- Improved Synthesis of Unsymmetrical Carbonate Derivatives Using Calcium Salts
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An effective synthetic method for unsymmetrical carbonate species has been developed. Calcium oxide and calcium hydroxide were found to be highly effective for this reaction, affording unsymmetrical carbonates in high yield and purity. Calcium chloride, which is a coproduct, serves as a water scavenger that can be easily removed. Additional drying processes and complicated purification steps are not necessary in this reaction. This improved process is important in terms of green sustainable chemistry principles.
- Hamada, Tomohito,Okada, Michiaki,Yamauchi, Akiyoshi,Kishikawa, Yosuke
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Read Online
- Methylchloroformate synthesis via direct interaction of palladium di(methoxycarbonyl) complexes with CuCl2: utilization in the synthesis of carbonates and carbamates
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ClCOOCH3 has been obtained in very good yield by reaction of (L2 = 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen)> with CuCl2.The in situ reaction of ClCOOCH3 with alcohols or amines produces carbonates or carbamates.
- Giannoccaro, Potenzo,Ravasio, Nicoletta,Aresta, Michele
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Read Online
- Bronsted Plots in the Reactions of 2,4-Dinitrophenyl Acetate and Methyl Phenyl Carbonate with Substituted Pyridines
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Rate constants are reported for nucleophilic attack of a series of 3- or 4-substituted pyridines on 2,4-dinitrophenyl acetate and methyl phenyl carbonate at 25 deg C, and ionic strength 0.2 M.The Bronsted plot obtained is curved for the acetate and linear for the carbonate.The first shows two linear regions (at low and high pKa values with slopes 0.85 and 0.2, respectively) and a curvature in between.The Bronsted slope for the carbonate is 1.3.The Bronsted curve can be accounted for in terms of a tetrahedral intermediate in the reaction path and a change in the rate-determining step from breakdown of the intermediate to its formation, as the substituted pyridine becomes more basic.A semiempirical equation based on these assumptions fits the experimental data.From the shape of the curved Bronsted plot, an equal leaving ability from the tetrahedral intermediate for 2,4-dinitrophenolate and a (hypothetical) pyridine of pKa = 7.3 is deduced.The influence of the group that does not leave on the relative leaving abilities of phenolates and pyridines is discussed.
- Castro, Enrique A.,Freudenberg, Margarita
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Read Online
- Light-induced synthesis of unsymmetrical organic carbonates from alcohols, methanol and CO2under ambient conditions
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The present work describes the first visible light-assisted, metal-free and organic base 1,1,3,3-tetramethyl guanidine (TMG) mediated synthesis of unsymmetrical methyl aryl/alkyl carbonates from the reaction of alcohols, methanol, and CO2 in high to excel
- Saini, Sandhya,Gour, Nand Kishor,Khan, Shafiur Rehman,Deka, Ramesh Chandra,Jain, Suman L.
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supporting information
p. 12800 - 12803
(2021/12/13)
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- Selective O-Methylation of Phenol with Dimethyl Carbonate over Catalysts Supported on CaO
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Abstract: In this work CaO-based catalysts were found to be efficient heterogeneous catalysts for the methylation of phenol with dimethyl carbonate (DMC) in a closed high pressure reactor. The optimization experiments have been carried out to obtain best phenol conversion and the results showed that CaO catalyst modified with KCl had the best catalytic performance. When the reaction was carried out at 200°C, with phenol to dimethyl carbonate molar ratio of 1 : 2, 15% KCl/CaO catalyst dosage of 3%, reaction time 9 h, 100% conversion of phenol and 95% selectivity towards anisole have been achieved. The structure and properties of the materials were thoroughly characterized by Fourier transform infrared spectrometry (FTIR), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET). The close correlation was found between surface basicity of the catalysts and their catalytic performance for phenol conversion and anisole selectivity.
- Chen, Shijun,Li, Shaoying,Tang, Ying,Xu, Zhongying,Zhang, Zhifang
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p. 496 - 506
(2021/08/23)
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- Synthetic method of carbonic ester compound
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The invention provides a synthetic method of a carbonic ester compound, and belongs to the technical field of battery electrolytic solution additives. The method comprises the following steps: adding dichloromethane and trifluoroethanol into a reaction ke
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Paragraph 0032-0038
(2021/06/06)
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- Diphenyl carbonate compound preparation method
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The invention relates to the field of diphenyl carbonate synthesis, and discloses a diphenyl carbonate compound preparation method, which comprises: in the presence of a catalyst represented by a formula (1-1) or a formula (1-2), carrying out a transesterification reaction on a phenol compound represented by a formula (II) and a diester carbonate compound represented by a formula (III), wherein R1, R2 and R3 are selected from a C1-C14 aliphatic hydrocarbon group, a C3-C14 cycloalkyl group, a C6-C14 aryl group, a C7-C14 alkylaryl group, a C7-C14 aralkyl group and a C10-C14 condensed ring aryl group, and X is halogen. The method is high in catalytic activity, high in selectivity and good in stability. Formula (1-1) is (H-[O-Si-(R1)2]n-O)x1-Ti-(OR3)y1X(4-x1-y1), and formula (1-2) is [Si(R2)xO]x2-Ti-(OR3)y2X(4-x2-y2).
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Paragraph 0110; 0111; 0119-0139
(2020/04/01)
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- Catalyst for preparing diphenyl carbonate compound, preparation method and applications thereof
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The invention relates to the field of diphenyl carbonate compound synthesis, and discloses a catalyst for preparing a diphenyl carbonate compound, a preparation method and applications thereof, wherein the catalyst is represented by a formula (1-1) or a formula (1-2), R1, R2 and R3 are selected from C1-C14 aliphatic hydrocarbon groups, C3-C14 cycloalkyl groups, C6-C14 aryl groups, C7-C14 alkaryl groups, C7-C14 aralkyl groups and C10-C14 condensed ring aryl groups, and X is halogen. The catalyst used in the method has high catalytic activity, high selectivity and good stability in a reaction for preparing diphenyl carbonate through a transesterification method. The formula (1-1) is (H-[O-Si-(R1)2]n-O)x1-Ti-(OR3)y1X(4-x1-y1), and the formula (1-2) is [Si(R2)xO]x2-Ti-(OR3)y2X(4-x2-y2).
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Paragraph 0119-0121
(2020/04/01)
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- Method for preparing diphenyl carbonate through interesterification
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The invention relates to a method for preparing diphenyl carbonate through interesterification of dimethyl carbonate and phenol. The problem of low activity of heterogeneous catalysts in the prior artis mainly solved. A catalyst is a titanium oxide system with high proportion exposure of a (001) crystal surface modified by a composite oxide. According to the technical scheme, catalyst activity and selectivity are improved effectively, the problem of low catalyst activity in a reaction of synthesis of the diphenyl carbonate through interesterification of the phenol and the dimethyl carbonate is well solved, and the method can be used for industrial production of the diphenyl carbonate.
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Paragraph 0053-0057
(2019/05/08)
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- Method for preparing diphenyl carbonate through phenol ester exchange
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The invention relates to a method for preparing diphenyl carbonate through dimethyl carbonate and phenol ester exchange reaction. The method mainly solves the problem of low activity of a heterogeneous catalyst in the prior art. A catalyst used in the method is titanium oxide with a (001) crystal face exposed at a high ratio. By means of the technical scheme, the activity and selectivity of the catalyst are effectively improved, the problem of low activity of the catalyst in the reaction of synthesizing the diphenyl carbonate through phenol and dimethyl carbonate ester exchange is well solved,and the method can be used for industrial production of the diphenyl carbonate.
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Paragraph 0048-0053
(2019/05/08)
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- Ti functionalized hierarchical-pore UiO-66(Zr/Ti) catalyst for the transesterification of phenyl acetate and dimethyl carbonate
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Titanates are frequently used as precursors to prepare transesterification catalysts with TiIV species. Unfortunately, it is challenging to control the dispersity of TiIV active sites on supports. Herein, a series of TiIV species is anchored on abundant linker vacancy sites by introducing point and large scale defects in UiO-66(Zr/Ti) with hierarchical-pore structure. The catalyst functionalized by titanium(iv) oxide bis(2,4-pentanedionate) shows excellent catalytic performance in the transesterification of dimethyl carbonate with phenyl acetate. The catalysts are characterized by XRD, FT-IR, N2 adsorption-desorption, XPS, SEM and STEM-HAADF techniques. The results demonstrate that the delicate mesopores in the support can not only exhibit a large surface area for the distribution of the active sites, but also provide better mass transfer performance. Meanwhile, the introduction of octahedral TiIV ions raises the activity of the catalyst via more coordinatively unsaturated ZrIV sites. Furthermore, using titanium(iv) oxide bis(2,4-pentanedionate) as a Ti source can effectively prevent the condensation of tetrahedral TiIV species anchored on the hierarchical-pore UiO-66(Zr/Ti) support.
- Jia, Bingying,Wu, Miaojiang,Zhang, Hua,Zeng, Yi,Wang, Gongying
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p. 16981 - 16989
(2019/11/14)
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- Preparation and catalytic property of Pb-Zr mixed oxides for methyl phenyl carbonate disproportionation to synthesize diphenyl carbonate
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Pb-Zr mixed oxides with 15.2 wt% PbO loading were prepared by four different preparation processes, and their catalytic performances for the disproportionation of methyl phenyl carbonate (MPC) to synthesize diphenyl carbonate (DPC) were evaluated. Physicochemical characterizations including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence spectroscopy (XRF), BET surface area measurement, H2-temperature programmed reduction (H2-TPR), ammonia temperature programmed desorption (NH3-TPD) and infrared spectroscopy of pyridine adsorption (Py-IR), as well as catalytic tests of MPC disproportionation reaction showed that catalyst preparation process exerted significant influence on the composition, structural property, catalytic performance of obtained catalysts, and the catalyst prepared by co-precipitation method (PbZr-CP) demonstrated better dispersion of active phase, larger specific surface area and more Lewis acid sites on the surface due to the strong interaction of Pb and Zr, and thus exhibited higher catalytic activity than those prepared by other processes.
- Wang, Songlin,Niu, Hongying,Wang, Jianji,Chen, Tong,Wang, Gongying
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- Production of diaryl carbonate
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The present invention provides a method for producing a diaryl carbonate and a method for producing an aromatic polycarbonate, and the method for producing the diaryl carbonate can remove the water, causing the degradation of a catalyst, in a manufacturing process of the diaryl carbonate without using a special device. The method for producing the diaryl carbonate of the present invention is a method for producing the diaryl carbonate from an aromatic monohydroxy compound and a dialkyl carbonate containing a compound represented by the following formula (1) in the presence of the catalyst, wherein The dialkyl carbonate contains 0.01 to 1000 mass ppm of the compound represented by the formula (1) in the dialkyl carbonate as a raw material (in the formula (1), R1, R2 R4 each independently represents an aliphatic group having 1 to 20 carbon atoms, and R3 represents a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms.
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Paragraph 0110; 0114; 0115; 0116
(2018/09/02)
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- Transesterification of dimethyl carbonate and phenol to diphenyl carbonate with the bismuth compounds
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Bismuth oxide was first employed for the transesterification of dimethyl carbonate with phenol to diphenyl carbonate, which has excellent catalytic activity. With 0.4?g Bi2O3, the phenol conversion of 46.4% and transesterification selectivity of 99.9% were attained. The characterization of the used sample by XRD, FTIR and solid-state 13C-NMR indicate that a new compound of bismuth phenoxide was formed with the disappearance of bismuth oxide. It was evidenced that the bismuth phenoxide act as the role of active phase in the transesterification, which was generated facilely in situ by the reaction of bismuth oxide added with the raw material of phenol. The bismuth phenoxide presents excellent reusability, after four consecutive runs, the phenol conversion remained above 45%, and the transesterification selectivity was maintained at 99.9%.
- Xiao, Zhongliang,Yang, Hao,Zhang, Hua,Chen, Tong,Wang, Gongying
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p. 2347 - 2352
(2018/08/06)
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- PRODUCTION METHOD OF ASYMMETRIC CHAIN CARBONATE
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A method for producing an asymmetric chain carbonate by reacting an alcohol with a halocarbonate ester compound in the presence of a basic magnesium salt.
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Paragraph 0125; 0132; 0137
(2019/01/04)
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- The method of transesterification process for production of diphenyl carbonate
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The invention relates to a method for preparation of diphenyl carbonate by ester interchange, and mainly solves the problems that a heterogeneous phase catalyst has low activity and selectivity, and proneness to inactivation. In the invention, dimethyl carbonate and phenyl acetate, whose mol ratio ranges from 0.1 to 5, serve as materials, react in the presence of a catalyst for 1-20 hours at a temperature of 120-190 DEG C to prepare diphenyl carbonate, wherein the weight ratio of the catalyst to the phenyl acetate ranges from 0.01 to 0.5, the catalyst is a mixture of two metal oxides AaOb/ BcOd; A is selected from Sn, Mn or Bi, and B is selected from Al, Ga, Fe, In, Zr or Cr. The method for preparation of diphenyl carbonate by ester interchange solves problems well and can be used in ester interchange of dimethyl carbonate and phenyl acetate for preparing diphenyl carbonate.
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Paragraph 0025; 0026; 0027-0040
(2018/04/01)
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- A ionic liquid catalyzed transesterification preparation of diphenyl carbonate method and device (by machine translation)
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The invention discloses a ionic liquid catalyzed transesterification preparation of diphenyl carbonate method and device, comprising the following steps: (1) phenol with dimethyl carbonate in the ionic liquid catalyst under the conditions of benzene methyl ester carbonate ester exchange reaction; (2) in the ionic liquid catalyst under catalytic conditions in the disproportionation reaction to obtain the product of the diphenyl carbonate; (3) at the vacuum degree of 5 - 7 mmHg under the condition of reduced pressure distillation, in purity 99.6% more than the product of the diphenyl carbonate. This invention adopts the liquid ion catalyst, by transesterification reaction, disproportionation rectification to realize the two-step process, avoiding the use of highly toxic phosgene, the corrosion of the apparatus small; without the use of noble metal as the catalyst, mild reaction conditions, the requirements for apparatus is relatively low, the cost is low; this method can make the product yield of the diphenyl carbonate ≥ 80%, purity ≥ 99.6%; the device of the invention is simple in structure, easy to operate, can be continuously produced, improve the productivity. (by machine translation)
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Paragraph 0030; 0031; 0041-0043; 0049; 0050; 0055-0059
(2017/08/31)
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- Zn-promoted synthesis of diphenyl carbonate via transesterification over Ti–Zn double oxide catalyst
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An environmentally friendly heterogeneous catalyst, Ti–Zn double oxide, was prepared using a sol–gel method and firstly used for the synthesis of diphenyl carbonate (DPC) via the transesterification of phenol and dimethyl carbonate. The catalyst exhibited excellent catalytic activity. Moreover, the effects of Ti to Zn molar ratio, calcination temperature and catalyst amount on the catalytic performances of Ti–Zn double oxide have been investigated. The characterization results of XRD, TGA–DSC, ICP-AES and NH3-TPD showed that amorphous TiO2 was the active sites, and amorphous ZnO was the promoter. Also the amount of Zn remarkably affected the acid amounts of the catalysts, and the calcination temperature not only influenced the acid amount, but also affected the acid strength. Besides, the weak surface acid sites were responsible for the synthesis of MPC and DPC, whereas the strong acid sites favored the formation of a by-product, anisole. The phenol conversion and the transesterification selectivity reached 41.2 and 98.2% over 0.3?g 5TiZn-250 for 8?h, respectively. Furthermore, the prepared catalyst could be reused for three runs without drastic decrease in activity. The slight decreased activity was attributed to the phase change of Ti–Zn double oxide and the leaching of Ti.
- Qu, Yingmin,Wang, Songlin,Chen, Tong,Wang, Gongying
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p. 2725 - 2735
(2017/04/18)
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- Preparation method of diphenyl carbonate
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The invention relates to a preparation method of diphenyl carbonate, and mainly solves the problems of low activity and selectivity of heterogeneous catalysts in the prior art. The method includes: a) contacting dimethyl carbonate and phenol with a catalyst to carry out ester exchange reaction, wherein dimethyl carbonate gradually enters the reaction system in the reaction process, at the same time a mixture of dimethyl carbonate and methanol are distilled off through a rectification column, thus obtaining a mixture containing methyl phenyl carbonate and the catalyst at the column bottom; b) further subjecting the mixture containing methyl phenyl carbonate and the catalyst to reaction, at the same time distilling off a disproportionated product dimethyl carbonate by the rectification column, thus obtaining the product diphenyl carbonate at the column bottom. Specifically, the catalyst is titanium dioxide microsphere@all-silicon Silica-1 molecular sieve core-shell catalyst, the core phase is TiO2 microspheres, and the shell layer is all-silicon Silica-1 molecular sieve. The technical scheme well solves the problems, and can be used for the industrial production of diphenyl carbonate from dimethyl carbonate and phenol.
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Paragraph 0047; 0048; 0065; 0066; 0069; 0070
(2017/05/16)
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- Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates
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An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2), was investigated as a “green” and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs.
- Lui, Matthew Y.,Yuen, Alexander K. L.,Masters, Anthony F.,Maschmeyer, Thomas
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p. 2312 - 2316
(2016/10/24)
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- Method for preparing diphenyl carbonate through transesterification
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The invention relates to a method for preparing diphenyl carbonate through transesterification. With prior arts, heterogeneous catalyst activity and selectivity are low, and the catalyst is prone to inactivation. The invention mainly aims at solving the above problems. According to the invention, dimethyl carbonate and phenyl acetate are adopted as raw material, and contact a catalyst for 1-20h under a reaction temperature of 120-190 DEG C, wherein a molar ratio of dimethyl carbonate to phenyl acetate is 0.1-5, and a weight ratio of the catalyst to phenyl acetate is 0.01-0.5. With the above reaction, diphenyl carbonate is produced. The catalyst is a binary mixed metal oxide AaOb/BcOd, wherein A is Sn, Mn or Bi; and B is Al, Ga, Fe, In, Zr or Cr. With the technical scheme, the problems are well solved. The method can be used in industrial productions for preparing diphenyl carbonate through the transesterification reaction of dimethyl carbonate and phenyl acetate.
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Paragraph 0025; 0026
(2017/03/14)
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- Alkyl and aryl 4,5-dichloro-6-oxopyridazin-1(6 H)-carboxylates: A practical alternative to chloroformates for the synthesis of symmetric and asymmetric carbonates
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Symmetric and asymmetric carbonates were synthesized by using alkyl or aryl 4,5-dichloro-6-oxopyridazin-1(6H)-carboxylates. Five aryl 4,5-dichloro-6-oxopyridazin-1(6H)-carboxylates were converted into the corresponding diaryl carbonates in good to excellent yields by treatment with potassium carbonate in refluxing THF. When the 4,5-dichloro-6-oxopyridazin-1(6H)-carboxylates were treated with aliphatic or aromatic alcohols in the presence of potassium tert-butoxide in toluene at room temperature, they gave the corresponding symmetric or asymmetric carbonates in moderate to excellent yields. Alkyl and aryl 4,5-dichloro-6-oxopyridazin-1(6H)-carboxylates are therefore efficient, stable, and ecofriendly alternatives to chloroformates.
- Moon, Hyun Kyung,Sung, Gi Hyeon,Yoon, Yong-Jin,Yoon, Hyo Jae
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supporting information
p. 1577 - 1581
(2016/06/14)
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- Ionic liquid catalysis transesterification preparation diphenyl carbonate's device
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This device discloses an ionic liquid catalysis transesterification preparation diphenyl carbonate's device, including reaction - rectifying column, first reboiler, first condenser, disproportionation ware, second condensing tower, distillation column, light component tower and product tower, export of reaction - rectifying column top of the tower and first condenser entry linkage, the export of first condenser divide into two branch roads, respectively with waste liquor recovery jar and reaction - rectifying column, export of reaction - rectification tata cauldron and disproportionation ware entry linkage, export of disproportionation ware top and second condenser entry linkage, the export of second condenser divide into two branch roads, be connected with waste liquor recovery jar and disproportionation ware respectively, export of disproportionation ware bottom and distillation column entry linkage, export of distillation column top and light component tower entry linkage, export and product tower entry linkage at the bottom of the light component tata. This device simple structure, easy operation, but serialization production can make result diphenyl carbonate's productivity >= 80%, purity >= 99.6%.
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Paragraph 0029; 0030; 0031
(2016/10/07)
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- INTEGRATED METHOD AND APPARATUS FOR THE PRODUCTION OF ARYL CARBONATES
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In an embodiment, a method for producing an alkyl aryl carbonate, comprises producing a dialkyl carbonate azeotrope stream comprising a dialkyl carbonate and an unreacted alkanol; purifying the dialkyl carbonate azeotrope stream in a dialkyl carbonate purification section comprising a distillation column and a pervaporation unit to provide a first purified dialkyl carbonate stream and a first purified alkanol stream; reacting the first purified dialkyl carbonate stream and an aromatic alcohol in the presence of a second transesterification catalyst in an alkyl aryl carbonate reactor to produce an alkanol product stream comprising an alkanol product and an unreacted dialkyl carbonate, and an alkyl aryl carbonate product stream comprising the alkyl aryl carbonate and an unreacted aromatic alcohol; and purifying the alkanol product stream in the dialkyl carbonate purification section.
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Paragraph 0071
(2016/10/11)
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- Acid-catalysed carboxymethylation, methylation and dehydration of alcohols and phenols with dimethyl carbonate under mild conditions
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Dimethyl carbonate (DMC) chemistry has been extended to include acid-catalysed reactions of different aliphatic alcohols and phenols. For the first time, p-toluenesulfonic acid (PTSA), H2SO4, AlCl3 and FeCl3 have been shown to aid carboxymethylation for primary aliphatic alcohols at catalytic loadings with quantitative conversion and selectivity. For carboxymethylation of secondary alcohols, stoichiometric PTSA and catalytic AlCl3 both gave quantitative conversion and selectivity. Stoichiometric FeCl3 and H2SO4 promoted dehydration of linear aliphatic alcohols. Additionally FeCl3 catalysed methylation of cyclohexanol, whilst AlCl3 resulted in methylation of phenolic compounds. This research expands the range of potential application for DMC in green chemistry.
- Jin, Saimeng,Hunt, Andrew J.,Clark, James H.,McElroy, Con Robert
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supporting information
p. 5839 - 5844
(2016/11/06)
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- Method for preparing diphenyl carbonate
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The invention relates to a method for preparing diphenyl carbonate to mainly solve the problems of low heterogeneous phase catalyst activity and low selectivity existing in the prior art. The method comprises the following steps: 1, allowing dimethyl carbonate and phenol to be in contact with a catalyst and to undergo an ester interchange reaction, wherein dimethyl carbonate gradually enters a reaction system in the reaction process, a dimethyl carbonate and methanol mixture is distilled off through a rectifying column, and a mixture containing methyl phenyl carbonate and the catalyst is obtained at column bottom; and 2, continuously reacting the mixture containing methyl phenyl carbonate and the catalyst, and distilling off a disproportionation product dimethyl carbonate through the rectifying column to obtain the product diphenyl carbonate at the column bottom, wherein he catalyst is a binary mixed metal oxide AaOb/BcOd, A is Sn, Mn or Bi, and B is Al, Ga, Fe, In, Zr or Cr. The method adopting the above technical scheme well solves the problems, and can be used in industrial production for preparing diphenyl carbonate from dimethyl carbonate and phenol.
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Paragraph 0030; 0031
(2017/01/02)
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- Methyl phenyl carbon ester preparation method
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The invention relates to a preparation method of methyl phenyl carbonic ester. Dimethyl carbonate and diphenyl carbonate serve as preparation raw materials. After diphenyl carbonate and a catalyst are placed in a rectification and purification reactor, the materials are slowly heated to 130-180 DEG C, dimethyl carbonate is dropwise added to the reactor slowly at the dropping speed of 0.5-15ml/ min, the temperature of reaction liquid is maintained for 1 hour, vacuum degree of the reactor is controlled to be 0.07-0.099MPa, the temperature of reaction liquid is slowly increased to 180-240 DEG C for rectification and purification, and the product of methyl phenyl carbonic ester is obtained when cut fractions at the temperature are collected. The preparation method of methyl phenyl carbonic ester can effectively resolve the problems that in the prior art, highly toxic raw materials are used, products obtained through reactions are toxic, product yield is not high, and a purification process is difficult and the like.
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Paragraph 0022; 0023
(2016/10/08)
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- Ester manufacturing method (by machine translation)
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PROBLEM TO BE SOLVED: To produce an ester compound by transesterification using an inexpensive and low toxic inorganic compound. SOLUTION: Transesterification of an ester compound and an alcohol compound is carried out under the presence of lanthanum nitrate (for example, lanthanum nitrate hexahydrate) and a phosphine compound (for example, tri-n-octylphosphine), thereby obtaining the ester product. For example, transesterification of dimethyl carbonate and benzyl alcohol is carried out under the presence of 1 mol% of lanthanum nitrate hexahydrate, and 2 mol% of tri-n-octylphosphine, thereby obtaining benzyl methylcarbonate at a yield of >99%. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0081; 0082
(2017/02/17)
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- CONTINUOUS METHOD FOR PREPARING AROMATIC CARBONATE USING A HETEROGENEOUS CATALYST AND A REACTION APPARATUS FOR THE SAME
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The present invention relates to a continuous method for the preparation of an aromatic carbonate by reacting a dialkyl carbonate and an aromatic hydroxy compound in the presence of a heterogeneous catalyst, and a reaction apparatus for the same. The cont
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Paragraph 0046; 0047; 0048; 0049
(2016/01/11)
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- Method of Preparing Aromatic Carbonate From Dialkyl Carbonate
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A method of preparing an aromatic carbonate includes reacting a dialkyl carbonate with an aromatic alcohol in the presence of a catalyst represented by Formula 1. With the method, aromatic carbonate can be prepared from a dialkyl carbonate in high yield u
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Paragraph 0041; 0043; 0049
(2015/11/27)
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- Synthesis of organic carbonates with alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates and ROH/AlCl3under ambient condition
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We demonstrated the synthesis of organic carbonates using alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates and alcohol in the presence of aluminum chloride. Alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates were reacted with alcohol in the presence of AlCl3 in toluene at room temperature to afford the corresponding unsymmetric and symmetric organic carbonates in good to excellent yields. These are efficient and convenient processes. Alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates are solid, stable and non-toxic CO2/CO2R(Ar) source. It is noteworthy that the reaction is carry out under an ambient and acidic conditions, the easy-to prepare and readily available starting materials and the quantitative isolation of reusable 4,5-dichloropyridazin-3(2H)-one.
- Sung, Gi Hyeon,Bo, Ram Kim,Ryu, Ki Eun,Kim, Jeum-Jong,Yoon, Yong-Jin
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p. 2758 - 2764
(2015/04/22)
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- Oxidative carbonylation of monohydroxy aryl compounds by methyl formate
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The field of the present invention relates to a process for continuously preparing alkylaryl carbonates and diarylcarbonates from methyl formate and at least one monohydroxy aryl compound in the presence of catalysts, and to the use thereof for preparatio
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Paragraph 0030
(2014/11/11)
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- METHOD AND APPARATUS FOR THE PRODUCTION OF DIARYL CARBONATE
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A method for production of diary carbonate, can comprise: introducing reactants to a first reactive distillation column (C21); recovering a first top stream (stream 5), a first bottom stream (stream 6), and a first side stream (stream 13); introducing the first bottom stream (stream 6) into a second reactive distillation column (C32) without passing through another reactive distillation column; recovering from the second reactive distillation column (C32) a second bottom stream (stream 15), and a second top stream (stream 16); introducing the first side stream (stream 13) to a first rectification column (C81); recovering from the first rectification column (C81) a third bottom stream (stream 12) and a third top stream (stream 14); introducing the first top stream (stream 5) into a second rectification column (C41); and recovering from the second rectification column (C41) a fourth top stream (stream 7) and a fourth bottom stream (stream 8).
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Paragraph 0042-0049
(2014/01/17)
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- METHOD AND APPARATUS FOR THE PRODUCTION OF DIARYL CARBONATE
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In an embodiment, a method for production of diaryl carbonate by reaction of a dialkyl carbonate and an aromatic alcohol in the presence of a transesterification catalyst, comprising: producing a first top stream (5) comprising dialkyl carbonate and alkyl alcohol from a first reactive distillation column (210); introducing a reactant stream (5') comprising the first top stream (5) to a first divided wall distillation column (DWC1 200) and separating the mixture with use of the first divided wall distillation column (DWC1 200); recovering from the first reactive distillation column (210) a first bottom stream (6) comprising alkyl aryl carbonate; and introducing the first bottom stream (6) into a second reactive distillation column (320) to produce a second bottom stream (15) comprising diaryl carbonate.
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Paragraph 0075-0084
(2014/01/17)
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- Method and apparatus for the production of diaryl carbonate
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A method for production of diaryl carbonate comprising: (a) introducing reactants to a first reactive distillation column (C21); (b) recovering a first top stream (stream 5), a first bottom stream (stream 6), and a first side stream (stream 13); (c) introducing the first bottom stream (stream 6) into a second reactive distillation column (C32) without passing through another reactive distillation column; (c1) recovering from the second reactive distillation column (C32) a second bottom stream (stream 15), and a second top stream (stream 16); (d) introducing the first side stream (stream 13) to a first rectification column (C81); (d1) recovering from the first rectification column (C81) a third bottom stream (stream 12) and a third top stream (stream 14); (e) introducing the first top stream (stream 5) into a second rectification column (C41); and (e1) recovering from the second rectification column (C41) a fourth top stream (stream 7) and a fourth bottom stream (stream 8). The apparatus comprising a first reactive distillation column (C21), a second reactive distillation column (C32), a first rectification column (C81), a second rectification column (C41), and a plurality of lines for transporting reactant and product streams is also claimed.
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Paragraph 0042 - 0047
(2014/01/17)
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- PROCESS FOR THE CONTINUOUS MANUFACTURE OF ARYL ALKYL CARBONATE AND/OR DIARYL CARBONATE USING VAPOR RECOMPRESSION
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In an embodiment, a process for preparing an alkyl aryl carbonate and a diaryl carbonate, comprising: reacting a dialkyl carbonate and an aromatic hydroxy compound in a production column 200, 300 to form the alkyl aryl carbonate and the diaryl carbonate; directing a bottom stream of the production column to a reboiler 205, 305, wherein the bottom stream comprises the alkyl aryl carbonate and the diaryl carbonate; heating the bottom stream in the reboiler 205, 305 with heat from an overhead stream of the production column 200, 300 to result in a heated bottom stream; directing a first portion of the heated bottom stream back into the production column 200, 300, wherein the first portion comprises phenol; and collecting the diaryl carbonate and the alkyl aryl carbonate from a second portion of the heated bottom stream.
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Paragraph 0051
(2014/04/03)
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- Methyl formate as a carbonylating agent for the catalytic conversion of phenol to methyl phenyl carbonate
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Methyl formate was used as a green and efficient carbonylating agent in the synthesis of methyl phenyl carbonate from phenol. Methyl formate showed better performance compared to toxic CO gas and the ability to produce other useful carbonylated products, e.g., dimethyl carbonate and dimethyl oxalate.
- Yalfani, Mohammad S.,Lolli, Giulio,Wolf, Aurel,Mleczko, Leslaw,Mueller, Thomas E.,Leitner, Walter
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supporting information
p. 1146 - 1149
(2013/06/05)
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- Non-symmetrical dialkyl carbonate synthesis promoted by 1-(3-trimethoxysilylpropyl)-3-methylimidazolium chloride
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An efficient synthesis of non-symmetrical dialkyl carbonates promoted by 1-(3-trimethoxysilylpropyl)-3-methylimidazolium chloride ionic liquid as a reaction medium is described. The ionic liquid can easily be recovered and reused several times without sig
- Kumar, Subodh,Jain, Suman L.
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supporting information
p. 3057 - 3061
(2013/10/01)
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- Aromatic carbonate, method of preparing the same, and polycarbonate prepared using the same
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A method of preparing aromatic carbonate from dialkyl carbonate includes reacting an aromatic hydroxyl compound and dialkyl carbonate in the presence of at least one type of samarium-containing catalyst represented by Formula 1, Formula 2, or a combinatio
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Page/Page column 5-7
(2013/11/19)
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- C,N-chelated organotin(IV) compounds as catalysts for transesterification and derivatization of dialkyl carbonates
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The potential catalytic activity of selected C,N-chelated organotin(IV) compounds (e.g. halides and trifluoroacetates) for derivatization of both dimethyl carbonate (DMC) and diethyl carbonate (DEC) was investigated. Some tri-, di- and monoorganotin(IV) species (LCN(n-Bu)2SnCl (1), LCN(n-Bu)2SnCl.HCl (1a), LCN(n-Bu) 2SnI (2), LCNPh2SnCl (3), LCNPh 2SnI (4), LCN(n-Bu)SnCl2 (5), L CNSnBr3 (6) and [LCNSn(OC(O)CF 3)]2(μ-O)(μ-OC(O)CF3)2 (7)) bearing the LCN moiety (LCN = 2-(N,N-dimethylaminomethyl) phenyl-) were assessed as catalysts for reactions of both DMC and DEC with various substituted anilines. The catalytic activities of 4 and 7 for derivatization of DMC with p-substituted phenols were studied for comparison with the standard base K2CO3/Silcarbon K835 catalyst (catalyst 8). The composition of resulting reaction mixtures was monitored by multinuclear NMR spectroscopy, GC and GC-MS techniques. In general, catalysts 1, 3 and 7 exhibited the highest catalytic activity for all reactions studied, while some of them yielded selectively carbonates, carbamates, lactam or substituted urea. Copyright
- Weidlich, Tomas,Dusek, Libor,Vystrcilova, Barbora,Eisner, Ales,Svec, Petr,Ruzicka, Ales
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p. 293 - 300
(2012/10/07)
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- Aromatic carbonate, method of preparing the same, and polycarbonate prepared using the same
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Disclosed herein is a method of preparing aromatic carbonate from dialkyl carbonate. The method includes reacting an aromatic hydroxyl compound and dialkyl carbonate in the presence of at least one type of samarium-containing catalysts represented by Form
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Page/Page column 5-7
(2012/07/14)
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- DBU-promoted nucleophilic activation of carbonic acid diesters
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The reactivity of carbonic acid diesters in the presence of the amidine base DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) has been investigated for the first time. Organic carbonates can be activated by DBU through the formation of N-alkoxycarbonyl ketene aminal 2 as the ultimate product. The latter species may form through deprotonation of the corresponding N-alkoxycarbonyl-amidinium cation 1+ by the amidine base. We have for the first time isolated and characterized, both in the solid state (X-ray crystal structure determination, IR) and in solution (NMR), a few 1+ chloride salts and studied their reactivity towards the organic base. The reactivity of both 1+ and 2 with methanol has also been explored. Ketene aminal 2 behaves as a "CO2R" carrier, as it can selectively transfer the alkoxycarbonyl group to the alcohol and regenerate the amidine base. Carbonic acid diesters can be activated by the amidine base DBU to give N-alkoxycarbonyl ketene aminal 2. The latter species may form through deprotonation of N-alkoxycarbonyl-amidinium cations 1+ by the amidine base and behave as carriers of the -C(O)OR group. Copyright
- Carafa, Marianna,Mesto, Ernesto,Quaranta, Eugenio
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p. 2458 - 2465
(2011/06/10)
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- Activated metallic gold as an agent for direct methoxycarbonylation
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We have discovered that metallic gold is a highly effective vehicle for the low-temperature vapor-phase carbonylation of methanol by insertion of CO into the O-H bond to form methoxycarbonyl. This reaction contrasts sharply to the carbonylation pathway well known for homogeneously catalyzed carbonylation reactions, such as the synthesis of acetic acid. The methoxycarbonyl intermediate can be further employed in a variety of methoxycarbonylation reactions, without the use or production of toxic chemicals. More generally we observe facile, selective methoxycarbonylation of alkyl and aryl alcohols and secondary amines on metallic gold well below room temperature. A specific example is the synthesis of dimethyl carbonate, which has extensive use in organic synthesis. This work establishes a unique framework for using oxygen-activated metallic gold as a catalyst for energy-efficient, environmentally benign production of key synthetic chemical agents.
- Xu, Bingjun,Madix, Robert J.,Friend, Cynthia M.
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experimental part
p. 20378 - 20383
(2012/02/06)
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- Transesterification of dimethyl carbonate with phenol using Br?nsted and Lewis acidic ionic liquids
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Transesterification reaction of dimethyl carbonate with phenol to methylphenyl carbonate and diphenyl carbonate using dibutyltin oxide catalyst in conjunction with Br?nsted and Lewis acidic ionic liquids was studied. It was observed that the use of ionic liquids significantly enhances the yield of diphenyl carbonate. The ionic liquid having p-toluenesulfonate as anion and metal halide (e.g. ZnCl2) as Lewis acid precursor exhibited higher activity and selectivity for diphenyl carbonate formation. Furthermore, the Br?nsted and Lewis acidity of ionic liquids was measured by IR spectroscopy using pyridine as a probe and their Lewis acidity order was also determined.
- Deshmukh, Krishna M.,Qureshi, Ziyauddin S.,Dhake, Kishor P.,Bhanage, Bhalchandra M.
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experimental part
p. 207 - 211
(2011/09/12)
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- METHOD FOR PREPARING AROMATIC CARBONATE COMPOUND
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Provided is a method for preparing an aromatic carbonate compound with a high yield and selectivity over a broader range of reaction temperatures by reacting an aromatic hydroxyl compound with a dialiphatic carbonate and/or aliphatic-aromatic carbonate co
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Page/Page column 11-13
(2010/08/09)
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- PROCESS FOR PREPARING DIARYL CARBONATES FROM DIALKYL CARBONATES
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The invention provides a process for preparing diaryl carbonates from dialkyl carbonates and aromatic hydroxyl compounds using at least two reaction columns, a process section for recovering the dialkyl carbonate used in the reaction and for removing the alcohol of reaction, one or more process steps for removing the by-products obtained in the process which have a boiling point between that of the dialkyl carbonate and that of the alkyl aryl carbonate formed during the preparation of the diaryl carbonate, and a process step for further purification of the diaryl carbonate obtained from the reaction columns.
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Page/Page column 24-27
(2010/02/17)
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- PROCESS FOR PREPARING DIARYL CARBONATES OR ALKYL ARYL CARBONATES FROM DIALKYL CARBONATES
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The invention relates to a process for preparing diaryl carbonates and/or alkyl aryl carbonates from dialkyl carbonates and aromatic hydroxy compounds using a reactive dividing wall column.
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Page/Page column 10
(2010/11/03)
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- Indium-catalyzed reaction for the synthesis of carbamates and carbonates: selective protection of amino groups
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We developed a simple, efficient, and selective method for preparing organic carbamates and carbonates using a catalytic amount of indium. A wide range of carbamates and carbonates were synthesized in high yields. The method is also applicable to the selective protection of amino groups under mild conditions.
- Kim, Joong-Gon,Jang, Doo Ok
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experimental part
p. 2688 - 2692
(2009/08/09)
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- PROCESS FOR THE PREPARATION OF DIARYL CARBONATE
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The invention relates to a process for the preparation of a diaryl carbonate by transesterification of an aromatic alcohol with a dialkyl carbonate in the presence of a transesterification catalyst during a period of time [ta], in which the aryl moiety is selected from unsubstituted phenyl and mono-, di- and trisubstituted phenyl groups, in which the alkyl moiety is selected from C2 to C4 linear and branched alkyl groups, in which the catalyst concentration is designated [ca], expressed as gram catalyst per gram of aromatic alcohol and dialkyl carbonate, in which the period of time [tm] and catalyst concentration [cm] are determined to arrive at a pre-set approach to the equilibrium for the transesterification of the aromatic alcohol with dimethyl carbonate to methyl aryl carbonate and methanol, in which the product [ca]*ta is at least 1.5* [cm]*tm, under otherwise the same reaction conditions.
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Page/Page column 19-23
(2008/12/07)
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- INDUSTRIAL PROCESS FOR PRODUCTION OF AROMATIC CARBONATE
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It is an object of the present invention to provide a specific process that enables an aromatic carbonate required for producing a high-quality high-performance aromatic polycarbonate to be produced industrially in a large amount (e.g. not less than 1 ton / hr) stably for a prolonged period of time (e.g. not less than 1000 hours, preferably not less than 3000 hours, more preferably not less than 5000 hours) from a cyclic carbonate and an aromatic monohydroxy compound. When producing an aromatic carbonate from a cyclic carbonate and an aromatic monohydroxy compound, the above object can be attained by carrying out a step of: (I) producing a dialkyl carbonate and a diol using a reactive distillation column having a specified structure, and (II) producing the an aromatic carbonate using a first reactive distillation column having a specified structure.
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Page/Page column 23-26
(2008/12/08)
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- METHOD OF PREPARING DIALKYLCARBONATES
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The present invention relates to a process of preparing dialkylcarbonates, and particularly to an improved process of preparing dialkylcarbonates, which comprises performing a reaction between an alcohol compound and a chloroformate derivative in the presence of an imidazole compound, thereby enabling to prepare dialkylcarbonates with high yield in a mild condition without using toxic raw materials and to easily separate impurities.
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Page/Page column 8; 10
(2008/06/13)
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- PROCESS FOR PRODUCING HIGH-PURITY DIARYL CARBONATE ON COMMERCIAL SCALE
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It is an object of the present invention to provide a specific process that enables a high-purity diaryl carbonate that can be used as a raw material of a high-quality and high-performance polycarbonate to be produced stably for a prolonged period of time on an industrial scale of not less than 1 ton / hr using as a starting material a reaction mixture containing an alkyl aryl carbonate obtained through a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound. Although there have been various proposals regarding processes for the production of reaction mixtures containing aromatic carbonates by means of a reactive distillation method, these have all been on a small scale and short operating time laboratory level, and there have been no disclosures on a specific process or apparatus enabling mass production on an industrial scale from such a reaction mixture of a high-purity diaryl carbonate that can be used as a raw material of a high-quality and high-performance polycarbonate. According to the present invention, there is provided a specific process that enables a high-purity diaryl carbonate important as a raw material of a high-quality and high-performance polycarbonate to be produced stably for a prolonged period of time on an industrial scale of not less than 1 ton / hr by taking as a starting material a reaction mixture containing an alkyl aryl carbonate that has been obtained through a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound and subjecting this starting material to a transesterification reaction using a reactive distillation column having a specified structure, and then subjecting a high boiling point reaction mixture obtained from the bottom of the reactive distillation column to separation and purification using a high boiling point material separating column A and a diaryl carbonate purifying column B which have specified continuous multi-stage distillation columns.
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Page/Page column 21-24
(2008/06/13)
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