• Volume 30,Issue 5,2013 Table of Contents
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    • >Functional materials
    • Controlled synthesis of carbon encapsulating metal cores nano-composites by chemical vapor deposition

      2013, 30(5).

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      Abstract:To control synthesis of carbon encapsulating metal nano-particles, the reations were carried out at 400 ℃ and using iron supported on sodium chloride as catalyst which contain about 0.3, 1.6, 3.3 and 5.2 wt% of iron. The samples were examined by scanning electron microscopy and high resolution transmission electron microscopy. The results show that carbon encapsulating Fe cores nano-particles with diameters in the range 20-50 nm and the mean diameter 30 nm were obtained using the catalyst containing 0.3wt% iron. When using the catalyst containing iron of 1.6 wt%, the product with diameters in the range 35-60 nm and the mean diameter 49 nm was obtained. While using the catalyst containing iron of 3.3 and 5.2wt%, there was no obvious difference in diameter of the two products, and the product with diameters in the range 40-100 nm and the mean diameter 65 nm was obtained.

    • >Surfactants
    • Synthesis of Amphiphilic Extended Copolymers and the Influence of Intermediate Polar Block on Emulsifying Properties

      2013, 30(5).

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      Abstract:The amphiphilic triblock copolymer poly(ethylene glycol)-co-polylactide-co-poly(ε-caprolactone) (PEG-PLA-PCL) with increasing PLA block ratio and corresponding diblock copolymer poly(ethylene glycol)-co-poly(ε-caprolactone) (PEG-PCL)were prepared using ring-opening polymerization of d,l- lactide and ε- caprolactone initiated by monomethoxy poly(ethylene glycol)(Mn=1900, 5000). The structure of the target copolymers was confirmed by means of FT-IR,1H-NMR spectra and GPC, then emulsifying properties of the copolymers and low molecular surfactants were studied and their relationship with the block ratio of the intermediate polar block PLA in triblock copolymers was discussed in detail. The results indicate that all of the copolymers can emulsify the toluene/water system and the emulsions were oil-in-water type. The copolymers show better emulsifying properties than the low molecular surfactants, and the emulsifying ability of the copolymers first increased and then decreased with the increase of PLA block ratio. It is because that the interactions with water and oil phase are enhanced by inserting intermediate polar block PLA, leading to a thicker interfacial membrane. To achieve optimum emulsifying performance, longer intermediate polar block was required for PEG1900-containing copolymers than that for PEG5000-containing copolymers.

    • Green Synthesis of Novel Alkyl Amidopropyl Trimethyl Quaternary Ammonium Surfactants

      2013, 30(5).

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      Abstract:C16/C18 alkyl amidoproyl trimethyl ammonium mono-methyl carbonate was synthesized via a high pressure process with tertiary amines and dimethyl carbonate, the chemical structure of which was confirmed using mass spectral fragmentation and FTIR spectroscopic analysis. In addition, several quaternary ammonium salts with new counterions X- (X= HCOO, CH3COO, CH3CH(OH)COO) were also synthesized by ion exchange reaction of methyl carbonate quaternary ammoniums with corresponding acids. The surface activities of these quaternary ammonium salts were studied. The results show that counterion chain length has effect on the surface tension.

    • Relationship between O/W Interfacial Tension and Composition of Decyl Naphthalene Sulfonate Surfactant

      2013, 30(5).

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      Abstract:An intermediate decyl naphthalene (DN) was synthesized by Lewis acidic ionic liquid catalyzed Friedel-Crafts alkylation reaction from naphthalene and α-decene, and the structure of DN was identified by FT-IR and 1H NMR. Decylnaphthalene sulfonates (DNS), the anionic flooding surfactants with identified structure,tunable composition and Krafft point below 0 ℃ were synthesized from DN following by sulfonation and neutralization, and the compositions of DNS were determined by HPLC-MS. The interfacial tensions of aqueous DNS solutions against normal paraffin simulated oil phases were measured. The experimental results showed that products DNS1-1 and DNS3 could decrease the O/W interfacial tensions to 10-3 mN/m within the lower surfactant concentrations of 0.25 wt.%~0.4 wt.% and played good salt tolerance simultaneously. It was noted that the composition stability and the phenomena of composition-dependent ultralow interfacial tensions were reproducible for different batches of DNS1-1.

    • Resin material application in the alkyl poly-glycosides decolorization technology

      2013, 30(5).

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      Abstract:The dynamic adsorption decolorization technology of alkyl poly- glycosides surfactant with weak basic anion-exchange resins was studied. The decolorization products of PH is no evident change, it also has good stability, high transparency and clarification, no flocculent deposition; no bad smell; inorganic salt is low quantity percent, operation method is brief and rapid, which macro-porous weakly basic anion exchange resins is easy regeneration. Absorbance is 0.058 at 470nm wavelength. At Strengthening Experimental, the absorbance is 0.051 within 72h.Through measurement technique of IR and gas chromatography proved that the structure of alkyl poly-glycosides surfactant remain unchanged.

    • Synthesis and Properties of Long Chain Fatty Alcohol Polyoxyethylene Ether Propionate

      2013, 30(5).

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      Abstract:A new kind of surfactant, fatty alcohol polyoxyethylene ether propionate ( symbolized as AEP), was synthesized with fatty alcohol polyoxyethylene ether, methyl acrylate , sodium hydroxide as raw materials. The structures of them are characterized by IR and MS. The surface tension and oil-water interfacial tension have been measured. The results show that the cmc and γcmc of C12AEP respectively are 0.236 mmol•L-1 and 26.63 mN•m-1 at 25℃. The micropolarity of the surfactant also are determined from the ratio of intensity of peaks(I3/I1) of pyrene fluorescence emission spectrum.The I3/I1 of C12AEP micelle shows that its micropolarity is smaller than that of traditional surfactants.The interfacial tension of AEP is influenced by hardness, salinity and the proportion of complex systems by mixing with amphoteric surfactant (B) . Ultralow interfacial tension of 3.98×10-3mN/m can be formed in the water-oil interface ,so AEP can be applied to the three exploitation of oil.

    • >Biological engineering
    • Research on the immobilization of S-adenosylmethionine synthetase with sodium alginate-gelatin

      2013, 30(5).

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      Abstract:S-adenosylmethionine(SAM) synthetase was immobilzed on sodium alginate-gelatin and then cross-linked with glutaraldehyde for improving the stability of the immobilized enzyme. Properties of the immobilized enzyme were identified. The results showed the optimal conditions for the immobilization of the enzyme were as follows: the mass fraction of sodium alginate, gelatin and calcium chloride was 2.0%, 1.0% and 4.0% respectively; the amount of enzyme was 2.5 mg/mL gel; the volume fraction of glutaraldehyde was 0.6%. The cross-linked immobilized enzyme showed a good stability compared with the free enzyme. After incubation at 50℃ for 5 h the immobilized enzyme maintained 72% of the original activity while the free enzyme lost all activity. The cross-linked immobilized enzyme showed a good stability in alkaline solution. It still kept more than 87% of the original activity when incubated in the buffer of pH 8.0~pH9.0 on 4 ℃ for 10 h. The cross-linked immobilized enzyme was employed to synthesize the SAM and it remained 65% activity after eight times repeated operations.

    • Chemo-enzymatic synthesis of D-serine

      2013, 30(5).

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      Abstract:The substrate DL-5-hydroxymethylhydation was synthesized in a chemical process from DL-serine by amino acid cyclization method with the yield of 93.5%. And then D-serine was produced by the biotransformation of DL-5-hydroxymethylhydation under the condition of pH 9.0,temperature of 38℃ and the conversion time for 42 hours with the yield of 81.7%.

    • >Modernization technology of traditional Chinese medicines
    • The research of extraction and measure technique and antioxidant activity of Flavonoids from leaves of Chenopodium glaucum L.

      2013, 30(5).

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      Abstract:Quantitative method of flavonoids from leaves of Chenopodium glaucum(FLCG) was optimized using UV-vis spectrophotometry. In order to research the optimized extract technology of FLCG, the single factor trials and response surface methodology were involved. Except these, the anti-oxidant function of FLCG was evaluated by O2-?and ?OH radical. The results showed that it was feasible to measure the contents of FLCG with 3% AlCl3 at 273.5nm. RSD was 1.42%,1.83%,0.86%and 0.60%, respectively. The optimal condition was as follows : the ethanol concentration was 57%, solid-liquid ratio was 1:20 and microwave power was 500W for 7.8 minutes. Under this procotol, the yield of FLCG was 3.292%. FLCG had excellent scavenging effect on ?OH and O2-? radical in this research, the scavenging effect of FLCG on antioxidant activity had a positive correlation with its concentration.

    • >Catalysis,separation and purification technology
    • Characterization of SO42-/ZrO2-MgO Solid Acid Catalyst and Its Catalytic Activity in the Synthesis of Cellulose Acetate Propionate

      2013, 30(5).

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      Abstract:Solid acid catalyst SO42-/ZrO2-MgO was prepared by impregnation and was characterized by means of XRD, FTIR, NH3-TPD. The characterization results indicated that the addition of Mg in SO42-/ZrO2 was beneficial to the formation of tetragonal crystalline t-ZrO2 and increase the acid strength and acid amount. The catalyst SO42-/ZrO2-MgO was used in cellulose acetate propionate (CAP) synthesis. The catalyst containing the ZrO2/MgO molar ratio of 15/1 and being calcined at 500 ℃ showed the best catalytic activity. The yield of CAP reacted at 50℃ for 8 h was up to 116.40%.

    • Purification, characterization and ring-opening polymerization of cyclic dimer of butylenes succinate

      2013, 30(5).

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      Abstract:Cyclic dimer of butylene succinate (CDBS) was purified from the crude cyclic oligomers of butylene succinate. The purified CDBS was characterized by 1H NMR spectrum and mass spectra. The purified CDBS was subjected to ring-opening polymerization (ROP) to obtain poly(butylene succinate) (PBS) with 1-dodecanol as the initiator and tin octoate as the catalyst. The resultant PBS was characterized by Fourier transform infrared (FTIR) spectroscopy and 1H NMR spectrum. The effect of ROP temperature, ROP time and catalyst content on molecular weight of PBS and conversion were also investigated. The results show that, ROP can obtain the high-molecular-weight PBS, the highest number-average molecular weight (Mn) reached about 63.3 kDa in 3 h at 220 °C.

    • >Perfumes and essences
    • Study on the Rosemary Essential Oil Refined by Molecular Distillation Technology and its Application in Cigarette

      2013, 30(5).

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      Abstract:Rosemary essential oil was refined by molecular distillation technology and its physicochemical properties, volatile components and smoking quality were studied and compared with the unrefined rosemary essential oil. Results showed the refined rosemary essential oil had lighter color, purer fragrance, higher volatile component content, lower relative density, refractive index and acid value. The unrefined and refined rosemary essential oil had same variety but different relative contents of volatile components. In the refined rosemary essential oil, there were an upward trend in the relative contents of those volatile components had lower relative molecular weight and boiling point, and a downward trend in the relative contents of those volatile components had higher relative molecular weight and boiling point. In addition, the refined rosemary essential oil actively improved the sweet feeling and aroma of the tested cigarette and its suitable additive content was 0.002‰. When the addition contents of the two rosemary essential oils were both 0.002‰, the refined one had better smoking quality.

    • Synthesis of 4-(4-acetyl-5-methyl-1H-pyrrol-2-yl)-2′3′4′-trihydroxybutyl cinnamate and its Application in Unblended Cigarette

      2013, 30(5).

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      Abstract:Abstract: Under alkaline conditions in aqueous solution, 2-methyl -3-acetyl-5-1′,2′,3′,4′-tetrahydroxy butyl pyrrole were obtained by the reaction of D-glucosamine hydrochloride with acetyl acetone at reflux temperature, then take this chemical compound as raw material, reacted with cinnamic acid to synthesis the 4-(4-acetyl-5-methyl-1H-pyrrol-2-yl)-2,3,4-trihydroxybutyl cinnamate in the presence of DCC which was used as dehydrating agent. Its structure was characterized and verified by 1H NMR, 13C NMR, IR, and HRMS spectral analysis. Then the pyrolysis of the target product at 300, 600, 900°C respectively, and the application of the oil in cigarette flavoring were studied as well. The results showed that benzaldehyde, 2-methyl pyridine, farnesol and so on were detected at three temperatures. It is proved that when the target was ammount to 0.2% in tobacco, which could play an important role in enhancing the aroma quality and volume of smoke, reducing irritancy and improving the aftertaste.

    • >Drug and cosmetic materials
    • Semi-synthesis of taxol by technological improvement

      2013, 30(5).

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      Abstract:The C-13 side-chain precursor (4R,5S)-2,4-diphenyl-4,5-dihydroxazole-5- carboxylic acid was prepared from Cinnamic acid via epoxidation of C=C double bond with Oxone,benzyl protection, Ritter reaction, hydrolyzation, and resolution with (+)-Quinidine. Thus by linking it to 7-TES-Baccatin Ⅲ, taxol could be synthesized. The yield is 4.5% in the overall steps. Some intermediates and the target product were identified by means of 1H-NMR, 13C-NMR and MS.

    • A Simple and Efficient Method for The Synthesis of Vascular Disrupting Agent AVE-8063

      2013, 30(5).

      Abstract (1147) HTML (0) PDF 0.00 Byte (0) Comment (0) Favorites

      Abstract:A new synthetic protocol leading to vascular disrupting agent (Z)-3′-amino-3,4,4′,5-tetramethoxylstilbene (AVE-8063) was successfully devised. Starting from 4-methoxyphenylacetic acid, (E)-2-(3-bromo-4-methoxyphenyl)-3-(3,4,5-trimethoxyphenyl) acrylic acid (Ⅲ) could readily be obtained through bromination and Perkin condensation. Amination of (Ⅲ) afforded (E)-2-(3-animo-4-methoxyphenyl)-3-(3,4,5-trimethoxyphenyl)acrylic acid (Ⅳ), which was subsequently decarboxylated in Cu/1,10-Phen/PEG-400 system under microwave conditions for 6 min to give the target product (Ⅴ) with 60.1% total yield. The structure of the product was verified by IR, MS and 1H NMR.

    • Modification of β-Cyclodextrin with Dimethyl Carbonate under Different Temperature

      2013, 30(5).

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      Abstract:The modification effect of β-cyclodextrin by dimethyl carbonate in the temperature range of 50℃ to 170℃ was systematically studied at atmospheric and high pressure respectively, using dimethyl carbonate as green modification reagent and anhydrous potassium carbonate as alkaline catalyst in N, N-dimethylformamide. The products were purified through preparative HPLC, and characterized by means of IR, ESI-MS, 1HNMR and 13CNMR. The results showed that methoxycarbonylation derivatives with low degree of substitution were prepared in the temperature range of 50℃ to 85℃, and the major compound was mono-methoxycarbonyl-β-cyclodextrin, of which the yield reached 60.91%; the methylation and methoxycarbonylation of β-cyclodextrin occurred simultaneously in the range of 90℃ to 140℃; while when operating at the temperature from 160℃ to 170℃, and the pressure of approximately 1.40 MPa, randomly methylated β-cyclodextrins with the substitution degree range of 7 to 9 were obtained with a high yield from 80% to 85%.

    • >Food and feedstuff chemicals
    • Extract optimization of cow leather collagen polypeptide with complex enzyme by response surface methodology

      2013, 30(5).

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      Abstract:In the study, an extract technology of cow leather collagen polypeptide with complex enzyme preparation was discussed, using the cow leather collagen as experimental raw material, which was made in our lab. The adding procedure and proportion of the two kinds of enzyme including the papain and trypsin, were determined, the hydrolysis degree of collagen as indicator. Meanwhile, the optimizing interval of technical factors was obtained by single factor method. The experimental results showed that the optimal conditions of collagen polypeptide extraction from collagen protein were as follows, the proportion of enzyme activity of the papain and trypsin was 3:1, addition of 650 u/ml enzyme preparation, hydrolysis temperature of 50℃, pH 7.0 for 7h. The hydrolysis degree can reach 32.02% under the optimization conditions.

    • >Water treatment technology and environmental protection
    • Effect of coagulation temperature on structure and property of PVDF/PES-C blend membrane

      2013, 30(5).

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      Abstract:PVDF/ PES-C blend membranes were prepared via TIPS method by using DBP and DMAc as mixed diluents. The effect of coagulation temperature on membrane structure and property were examined. The membrane structure was observed through SEM and pure water flux was tested. The crystal property of membrane was examined with DSC and XRD method. The waste water treatment property was also checked by using the membrane in MBR. Both the highest melting temperature and the content of α crystal form in blend membrane increased along with the increase of coagulation temperature. A thinner skin layer and a porous support layer formed when the coagulation temperature was 25℃. At this temperature, the pure water flux and sewage flux had a maximum value and the MBR remove ratio of COD and NH4 -N reached the discharge standard.

    • >Oil field chemicals and petroleum additives
    • Study on a Hydrophobically Associating Cationic Polymer Applied for Acid Thickener

      2013, 30(5).

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      Abstract:Abstract: A hydrophobically associating cationic polymer P (DMC-HDMC) has been synthesized in aqueous solution by radical copolymerization, of which has been characterized in terms of infrared spectrum and fluorescence spectrum. Its acid solution properties have also been studied compared with polymer PDMC. Results have shown that, the structure of P (DMC-HDMC) was in consistent with what we have expected bearing long methane chain (CH2) 16; hydrophobic domain formed in aqueous solution and the critical associating concentration(CAC) of P (DMC-HDMC) was about 1700ppm; in 20wt% HCl solution, when the concentration of P (DMC-HDMC) were 0.16wt% (CAC), their corresponding outlet time were 20.47s and 40.8s respectively; apparent viscosity of PDMC in acid solution gradually decreased with increase of acid concentration, while P (DMC-HDMC) changed little and even slightly increased as a whole.

    • Synthesis and Evaluation of Fluid Loss Additive SJ-1 for Polyoxyethylene type

      2013, 30(5).

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      Abstract:Abstract: To improve the poor performance of fluid loss additive in high temperature resistance and salt resistance, this paper has introduced a novel monomer which has specific structure. The 2-acrylamido-2-methyl-propanesulfonic acid (AMPS), acrylamide(AM) and JM containing molecular side chain polyoxyethylene(C2H4O)n have been involved in the copolymerization of this filtrate reducer for drilling fluid SJ-1 of which performance has been evaluated. We have also discussed a serial of experimental factors and obtained the optimum scheme of copolymerization, which is, monomer mass is 15%, temperature of reaction is 60℃, dosage of initiator is 0.2%, molar ratio of monomer AM:AMPS:JM is 14:5:1. The results of infrared characterization have confirmed that the structure of our product is consistent with that of what we designed. Moreover, this polymer has shown good temperature resistance (200℃) and salt resistance (salt concentration up to 30%).

    • >Adhesives
    • Preparation and Characterization of Polyurethane Dispersions with MDI by Pelleting Process

      2013, 30(5).

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      Abstract:With Diphenylmethane diisocyanate(4,4,-MDI),2,2-(hydroxymethyl butyric acid(DMBA), poly(1,4-butylene adipate glycol) (PBA ,Mn=3000),1, 4 - butanediol(BG)and triethylamine(TEA), polyurethane dispersions(PUDs) was prepared by pelleting process. Results showed that the average particle sizes and particle size distribution of PUDs were mostly in the range of 59~215nm and 20~200nm respectively. The viscosities of PUDs were mostly less than 960mPa.s and increased with the increased of carboxyl content. The viscosity of PU acetone solutions were greater than 5000mPa.s and had trend of rise-fall with the increase of R value[R= n (-NCO)/n(-OH)]. TEM analysis showed spherical shapes of the particles with different sizes and multivariate distribution. The water absorption of the PUDs films were less than 2%.

    • >Building chemicals
    • Preparation and Performance of Polycarboxylate Terpolymer Superplasticizer MAPEG-HEA-SMAS

      2013, 30(5).

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      Abstract:Polycarboxylate terpolymer superplasticizer of MAPEG-HEA-SMAS was sunthesized by copolymerization with esterification intermediate(MAPEG),hydroxyethyl acrylate(HEA)and sodium methallyl sulfonate(SMAS)as main raw materials. The influence of molar ratio of monomer,dosage of initiator,reaction temperature and reaction time on the copolymerization were investigated. The structure was characterized by IR. Relative molecule mass and its distribution of superplasticizer is measured by GPC, and the microstructure of cement is characterized by SEM. The results show that when the molar ratio of MAPEG to MA to SMAS is 1.0:1.0:1.5,the polymerization reaction temperature is 88℃,the polymerization reaction time was 7.5h, the dosage of initiator is 3.5% of total monomer mass and the relative molecule of PEG mass is 1000,the superplasticizer prepared under this condition would exhibit good performance.The original fluidity of cement grout can reach 308mm with 0.45% percentage mass content of this superplasticizer(mass fraction).GPC shows that the mean molecular weightMn)and polydispersity Mw/Mn of the superplasticizer is 7752 and 2.091.SEM shows the amount of macropors of cement added with the polymerization reduce, and the crystals grow more dense.

    • >Fine chemical intermediates
    • Synthesis of 5-fluoro-6-ethyl-4- hydroxy-pyrimidine

      2013, 30(5).

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      Abstract:The key intermediate of voriconazole, 5-fluoro-6-ethyl-4-hydroxy-pyrimidine was synthesized by a "One pot" ammoniated and cyclization reaction with α-fluoro-ethyl propionyl as raw material. The optimal reaction conditions is: sodium methoxid, ammonia stirred in methanol at room temperature for 5 hours, then added carboxamide; stirred under reflux for another 5 hours; the over all yield of is 63%.

    • Analysis of Chemical Component of Lignin Extract from Malania oleifera

      2013, 30(5).

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      Abstract:Lignins were extracted from Malania oleifera shell and branch by traditional alkaline method, ultrasound-assisted method and microwave-assisted method.The yields and the contents of lignins in Malania oleifera shell and branch were determined. Meanwhile, the lignins obtained were structurally analyzed by infrared and (IR) and UV spectroscopy. The contents of lignin in Malania oleifera shell and branch were 44.41(±0.65)% and 34.57(±0.52)% respectively by Klason method, the lignins extraction rates reached 45.21(±0.59)% and 63.78(±0.73)% respectively from Malania oleifera shell and branch under the conditions of ultrasound- assisted extraction at 40℃ water bath for 1 hour with 0.5 mol/L KOH water as the solvent and the solvent/material ratio of 30:1 (mL/g). UV and IR spectral analyses showed that the lignin extracted by ultrasound-assisted method remained its original structure,there were many syringyl and guaiacyl groups in Malania oleifera shell and branch. And compared the relative molecular weight of lignins extracted by three different extraction methods with viscosity method.

    • Synthesis of 2-Bromo-6-Fluorotoluene derivates

      2013, 30(5).

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      Abstract:2-Bromo-6-fluorobenzyl bromide,2-Bromo-6-fluorophenyl methanol, 2-Bromo-6-fluorobenzoic acid and 2-Bromo-6-fluorobenzaldehyde were prepared from 2-Bromo-6-fluorotoluene by bromination,hydrolysis,oxidation and Sommlet reactions.And the synthesis process had been studied in this paper.The result showed that HBr/H2O2 as brominate agent,the yield of 2-Bromo-6-fluorobenzyl bromide was 90.3%;ethanol as solvent,the yield of 2-Bromo-6-fluorophenyl methanol was 92.8%;In the oxidation reaction,2-Bromo-6-fluorobenz- oic acid gived 58.2% with KMnO4,and under the condition of n(2-Bromo-6-fluoro benzyl bromide):n(Methenamine)=1.0:1.3,the yield of 2-Bromo-6-fluorobenzaldehyde was 79%.All products structures were characterized by nuclear magnetic resonance and infrared.