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Structure of 872-36-6 * Storage: {[proInfo.prStorage]}
With 4-tert-Butylcatechol; triethylamine In ethyl acetate at 25 - 30℃; for 1.66667 h; Flow reactor; Large scale
61.3 kg (500 µM) chlorinated ethylene carbonate with the 151 kg (1500 µM) triethylamine, 120 kg ethyl acetate and 61.3g para-tertiary butyl catechol in fully dissolved after mixing in the mixer, to 0.05 m/s velocity of flow injection level in a tubular reactor, in the 25 - 30 °C reaction 100 minutes after filtering to remove the solid, triethylamine hydrochloride for 30percent in liquid caustic soda and processing, by the steam (0.25 mpa) indirect heating of the liquid triethylamine through after the condenser cooling liquid in the dechlorination section to apply, the filtrate is distilled under reduced pressure recovering ethyl acetate rectifying after, pressure is 0.098 mpa, collection 160 °C -165 °C fraction is vinylene carbonate, the yield is 96.5percent, GC content of 99.5percent.
95%
With 3-amino-2-propanol In ethyl acetate at 4℃; for 3 h;
(a) 10 g of Chloro ethylene carbonate prepared in step (a) was dissolved in 10 L of ethyl acetate, and 30 g of a catalyst (the ratio of copper oxide, zinc oxide and nickel oxide was 1: 1: 1), 12 mol of isopropanolamine and then reacted at 4 ° C for 3 hours to produce Vinylene Carbonate; (a) The product obtained in step (b) was subjected to suction filteration and the residue was taken and placed in 4 ° C n-hexane. The mixture was stirred and centrifuged. The crystals were vacuum dried at 0 ° C and the final yield of vinylene carbonate is 95percent (based on ethylene carbonate), purity is 99.5percent, free chlorine content is 3 ppm, water content is 3 ppm.
85%
at 55℃; for 5 h;
(B) Take 10mol chlorinated ethylene carbonate prepared in step (a) dispersed in 50LMethyl silicone oil, followed by addition of 12.25g of p-benzoquinone, 15mol of ethanolamine at 55 for 5 hours to generateVinylene carbonate(C) The product obtained in step (b) was subjected to suction filtration, and the filtrate was subjected to vacuum distillation (temperature 55 ° C) in a nitrogen-sealed environment (nitrogen content of less than 0.5 ppm, absolute pressure of 100 kPa) The final yield of vinylene carbonate was 85percent (as ethylene carbonate), with a purity of 98.5percent, a free chlorine content of 3 ppm and a water content of 3 ppm.
80%
for 0.5 - 6.5 h; Gas phase
Example 3 (Fluidized Bed Experiment); The apparatus is shown in FIG. 1.A Quartz glass reactor (R1) which has an internal diameter of 50 mm and a height of 700 mm was used for carrying out the experiment. A centrally mounted paddle stirrer with offset paddles at a height of 150 mm was present in the reactor. The stirrer is sealed from the atmosphere by means of a gland. The fluidized bed is brought to reaction temperature and kept at said temperature by means of external electrical heating. A stream of chloroethylene glycol carbonate that was vaporized in a gentle manner in an upstream evaporator (W1) after feeding via a pump in a stream of nitrogen was into the reactor. The gas emerging from the reactor was condensed by cooling, and the samples taken every 30 minutes from the collecting container (B1) were analysed by gas chromatography. The waste gas is scrubbed HCl-free with the aid of an alkaline scrubber (B2). The starting material chloroethylene glycol carbonate was added at about 4 g*min-1. In addition, an inert gas stream of 2.5 1*min-1 was introduced into the reactor. 180 g of a catalyst impregnated with ZnCl2 as described in abovementioned Example 2 were present in the reactor. The mean particle size determined by laser diffraction was 126 μm. Complete conversion were initially observed. The secondary components detected by gas chromatography were substantially acetic acid and chloroacetaldehyde, and the main product was VC. The conversion was stable for several hours and then decreased slowly as a result of coking of the catalyst. The variation of the conversion and the selectivities with respect to the by products is listed in Table 1 below.
69%
at 400℃; for 2 - 50 h; Gas phase
Comparative Example (Tubular Reactor, Fixed Bed)The experimental setup corresponded to that outlined in FIG. XX (1?). with the difference that the fluidized-bed reactor was replaced by a tubular reactor having a stationary catalyst bed. The reactor tube was about 2 m long and electrically thermostated and had an internal diameter of 40 mm. 2300 ml=1180 g of catalyst, prepared as described in Example 1, were introduced. The catalyst bed had a height of about 183 cm.6 thermocouples which permit monitoring of the internal temperature were mounted along the bed axis.In a nitrogen stream, the reactor was heated to 400° C. and the CGC metering into the evaporator was started.The catalyst is loaded with 1000 g of CGC per hour, evaporated in a nitrogen stream of 50-60 1(S.T.P.)/h. The temperature variation in the reactor tube and the reduction of the conversion after 50 hours showed that the catalyst bed had to be regenerated.At this point in time, VC had been obtained in an average yield of 69percent of theory.
112.31 g
Stage #1: for 0.2 h; Inert atmosphere Stage #2: at 40℃; for 3 h; Inert atmosphere
Weighing 250g content of 81percent chlorinated ethylene carbonateAnd 1 g of BHT were charged into a three-necked flask;The flask was purged with nitrogen for 12 minutes;Open electric mixing,Heating and setting the temperature to 40 ° C,Under nitrogen protection,The solution was slowly added dropwise to the flask through a constant-pressure dropping funnel500 g of triethylamine / DMC solution,Dropping time control in 1.5h,After the dropwise addition,Continue to heat reaction to stop reaction after 1.5h,While hot filter,The filter cake was washed with 200 g of DMC,The vacuum distillation operation was then carried out at a vacuum of 2 mm Hg,Fractions of 41-41 ° C were collected,Calculated:Content 98.56percentThe yield was 79percent.
Reference：
[1] Patent: CN104844556, 2017, B, . Location in patent: Paragraph 0029; 0030
[2] Patent: CN106699720, 2017, A, . Location in patent: Paragraph 0017
[3] Patent: CN106632225, 2017, A, . Location in patent: Paragraph 0017; 0018; 0019; 0020; 0021
[4] Patent: US2009/176997, 2009, A1, . Location in patent: Page/Page column 2-3
[5] Patent: WO2006/119911, 2006, A1, . Location in patent: Page/Page column 4
[6] Patent: US2009/176997, 2009, A1, . Location in patent: Page/Page column 3
[7] Patent: WO2006/119911, 2006, A1, . Location in patent: Page/Page column 5
[8] Journal of the Chemical Society, 1957, p. 618,620
[9] Journal of the American Chemical Society, 1955, vol. 77, p. 3789,3791
[10] Patent: US6395908, 2002, B1,
[11] Patent: CN105384718, 2016, A, . Location in patent: Paragraph 0035; 0036; 0037
[12] Patent: CN105384720, 2016, A, . Location in patent: Paragraph 0024
2
[ 5130-24-5 ]
[ 872-36-6 ]
Yield
Reaction Conditions
Operation in experiment
95.6%
at 34 - 49℃; for 0.0555556 h; Flow reactor; Sonication; Inert atmosphere
(1) The apparatus used in the method comprises an enhanced mass transfer type microchannel reactor 1, a meter, The microfilter 12, the enhanced mass transfer type microchannel reactor comprises a preheater-4, a preheater 25, an ultrasonic device 11, and a plurality of The microchannel module 6 made of ceramic, each microchannel module 6 comprises a core structure having a core structure, a hydraulic forceA spiral tubular microchannel 7 having a diameter of 0.5, an exhaust valve 8, a nitrogen replacement valve 9, and an ultrasonic device 11 are provided in a spiral tube microThe outer wall of the track 7 is provided with a discharge valve 10 on one of the outermost side of the microchannel module, (2) The mixture was mixed with vinyl carbonate and vinylsulfite to obtain a mixed solution, and the mixture was measured by measuring Chestnut 2 Input Preheater-4 Preheat to 34 °C, triethylamine through the metering pump two 3 was fed to preheater two 5 and preheated to 34 deg.C, The microchannel module 6 was replaced with nitrogen gas by means of a nitrogen replacement valve 9, and the preheated mixed solution, triethylamine Is fed to the helical tubular microchannel 7 in the outermost microchannel module 6 without the discharge valve 6 and heated to 49 °C The post-mixing reaction was carried out for 200 s, the molar ratio between vinyl chlorocarbonate and triethylamine was 1: 1.9 and the molar ratio of vinyl chlorocarbonate and The flow rate of triethylamine was controlled, the flow rate of ethylene carbonate was 0.3 mL / miη, the flow rate of triethylamine was 0.5 mL / min, After the completion of the product from the exhaust valve 8 out, transferred to the micro-filter 12 to get the crude filter, measured GC, ethylene carbonate content For 94.3percent, the crude product into the rectifier distillation distillation to obtain vinylene carbonate, distillation kettle pressure 10mmHg, the temperature of the fraction of the product was sampled at 35-45 °C and analyzed. The content of vinylene carbonate was 99.98percent, the yield was 95.6percent, the water Min 0.1ppm, free acid 0.1ppm.
Reference：
[1] Patent: CN106749155, 2017, A, . Location in patent: Paragraph 0027-0056
A mixture of 4-bromobenzeneacetamide (0. 5 g, 2.3 mmol) and <strong>[872-36-6]vinylene carbonate</strong> (241 mg, 2.80 mmol) in polyphosphoric acid (1. 5 g) was heated at 170C for 3 h. The residue was added to water (25 ML) and extracted with ethyl acetate (10 mL x 3). The combined organic extracts were washed with water and brine, dried and evaporated. The residue was purified by column chromatography using petroleum ether: ethyl acetate (4: 1) as eluent to give the sub-title compound (165 mg, 0.693 mmol, yield: 30%). IH NMR (CDC13, 270 MHz): 8 7.54 (s, 1H), 7.44 (d, J= 8.6 Hz, 2H), 7.15 (d, J= 8.6 Hz, 2H), 7.01 (s, 1H), 4.04 (s, 2H) 3C NMR (CDC13,67. 5 MHz): 8 162.5, 138.8, 134.2, 131.7, 130.4, 127.1, 121.0, 33.9 IR (neat): 2356, 1571, 1489, 1071 CM~L
1,7,8,9-tetrachloro-10,10-dimethoxy-3,5-dioxa-tricyclo[5.2.1.02,6]dec-8-en-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
94%
at 60 - 90℃; for 67h;
Preparation 1; 1,7,8,9-tetrachloro-10,10-dimethoxy-3,5-dioxa-tricyclo[5.2.1.02,6]dec-8-en-4-one; In a 500 mL 3N RB flask equipped with a water condenser, N2 flow adapter and thermometer, was placed 5,5-dimethoxy-1, 2,3, 4-tetrachlorocyclopentadiene (20.7 g, 0. 078 mol) and <strong>[872-36-6]vinylene carbonate</strong> (6. 7 g, 0.078 mol). The mixture was heated to 90 C for 4 h, then at 60 C for 63 h. The reaction was judged complete by TLC and upon cooling, the product solidified, was recrystallized from THF and filtered to provide a white solid (25.80 g, 94%). (TLC 20% EtOAC/hexanes Rf 0.29) ; 1H NMR (400 MHz, CDCl3) delta 5. 13 (s, 2H), 3.59 (s, 3H), 3.56 (s, 3H); GCMS m/z 348 (M) + ; mp 160-162C ; Anal. Calcd. for C10H8Cl4O5 : C, 34.32 ; H, 2.30. Found C, 34.32 ; H, 2.27.
With triethylamine; In diethyl ether; for 20h;Heating / reflux;
VC was synthesized according to the method of J. Am. Chem. Soc., 75, 1263 (1953) and J. Am. Chem. Soc., 77, 3789 (1955). That is, chlorine gas was blown into 600 g of EC previously purified by distillation and a reaction was carried out, under irradiation by ultraviolet light, at 65 C. for 24 hours. After the reaction, 560 g of monochloroethylene carbonate was obtained by vacuum distillation. Then, 493 g of monochloroethylene carbonate was dissolved in 500 ml of dry diethyl ether, 440 g of triethylamine was dropwise added thereto under refluxing over 6 hours, and the resultant mixture was stirred for 14 hours, while refluxing. Thereafter, the solid triethylamine hydrochloride was filtered and washed by a mixed solvent of ether and n-hexane. The filtrate was processed by distillation to distill off the solvent and the excess amine, then was processed by distillation under 30 mmHg reduced pressure to obtain 290 g of VC fraction. This VC was further rectified under 30 mmHg reduced pressure to obtain 104 g of VC having a boiling point of 73 C. This VC is referred to as ?conventional synthesis method VC? hereinbelow.
With triethylamine; In Dibutyl carbonate; at 50℃; for 20h;
Monochloroethylene carbonate was synthesized by the above-mentioned method (2). 494 g of the monochloroethylene carbonate obtained was dissolved in 500 ml of dibutyl carbonate (DBC) and fed into a 2 liter reactor. 440 g of triethylamine was dropwise added thereto at 50 C. over 6 hours for a reaction and the resultant mixture was stirred for a further 14 hours. Then, the reaction solution was cooled to room temperature and the triethylamine hydrochloride was obtained by filtration and sufficiently washed with DBC. 2100 g of the filtrate obtained was processed by distillation under 30 mmHg reduced pressure to distill off the excess triethylamine, to thereby obtain 390 g of VC fraction. The VC was treated by a silica gel column, then rectified under 30 mmHg reduced pressure to obtain 195 g of VC with extremely little impurities and a boiling point of 73 C. The VC thus obtained is referred to as ?high purity VC? hereinbelow
2-{4-[4-Fluoro-3-(1,3-oxazol-2-yl)phenyl]-2-isopropyl-1H-imidazol-5-yl}-6-methylpyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
40%
With polyphosphoric acid; at 160℃; for 3h;
(131d) 2-{4-[4-Fluoro-3-(1,3-oxazol-2-yl)phenyl]-2-isopropyl-1H-imidazol-5-yl}-6-methylpyridine Vinylene carbonate (0.10 g, 1.2 mmol) and polyphosphoric acid (2.0 g) were added to 2-fluoro-5-[2-isopropyl-5-(6-methylpyridin-2-yl)-1H-imidazol-4-yl]benzamide (0.086 g, 0.25 mmol) obtained in Example (131c). The resulting mixture was stirred at 160C for 3 hr. The reaction solution was cooled to room temperature and was neutralized with a 10% sodium hydroxide aqueous solution. After extraction with ethyl acetate, the organic layer was washed with water and brine, and then dried with anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The resulting crude product was purified by high-performance liquid chromatography (GL Science ODS-3, eluding solvent; water: acetonitrile = 95: 5 to 5: 95) to obtain 0.037 g (yield: 40%) of the title compound as a white amorphous form. 1H-NMR (500 MHz, CDCl3) delta ppm: 8.32 (1H, dd, J = 2.0, 7.4 Hz), 7.74 (1H, s), 7.69 (1H, m), 7.41 (1H, m), 7.30 (1H, s), 7.25-7.21 (2H, m), 6.95 (1H, d, J = 7.3 Hz), 3.15 (1H, m), 2.50 (3H, s), 1.38 (6H, d, J = 6.9 Hz). MS(ESI) m/z: 363 (M+H)+
To a solution of <strong>[685115-77-9]1-(3,5-dichloropyridin-4-yl)piperidine-4-carboxamide</strong> 23 (0.10 g, 0.36 mmol) in polyphosphoric acid (5 ml.) at 80 0C was added vinylene carbonate (35 mg,0.40 mmol). The mixture was heated at 170 0C for 4 hours, cooled to r.t. and poured into water (200 ml_). The mixture was extracted with ethyl acetate (3 x 50 ml.) and the combined organic extracts were washed with water (100 ml_), a saturated solution of sodium hydrogen carbonate (50 ml_), water (50 ml_), brine (50 ml_), dried (MgSO4) and concentrated under reduced pressure to furnish a colourless oil (12 mg). The crude product was purified by preparative tic on silica gel (CH2CI2, MeOH, 10:1 then hexane,EtOAc, 1 :1 ) to furnish the title compound as a white solid (13 mg, 12%), LC-MS (ESI) Rt 2.66 min, m/z 298 (100%, M+); m/z (ESI) Ci3H14CI2N3O requires 298.0508 found [M+H]+ 298.0507.
2-bromo-9,10-dihydro-9,10-ethanoanthracene-11,12-diol cyclic carbonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99%
for 18h;Reflux;
2-Bromoanthracene 11 (2.05 g, 8.0 mmol, 1 equiv.) and vinylene carbonate (3.68 mL, 5.00 g, 58 mmol, 7.3 equiv.) were heated under reflux with stirring for 18 hours, slowly forming a dark brown solution. The consumption of 11 was monitored by thin-layer chromatography (2% CH2Cl2/hexane, Rf=0.31). The mixture underwent rotary evaporation under high vacuum to remove the excess vinylene carbonate, providing the cyclic carbonate intermediate 12 as a light-brown solid (2.74 g, >99%). 1H NMR (CDCl3): delta 7.52 (dd, 1H), 7.37 (m, 3H), 7.27 (m, 3H), 4.88 (m, 2H), 4.66 (m, 2H).
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