅡ.Results revealed that no low polar ingredient was found in two-step method which was inferior to one-step method.Finally,photo curing agent of N,N’-diallyladipamide and N-allyl benzoylamide were prepared both with a yield of over 90%.

Synthesis 3-deoxy-1, 2-O-isopropylidene-α-D-xylofuranose

AtorvastatinCa(Lipitor)is a blood-lipid lowering drug produced by Pfizer.As the most widely prescribed branded cholesterol-lowering drug and most widely prescribed medicine in the world,it greatly lowers LDL cholesterol and TG levels.In this thesis the way to synthesis of 3-Deoxy-1,2-O-isopropylidene-α-D-xylofuranose were studied.It is an asymmetric intermediation of the Atorvastatin’s side chain,also is a key intermediation of medication and natural product.Several methodologies have been reviewed to synthesize 3-Deoxy-1,2-O-isopropy -lidene-α-D-xylofuranose,it was finally synthesized from D-xylose.Arising from the protection of hydroxyl group in D-xylose by acetone,Selective removal of the 3,5-O-iso -propylidene group of D-xylose(1,2-O-isopropylidene-α-D-xylofuranose 2).Benzoylated the 5-hydroxyl group of 2(5-O-benzoyl-1,2-O-isopropy-lidene-a-D-xylofuranose 3).Then replance 3-hydroxyl group of 3 by the iodide group(3-iodo-5-O-benzoyl-1,2-O-isopropy -lidene-α-D-xylofuranose 9).Next step removal of the iodide group of 9(3-deoxy-5-Obenzoyl-1,2-O-isopropylidene-α-D-xylofuranose 10). Last one to do was deprotection of hydroxyl group in the 5 position of 10(3-Deoxy-1,2-O-isopropylidene-α-D-xylofuranose 11).The total yield was 34%.In the studied some useful compound were synthesized,and their technical conditions were discussed.It is a new 6 steps route to synthetic 3-Deoxy-1,2-O-isopropylidene-α-D-xylofuranose This method is easy to apply,sufficiently mild and less harmful to the environment.The reductive reagents(e.g.,tributyltin hydride[n-Bu3SnH].)have often been used in many radical reactions.However,organotin compounds are toxic and expensive,and are difficult to be completely removed from the desired reaction products.So,in this thesis avoided to use them.

The Synthesis of 2′,3′-seconucleoside Intermediate

The present thesis relates to the synthesis of 2′-O-benzoyl-5′-O-(4,4′-dimethoxytrityl) N4-acetyl-2′,3′-secocytidine and 2′-O-benzoyl-5′-O-(4,4′-dimethoxytrityl)-N2-isobutyryl-2′,3′-secoguanosine. They are an important intermediate for the preparation of oligonucleotide. So the research on synthesis of the nucleoside derivatives was of great practical significanc. The final products were identified by IR and 1H NMR.The synthesis of 2′-O-benzoyl-5′-O-(4,4′-dimethoxytrityl)-N4-acetyl-2′,3′-secocytidine comprises the following steps: DMT-Cl(4,4′-dimethoxytritylchloride) reacted with N4-acetylcytidine in prydine is converted to 5′-O-(4,4′-dimethoxytrityl)-N4-acetylcytidine, which is oxidated by NaIO4 and reductived by NaBH4 to give5′-O-(4,4′-dimethoxytrityl)-N4-acetyl-2′,3′-secocytidine. Acylatel with benzonychloride affords final product in the total yield 41%.Preparation of the 2′-O-benzoyl-5′-O-(4,4′-dimethoxytrityl)-N2-isobutyryl-2′,3′-secoguanosine starts from guanosine. Guanosine is acylated by isobutyryl chloride provide N2-isobutyrylguanosine. DMT-Cl reacted with N2-isobutyrylguanosine in prydine is converted to 5′-O-(4,4′-dimethoxytrityl)-N2-isobutyrylguanosine, which is oxidated by NaIO4 and reductived by NaBH4 to give 5′-O-(4,4′-dimethoxytrityl)-N2-isobutyryl-2′,3′-secoguanosine. Acylatel with benzony chloride affords the key intermediate is formed in 28% yield.

Syntheses, Characterization, Structure and Properties of Complexes with Terpyridine and Terpyridine-like Ligands

One of the most important used in modern coordination chemistry is the aspect of N-heteroaromatic ligands, which largely based on pyridine, 2,2′-bipyridine, melamine, and 2,2′:6′,2″-terpyridine (simply terpyridine), have become an ever-expanding synthetic, application and structural frontier. Terpyridine ligands and the tailored terpyridine derivatives (especially 4′- functionalized terpyridines) are stronge tridentate ligands and have much advances and ever-expanding potential applications. Their well-known characteristics are applied in the fields of optical, catalytic, molecular recognition, gas storage, solar cell and so on. Also they could self-assemble lots of intriguing topological structures.Firstly, this thesis focuses on the synthesis of three 4′- functionalized terpyridine with 4-hydroxyphenyl、2-furyl and carboxylic acid. Several coordination compounds have been prepared by the reaction of d10 metals (Cd2+、Zn2+) with these ligands. All compounds are characterized by elemental analysis, IR, emission spectra and single-crystal X-ray diffraction.On the other hand, we think melamine and 2,6-bis(2-furyl)pyridine are very useful terpyridine-like ligands. Three novel melamine complexes with copper(II) including sandwich and extensive hydrogen bonds were obtained. Moreover, a new ligand of 4-(4′-Hydroxyphenyl)-2,6-bis(2-furyl)pyridine has been synthesized and may be uesd as pH sensor.In detail, the work is divided into six chapters as following:In Chapter 1, the research background of the synthesis of 4′-functionallized terpyridine and the current survey of terpyridine coordination compounds in particular optical properties and supermolecular assemblies are concisely introduced. A survey of melamine and 2,6-bis(2-furyl)pyridine are also mentioned.In Chapter 2, the cadmium(II) complex, Cd(p-HO-ptpy)Cl2, p-HO-ptpy being a tridentate ligand 4′-(4-hydroxyphenyl)-2,2′:6′,2″-terpyridine has been synthesized and the crystal structure is determined using X-ray crystallography. Furthermore, its luminescent and electrochemical properties compared with the ligand have been investigated.In Chapter 3, the cadmium(II) complex, [Cd(ftpy)I2]·CHCl3, which ftpy being a ligand of 4′-(2-furyl)-2,2′:6′,2″-terpyridine has been synthesized. Furthermore, its crystal structure and luminescent properties compared with the ligand have been investigated.In Chapter 4, five mononuclear complexes c1-c5 and a mononuclear polymer c6 containing the ligand of 2,2′:6′,2″-terpyridine-4′-carboxylic acid (Hctpy) were prepared by hydrothermal method. The metallic ions in c1-c5 have distorted octahedral coordinations with six nitrogens from two molecules of Hctpy. But 1D chain structure of complex c6 is built by carboxylic acid of Hctpy and resulted in the enhanced emission band. The coordination mode of c6 has never been reported.In Chapter 5, a new ligand of 4-(4-Hydroxyphenyl)-2,6-bis(2-furyl)pyridine had been synthesized by two methods. Furthermore, this compound exhibits novel ultraviolet and electrochemical properties under the influence of pH value. The reason and the mechanism of Hpfpy may be tentatively assigned.In Chapter 6, three copper(II) coordination compounds have been synthesized and researched by cyclic voltammograms. Two novel melamine coordination compounds of them including the copper directly bonded to the aromatic rings of melamine have extensive hydrogen bonds and consolidate a 2-D sheets. Interestingly, one is a dinucear complex with a paddle wheel structure in which the apical positions are occupied specially by two different donor ligands.

Study on Synthesis and Properties of Linear and Hyperbranched Fluorinated Polyesters

Fluorinated materials have excellent performance such as chemical stability, water resistance, oil resistance and pollution resistance etc. However, the high fluorine content (76 % fluorine content for PTFE) results into the traditional fluorinated polymers high cost and poor processability. Fluorinated polymers possessing both low fluorine content and low surface energy are desirable for broadening their application field. In an effort to overcome the above drawbacks, the present work was carried out to synthesize a series of polyesters with different fluorine content. Their chemical structure and surface properties were investigated.Fluorinated monomer N-hydroxyethyl perfluorooctanamide (HPFOA) was synthesized from perfluorooctanoic acid (PFOA) and ethanolmine. Its chemical structure was confirmed by FTIR, Mass spectroscopy and metling measurement methods.Fluorinated Polybutylene terephthalates (FPBT) containing different content from 0% to 10% were synthesized from dimethyl terephthalate, 1,4-Butanediol and N-hydroxyethyl perfluorooctanamide(HPFOA), using tetrabutyl titanate as catalyst. Their chemical structures and surface properties were examined through FTIR, DSC and water contact angle measurement etc. The effects of fluorine content on surface properties of FFPBT films were discussed. The results showed that surface energies of FPBT decreased evidently with the increase of fluorine content.Fluorinated polybutylene isophthalates (FPBI) containing different fluorine content were synthesized from dimethylisophthalate, 1,4-Butanediol and N-hydroxyethyl perfluorooctanamide, using tetrabutyl titanate (TBT) as the catalyst. Their chemical structures and surface properties were investigated by FTIR spectroscopy, attenuated total reflection FTIR spectra (ATR-FTIR), X ray photoelectron spectroscopy (XPS) as well as water and hexadecane contact angle measurement methods. The results showed that the fluorine-containing groups could migrate and enrich on the surfaces. When the fluorine content was 10 mol%, the calculated surface energy was 15.07 mJ/m2 which was lower than polytetrafluorethylene (22 mJ/m2), exhibiting excellent water and oil repellency.A series of hyperbranched fluoropolymer(HBFP) which contained different fluorine content were synthesized from pentaerythritol, dimethylisophthalate, 1,4-butanediol, N-hydroxyethyl perfluorooctanamide, using tetrabutyl titanate as the catalyst. The hydroxyl values of HBFPs, which was determined by acetic anhydride-pyridine method, were 27-107mg/g. The chemical structures were confirmed by FTIR spectroscopy. The degree of branch was regulated by the pentaerythritol content and determined by 13C-NMR. Their curing kinetics was studied by DSC using diisocyanate as curing agent. The curing kinetics parameters, including the activation energy, frequency factor and reaction order were calculated with Kissinger and Crane methods. Their values were 158.67 kJ /mol, 2.25×1015 and 0.95, respectively. The results show that the curing reaction was complex reaction, closing to the first order reaction. The experiment provides reference to curing process of identical polyhydroxy hyperbranched polyester.

Study on Synthesis, Photocuring and Thermal Degradable Property of Cycloaliphatic Diepoxides

Cycloaliphatic epoxies have drown much attention by the electronic packing materials. With smaller of the of line width and the higher integration of integrated circuit, as well as the high technology content of the industry, there are more strict requirements to the performances of the package materials, for example, the short curing time, heat resistance, little hygroscopicity, low cost, colorlessness, little ion and impurity. With the development of the semiconductor device, It shows many advantages in the microelectronic and optoelectronic field. Firstly, compared with the badness of the epoxides prepared from epichlorohydrin, the chlorine-free preparation process of cycloaliphatic epoxide avoids the demolishment to the microcircuit that chlorine would do. Secondly, the fact that there was no aromatic group in the molecular of cycloaliphatic epoxide endowed the resin with the capacity to resist the ultraviolet and the carbonization caused by the arc. Additionally, the comparatively low viscosity meets the demand of the packaging industry of integrated circuit.Besides, with the growing PC computer, there was serious pollution of the chips. It was high time studying the reworkable epoxy to build a green society. The photocrosslink epoxy stands more contribution due to the UV-photocrosslink technology. In this paper, fore cycloaliphatic epoxide was synthesized, all of them were chloro-free, benzene-free epoxide with low viscosity. The curing time were considerably short, the gel content and degradable temperature were high showing good prospect in the electronic packaging materials.Radical addition reaction, etherification and epoxidation reaction were used to synthesize several new diepoxide monomers. Their chemical structures were confirmed through IR spectra and ~1H-NMR spectra. RTIR was used to study the curing process; TGA was measured to evaluate the degradable property of the polymer. The utter aim was to find simple synthesis method, good yield monomer with fast curing rate and modest degradable temperature. From this systematic study we can conclude that cycloaliphatic epoxy was excellent environmental protect electronic material with fast curing rate and modest degradable temperature.

Study on the Synthesis of 4-Chlorophthalic Anhydride

4-Chlorophthalic anhydride is an important chemical intermediate which is broadly used in producing dyes, plastic, medicines, and pesticides. Currently, looking for some industrial potential synthesis routes, in which the technologcial conditions are reasonable and the materials can be easily obtained, has already become the point of research.Two routes that using phthalic anhydride and butadiene respectively as the starting material to synthesize 4-chlorophthalic anhydride are researched in this paper. In the route of using phthalic anhydride as the starting material, 4-chlorophthalic anhydride is synthesized through three consecutive reactions. Phthalic anhydride is firstly nitrified by oil of vitriol and nitric acid. Then the targeted product 4-nitrophthalic acid is separated from 3-nitrophthalic acid through two methods named extraction and esterification-hydrolysis. The optimum reaction conditions of both the two methods are obtained by orthogonal experiments. Under the optimum reaction conditions of the extraction method, the yield and purity of 4-nitrophthalic acid are of 53.4% and 83%, respectively. The relating results of the esterification-hydrolysis method are of 48.3% and more than 99%, respectively. 4-Nitrophthalic anhydride is obtained in 86.2% yield by the dehydration of 4-nitrophthalic acid. Finally, 4-chlorophthalic anhydride is obtained by the chlorination of 4-nitrophthalic anhydride and its acid. 3-chlorophthalic anhydride is found in the chlorination product by the analysis of HPLC/MS. The total yield of both the two isomers is of 89-95%.In the route of using butadiene as the starting material, tetrahydrophthalic anhydride is firstly synthesized by the Diels-Alder reaction of butadiene with maleic anhydride in a yield of as high as 99.1%. Tetrahydrophthalic acid is obtained by the hydrolysis of Tetrahydrophthalic anhydride in 85.9% yield. Then, tetrahydrophthalic anhydride and its acid are treated by chlorine in different solvents. The product of chlorination in water is 4,5-dichlorocyclohexane-1,2-dicarboxylic acid. Finally, the dehydrochlorination and aromatization reactions of 4,5-dichlorocyclohexane-1,2-dicarboxylic acid are explored in this paper.

Synthesis and Application of Red and Blue Dyes for Synthetic Fibers

As the most important textile fiber, synthetic fiber whose yield is 50.3% of the total fibre yield in the world contributes greatly to the textile industry and social economic development. As special dye for synthetic fibers, such as acetate fiber and polyester fiber, disperse dye has high demand in the textile market, with azo disperse dye and anthraquinone disperse dye as the most popular ones. Azo disperse dye is valuable for its outstanding coloring intensity and easy manufacturing process, while anthraquinone disperse dye boasts for high light fastness and excellent dyeing effects. At present, study on dyeing of some novel hydrophobic synthetic fibers, such as polylactic acid fiber, supermicro polypropylene fiber, etc, becomes focus, since traditional disperse dyes cannot get satisfactory dyeing effect on such fibers while there are lack of novel dyes synthesized according to the special characteristics of such fibers. Moreover, study on structure-activity relationship is quite insufficient.A series of 6-acetamido-4-hydroxy-3-(phenyldiazenyl)naphthalene-2- sulfanilamide was synthesized with linear alkyl groups which may increase the affinity between dyes and synthetic fiber as PLA and PP. The affinity could be adjusted by changing the length of alkyl groups in order for dyeing different fibers. By diazotization-coupling reaction, amido protecting reaction, chlorosulfonylation, and sulfonamination reaction, such dyes were synthesized and applied on the dyeing of PLA, PP and PET. Under optimal conditions, dyeing exhaustions, K/S and fastness were achieved, which showed that affinties could be adjusted by changing the length of alkyl groups: For PLA and PP, C8 got the best effect while for PET, C4 was the best one.For study on structure-activity relationship, 7 1,4-disubstituted anthraquinone dyes with linear alkyl groups or aryl groups were selected on the dyeing of PLA, PP and PET. The study showed that: For PLA and PP, anthraquinone dyes with linear alkyl groups got better effects, while for PET, anthraquinone dyes with aryl groups were better. Such results were coincident with similarity and mutual attraction theory.

Synthesis of New Chiral Ligands and Their Application in Asymmetric Transfer Hydrogenation of Aromatic Ketones

The second chiral alcohol which can be prepared by many ways is a kind of important intermediate in the synthesis of drug, pesticide and spice etc,a great of progress with fruitful results has been made by previous investigators, especially for the asymmetric hydride reaction .However, asymmetry transfer hydrogenation under mild conditions was just successfully reported in recent years, even so, there are still many difficulties for practical application. Thus, it is pivotal to design excellent chiral ligands and select ordinary catalytic conditions. On this background, we designed and synthesized some kinds of new chiral ligands, their properties on asymmetric transfer hydrogenation of aromatic ketones were also studied carefully.1. 9-Amino(9-deoxy)epicinchonine was synthesized from cinchonine through the Mitsunobu reaction and treated with 8-quinolinesulfonyl chloride, benzenesulfonyl chloride, p-toluenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride respectively to give four chiral sulfonamides, these sulfonamides were used as ligands for transfer hydrongenation of acetophenone.The optimal catalytic conditions and results are as follow: for 9-(8-quinoline sulfonamino)-(9-deoxy)epicinchonine: the higheat yield (90.8%) can be obtained when acetophenone/Ru/KOH(mole ratio)=50/1/1.25;for 9-(benzene sulfonamino)-(9-deoxy) epicinchonine,9-(toluene sulfonamino)-(9-deoxy) epicinchonine and 9-(p-chlorobenz- ene sulfonamino)-(9-deoxy)epicinchonine: the higheat yields(60.9%、96.0%、45.5% respectively) can be obtained when acetophenone/Ru/KOH=50/1/2.5.All the reactions were occurred with isopropanol as both hydrogen source and solvent at 80℃for 48 h, KOH was used as a base, all of which obtained no enantioselectivities.2. Chiral amino amides hydrochloride were easy to synthesize with Boc as the protection group for the amino group of L-proline, then diamines were doubly acylated with Boc-L-proline with condensation agents(DCC) to provide the Boc-protected bisamides, N-Boc-protecting groups were removed selectively and afforded dihydrochloride at the same time with dry HCl in methanol. Their application to asymmetric transfer hydrogenation of acetophenone in aqueous media was researched. The optimal catalytic condition is keton/Ru/L /HCOONa=100/1/1/500,used degassed water as solvent at 40℃for 24 h, the classic conversion rate for N,N′-Bis[(L)-prolyl]ethylenediamine dihydrochloride(98.2%), for N,N′-Bis[(L)-prolyl] phenylenediamine dihydrochloride(75.2%),for 4,4′-N,N’-Bis[(L)-prolyl] diaminodiphe- nyl ether dihydrochloride(97.7%), for 4,4′–N,N′-Bis[(L)-prolyl] diamino- biphenyl dihydrochloride(97.7%) was achieved, and 33.4%, 55.8%, 64.1%, 70.4% enantiomeric excess was obtained respectively, through the experiments the excellent ligand was screened and afforded excellent conversion rates and good enantioselectivities in asymmetric transfer hydrogenation of aromatic ketones .3. New chiral amino alcohols (1S,2R)-1-(N-methyl-cyclohexylamine)-2-hydroxy -7,7-dimethyl bicyclo[2.2.1] heptane and (1S,2R)-1-(N-methyl-piperidyl)-2-hydroxy- 7,7-dimethyl bicyclo[2.2.1] heptane were synthesized from (+)-camphor. After sulfonation of the camphor, 10-camphorsulfonic acid was first synthesized , followed by reaction with thionyl chloride, potassium permanganate to obtained (1S)-7,7- dimethyl bicyclo[2.2.1] heptane -1- carboxyl -2- Keto by step gradually, treated the product with thionyl chloride to form acyl chloride , after the operation of amidation and reduction to give products.The new ligands had been applied in transfer hydrogenation of acetophenone without any catalytic activities. Treated the amino alcohols with HCl/CH3OH to obtained two chiral amino alcohols hydrochloride, both of them were used in transfer hydrogenation. However, only 2.8% of conversion rates without enantioselectivities were obtained.