There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.
Type
HazMat fee for 500 gram (Estimated)
Excepted Quantity
USD 0.00
Limited Quantity
USD 15-60
Inaccessible (Haz class 6.1), Domestic
USD 80+
Inaccessible (Haz class 6.1), International
USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic
USD 100+
Accessible (Haz class 3, 4, 5 or 8), International
USD 200+
Structure of 1589-47-5 * Storage: {[proInfo.prStorage]}
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Organic Process Research and Development, 2017, vol. 21, # 10, p. 1682 - 1688
2
[ 187737-37-7 ]
[ 57-55-6 ]
[ 107-98-2 ]
[ 1589-47-5 ]
[ 75-56-9 ]
Reference：
[1] Patent: EP1258483, 2002, A1, . Location in patent: Example 1-2
[2] Patent: EP1258483, 2002, A1, . Location in patent: Page 5
[3] Patent: EP1247805, 2002, A1, . Location in patent: Example 1-2
[4] Patent: US6372924, 2002, B1, . Location in patent: Example 1
[5] Patent: US6372924, 2002, B1, . Location in patent: Example 20
[6] Patent: US6372924, 2002, B1, . Location in patent: Example 16-19
3
[ 67-56-1 ]
[ 124-38-9 ]
[ 75-56-9 ]
[ 108-32-7 ]
[ 107-98-2 ]
[ 1589-47-5 ]
Yield
Reaction Conditions
Operation in experiment
54.8%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[2] Journal of Chemical Research, 2011, vol. 35, # 11, p. 654 - 656,3
4
[ 67-56-1 ]
[ 124-38-9 ]
[ 75-56-9 ]
[ 108-32-7 ]
[ 57-55-6 ]
[ 107-98-2 ]
[ 1589-47-5 ]
[ 616-38-6 ]
Yield
Reaction Conditions
Operation in experiment
13.2%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
12.5%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
5.8%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
23%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
7.8%
at 130℃; for 8 h; Autoclave; High pressure
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[2] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[3] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[4] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[5] Journal of Chemical Research, 2011, vol. 35, # 11, p. 654 - 656,3
[6] Journal of Chemical Research, 2011, vol. 35, # 11, p. 654 - 656,3
[7] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[8] Frontiers of Chemistry in China, 2011, vol. 6, # 1, p. 21 - 30
5
[ 17639-76-8 ]
[ 1589-47-5 ]
Reference：
[1] Canadian Journal of Chemistry, 1964, vol. 42, p. 990 - 1004
[2] Patent: US2011/86882, 2011, A1, . Location in patent: Page/Page column 22; 23
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min.
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
Reference：
[1] Synthetic Communications, 2011, vol. 41, # 6, p. 891 - 897
[2] Polish Journal of Chemistry, 1986, vol. 60, # 4-6, p. 593 - 598
[3] Journal of the American Chemical Society, 1946, vol. 68, p. 680
[4] Zhurnal Obshchei Khimii, 1944, vol. 14, p. 1039,1041[5] Chem.Abstr., 1946, p. 7153
[6] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 21, p. 123
[7] Journal of the American Chemical Society, 1946, vol. 68, p. 680
[8] Zhurnal Obshchei Khimii, 1944, vol. 14, p. 1039,1041[9] Chem.Abstr., 1946, p. 7153
[10] Bulletin des Societes Chimiques Belges, 1930, vol. 39, p. 399
[11] Journal of the American Chemical Society, 1950, vol. 72, p. 1251
[12] Synthesis, 1981, # 4, p. 280 - 282
[13] Journal of Organic Chemistry, 1988, vol. 53, # 10, p. 2300 - 2303
[14] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1993, # 2, p. 199 - 203
[15] Journal of the American Chemical Society, 1955, vol. 77, p. 2420,2423
[16] Journal of the American Chemical Society, 1955, vol. 77, p. 2420,2423
[17] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1981, p. 2927 - 2929
[18] Journal of Catalysis, 2008, vol. 258, # 1, p. 14 - 24
[19] Patent: US2009/187049, 2009, A1, . Location in patent: Page/Page column 3
[20] Patent: US2009/187049, 2009, A1, . Location in patent: Page/Page column 3
[21] Patent: WO2009/134630, 2009, A1, . Location in patent: Page/Page column 8-9, 14
[22] Applied Catalysis A: General, 2010, vol. 377, # 1-2, p. 107 - 113
[23] New Journal of Chemistry, 2010, vol. 34, # 11, p. 2534 - 2536
[24] Kinetics and Catalysis, 2011, vol. 52, # 3, p. 386 - 390
[25] Kinetics and Catalysis, 2011, vol. 52, # 3, p. 386 - 390
[26] RSC Advances, 2016, vol. 6, # 75, p. 70842 - 70847
[27] Journal of Molecular Catalysis A: Chemical, 2016, vol. 423, p. 22 - 30
[28] ChemCatChem, 2017, vol. 9, # 9, p. 1641 - 1647
[29] Catalysis Science and Technology, 2017, vol. 7, # 3, p. 725 - 733
[30] RSC Advances, 2018, vol. 8, # 8, p. 4478 - 4482
[31] Chinese Journal of Catalysis, 2017, vol. 38, # 5, p. 879 - 888
[32] Patent: US1976677, 1929, ,
[33] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 19, p. 210
[34] Patent: US1730061, 1925, ,
[35] Patent: US2807651, 1956, ,
[36] Patent: US2807651, 1956, ,
10
[ 67-56-1 ]
[ 187737-37-7 ]
[ 57-55-6 ]
[ 107-98-2 ]
[ 74-98-6 ]
[ 1589-47-5 ]
[ 75-56-9 ]
Yield
Reaction Conditions
Operation in experiment
11.8 %Chromat.
at 60℃; for 12 h; Autoclave; Supercritical conditions
General procedure: PO synthesis reaction from propylene in presence of ex situ H2O2, as oxidizing agent, were performed in a 3 mL round bottom glass reactor in which the stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of TS-1 catalyst (2.5 mg), methanol (1.2 g), and propylene (9 mmol) were added, followed by the addition of the oxidant, 35percent wt H2O2 in water (0.4 mmol). Then, the mixture was heated at 60°C, and the reaction was monitored for 5 h. The experiments for the direct synthesis of PO with in situ generated H2O2 were carried out in a 15 mL stainless steel reactor which contained a relief valve, for safety. The stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of catalyst (15 mg), acidity inhibitor (ammonium acetate, 0.01 g) and co-solvent (0.2 gof different co-solvents) were added to the reactor, followed by the addition of propylene (2 mmol) and CO2, reaching carbon dioxide vapor pressure (>55 bar). Oxygen and hydrogen were added to the reactor by means of high pressure burettes, and then the reactor was heated up to desired temperature (ranging from room temperature to 80°C, according each experiment). The reaction experiments were carried out for 5 h, unless otherwise stated. At the end of the reaction, the reactor was cooled down and the pressure was slowly released by venting, accumulating the gaseous mixture in an inert gas sampling bag. 3-pentanone was used forrecovering any product that could be retained on the reactor walls. The amount of formed products, i.e., propylene oxide, acetone, propionaldehyde, acrolein, isopropanol, 1-methoxy-2-propanol (MP1), 2-methoxy-1-propanol (MP2), propylene glycol (PG) and propylene carbonate were analyzed using a Shimadzu Gas chro-matograph GC-2010 Plus provided with FID detector and 20 m length, 0.10 mm ID, 0.10 m df. Permabond FFAP column. The amounts of propane and unreacted propylene, oxygen and hydrogen were analyzed using a Bruker 450-GC which contains two different independent channels. The first one is provided with a thermal conductivity detector (TCD) and three different columns: Hayesep N (0.5 m length), Hayesep Q (1.5 m length) and molsieve 13× (1.2 m length), using argon as carrier. The second one is provided with two different flame ionization detectors (FID) and three different columns: capillary column CP-Wax (1 m length and 0.32 mm ID), CP-Porabond Q (25 m length and 0.32 mm ID) and CP-Wax (5 m length and 0.32 mm ID).
Reference：
[1] Journal of the American Chemical Society, 1950, vol. 72, p. 1251
[2] Patent: US2555950, 1949, ,
[3] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1995, # 3, p. 271 - 282
12
[ 67-56-1 ]
[ 124-38-9 ]
[ 75-56-9 ]
[ 107-98-2 ]
[ 1589-47-5 ]
Reference：
[1] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
[2] Journal of Organometallic Chemistry, 2015, vol. 794, p. 231 - 236
Reference：
[1] Journal of the American Chemical Society, 1968, vol. 90, # 16, p. 4323 - 4327
[2] Journal of the American Chemical Society, 1973, vol. 95, p. 2184 - 2193
[3] Bulletin de la Societe Chimique de France, 1960, p. 1813 - 1826
[4] Journal of the American Chemical Society, 1978, vol. 100, p. 3838 - 3846
[5] Kinetics and Catalysis, 2011, vol. 52, # 3, p. 386 - 390
[6] Chemistry - A European Journal, 2014, vol. 20, # 46, p. 14976 - 14980
16
[ 7440-32-6 ]
[ 187737-37-7 ]
[ 98-85-1 ]
[ 107-98-2 ]
[ 1589-47-5 ]
Reference：
[1] Patent: US5214168, 1993, A,
17
[ 67-56-1 ]
[ 75-56-9 ]
[ 107-98-2 ]
[ 1589-47-5 ]
[ 127-00-4 ]
Reference：
[1] Chemical Communications, 2008, # 11, p. 1287 - 1289
[2] Chemical Communications, 2008, # 11, p. 1287 - 1289
18
[ 67-56-1 ]
[ 187737-37-7 ]
[ 107-98-2 ]
[ 74-98-6 ]
[ 1589-47-5 ]
[ 75-56-9 ]
Yield
Reaction Conditions
Operation in experiment
17.6 %Chromat.
at 60℃; for 7 h; Autoclave; Supercritical conditions
General procedure: PO synthesis reaction from propylene in presence of ex situ H2O2, as oxidizing agent, were performed in a 3 mL round bottom glass reactor in which the stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of TS-1 catalyst (2.5 mg), methanol (1.2 g), and propylene (9 mmol) were added, followed by the addition of the oxidant, 35percent wt H2O2 in water (0.4 mmol). Then, the mixture was heated at 60°C, and the reaction was monitored for 5 h. The experiments for the direct synthesis of PO with in situ generated H2O2 were carried out in a 15 mL stainless steel reactor which contained a relief valve, for safety. The stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of catalyst (15 mg), acidity inhibitor (ammonium acetate, 0.01 g) and co-solvent (0.2 gof different co-solvents) were added to the reactor, followed by the addition of propylene (2 mmol) and CO2, reaching carbon dioxide vapor pressure (>55 bar). Oxygen and hydrogen were added to the reactor by means of high pressure burettes, and then the reactor was heated up to desired temperature (ranging from room temperature to 80°C, according each experiment). The reaction experiments were carried out for 5 h, unless otherwise stated. At the end of the reaction, the reactor was cooled down and the pressure was slowly released by venting, accumulating the gaseous mixture in an inert gas sampling bag. 3-pentanone was used forrecovering any product that could be retained on the reactor walls. The amount of formed products, i.e., propylene oxide, acetone, propionaldehyde, acrolein, isopropanol, 1-methoxy-2-propanol (MP1), 2-methoxy-1-propanol (MP2), propylene glycol (PG) and propylene carbonate were analyzed using a Shimadzu Gas chro-matograph GC-2010 Plus provided with FID detector and 20 m length, 0.10 mm ID, 0.10 m df. Permabond FFAP column. The amounts of propane and unreacted propylene, oxygen and hydrogen were analyzed using a Bruker 450-GC which contains two different independent channels. The first one is provided with a thermal conductivity detector (TCD) and three different columns: Hayesep N (0.5 m length), Hayesep Q (1.5 m length) and molsieve 13× (1.2 m length), using argon as carrier. The second one is provided with two different flame ionization detectors (FID) and three different columns: capillary column CP-Wax (1 m length and 0.32 mm ID), CP-Porabond Q (25 m length and 0.32 mm ID) and CP-Wax (5 m length and 0.32 mm ID).
Reference：
[1] Applied Catalysis A: General, 2016, vol. 523, p. 73 - 84
potassium methanolate; In 2-methoxypropanol; at 130℃; for 1.16667 - 2.16667h;Product distribution / selectivity;
EXAMPLE 1; Reaction Runs; Comparison Run 1A: Methanol (132 g), propylene oxide (110 g), and a 2-methoxy-1-propanol recycle mixture (60 g) are added to a stainless steel reactor and the temperature of the reaction mixture is raised to 130 C. A potassium methoxide catalyst mixture (1.27 g, of 25 wt. % KOCH3 in methanol) is added to the reaction mixture and stirred. Samples are taken from the reaction mixture periodically (at 1 h and 10 min and at 2 hr and 10 min after catalyst addition) and analyzed for carbonyl content and UV absorbance. Results are shown in Table 1.
With sodium tetrahydroborate;potassium methanolate; In 2-methoxypropanol; at 130℃; for 1.16667 - 2.16667h;Product distribution / selectivity;
Run 1B: Run 1B is run according to the procedure of Comparison Run 1A with the exception that NaBH4 is added to the reaction mixture with the methanol, resulting in a 0.3 ppm NaBH4 concentration in the reaction mixture. Results are shown in Table 1.
1-methyl-1H-imidazole; at 80℃; under 2311.54 - 3345.86 Torr; for 5h;Inert atmosphere;Product distribution / selectivity;
The reactor is a 2-liter, stainless steel, batch reactor equipped with an agitator, an electric heater, an internal water-cooled cooling coil, a dip tube for sampling, an internal thermowell, various injection ports, and pressure relief venting. The reactor charge contains the desired amounts of alcohol and catalyst pressurized with nitrogen to 30-50 psig (0.207- 0.345 mPa). The desired alkepsilonne oxide is administered to the system using a stainless steel addition cylinder suspended on a weigh cell. Cylinder nitrogen pressure is applied to the <n="10"/>addition cylinder to aid in the transfer of oxide to the reactor. Pressure, temperature and weigh cell data are collected for each run with a stripchait recorder. The reaction temperature is maintained constant by the addition of cooling water in the cooling coils to offset the heat of reaction. Progress of the reaction is monitored by the pressure of the reactor. The reaction half-life is determined by measuring the time it takes for the pressure in the reactor to fall one-half of the total pressure drop achieved in the course of the reaction. Reactions are run until the pressure stabilizes; the reactor is then cooled to room temperature and drained. The reactions typically run for 120 to 180 minutes. Samples are taken immediately before oxide is added to the reactor and at the completion of the reaction. The samples are analyzed for composition by gas chromatography.The alcohol/phenol, oxide and catalyst, and their respective amounts, and the reaction temperature and time, arc reported in Table IA. The half-life of the reaction and the final composition of the products and by-products are reported in Tables 1 B, 1 C and 1 F.
With calcined brucite; at 120℃; for 7.5h;Autoclave;
General procedure: Brucite and LDHs were tested in the synthesis of 1-methoxy-2-propanol from methanol and propylene oxide (PO) at 120 and140C. PO (99.5%) was purchased from Acros Organic. Commercialmethanol was used without any further purification. The reac-tion was carried out in a stainless steel autoclave reactor with aninner volume of 25 cm3. The standard procedure was as follows:7.4 mmol PO, MeOH (MeOH/PO = 8 mol/mol) and catalyst (3 wt.%)were introduced into the autoclave. After running at 120 or 140Cfor 1 or 7.5 h under magnetic stirring, the reactor was cooled downto room temperature. The products were analyzed by a gas chro-matograph (Agilent 7820) with a flame ionization detector on aHP-5 capillary column, after separation by centrifugation of the cat-alysts. n-Propanol was used as the internal standard to calculate the amount of the products.
With 1-ethyl-3-methylimidazolium acetate; at 120℃; for 2h;Autoclave; Ionic liquid; Green chemistry;
General procedure: Reactions were performed in a stainless-steel autoclave reactor of inner volume 100 mL. A typical procedure was as follows. PO and n-butanol in molar ratios of 1-10 and a certain amount of catalyst were introduced into the autoclave. After running the reaction at 80-140 C for 30-240 min under magnetic stirring, the reactor was cooled to room temperature to give the target products. The mixtures after reaction were analyzed using a gas chromatography (GC) system (Shimadzu GC-2010 plus) with a flame ionization detector and a capillary column (HP-INNOWax), combined with electrospray quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS; Bruker QTOF II); mass spectrometric ?negative ion fishing? was used [45]. The reusability of the IL catalysts was also investigated, using EmimOAc as an example. The recycling of EmimOAc used in the synthesis of propylene glycol butyl ether at 100 C for 30 min was investigated. After the reaction, the products and excess reactants were removed and the IL catalyst was separated from the reaction mixture by vacuum distillation and dried at 70 C for more than 5 h for reuse. The structure and purity of the recovered EmimOAc were checked using 1H NMR spectroscopy.
With molecular sieve TS-A; In acetone; at 65℃; under 7500.75 Torr; for 1h;
Propylene oxide, methanol, acetone as a solvent and the molecular sieve TS-A prepared in Preparation Example 1 as a catalyst were continuously fed into a moving bed reactor,Carry out contact reaction. Among them, propylene oxide is fed from the lower feed port of the reactor,The mixture of methanol and solvent and the catalyst are fed into the reactor from the liquid phase feed port and the solid phase feed port at the top of the reactor, respectively. among them,The feed rate of propylene oxide is 50 mL / min, the molar ratio of propylene oxide to methanol is 1: 2, and the weight ratio of solvent to propylene oxide is 10: 1.The weight ratio of propylene oxide to catalyst is 8: 1, the temperature in the reactor is 65 ,The pressure in the reactor was 1.0 MPa. During operation,The catalyst output from the bottom of the reactor is directly recycled without regeneration.The reaction mixture obtained 1h and 12h after the start of the reaction was analyzed by gas chromatography,And calculate the propylene oxide conversion rate and propylene glycol monomethyl ether selectivity. The results are listed in Table 1.
Production Example 6-12-Methoxypropan-1-ol To a diethyl ether (60.0 mL) solution of lithium aluminum hydride (641 mg, 16.9 mmol), was added methyl 2-methoxypropionate (2.00 g, 16.9 mmol) while stirring on ice, and the mixture was stirred at room temperature over one day and night. After the reaction was completed, aqueous ammonia was added while cooling on ice, and the mixture was filtered with Celite and the solvent was distilled off under reduced pressure to obtain a crude compound (1.60 g, 17.8 mmol)1H-NMR (CDCl3) delta: 1.12 (d, J=6.0 Hz, 3H), 3.38 (s, 3H), 3.41-3.49 (m, 2H), 3.55-3.63 (m, 1H).
With C2H3N4(1-)*0.5C8H4O4(2-)*Zn(2+); for 6h;Heating;
In a typical reaction run, 1 mL epoxides, 10 mL alcohol and0.2 g Zn(atz)(bdc)0.5 were put into a 25 mL stainless steelpressure reactor and heated to 60 C and kept for a desiredreaction duration. After the reaction, the reactor was cooledin ice water, and the catalyst was separated by filtration andthe filtrate was quantitatively analyzed by GC (ThermoFisher, Trace 1300).
EXAMPLE 10 0.53 g of 5alpha-(2'-chloro-3'S-hydroxy-5'-cyclopentyl-pent-1'-trans-1'-enyl)-2alpha,4alpha-dihydroxy-cyclopentan-1alpha-ethanal-gamma-lactol-3',4-bis-DIOX-ether in 8 ml of acetone and 8 ml of 2N oxalic acid was refluxed for 1 hour and 30 minutes. After evaporation of the acetone in vacuo and extraction with ethyl acetate, 0.36 g were obtained of 5alpha-(2'-chloro-3'S-hydroxy-5'-cyclopentyl-pent-1'-trans-1'-enyl)-2alpha,4alpha-dihydroxy-cyclopentane-1alpha-ethanal-gamma-lactol. By treatment with 3 mg of p-toluensulfonic acid in benzene 3 ml of methyl orthoformate, under the conditions outlined in Example 10, 0.34 g of the lactol-methyl ether were obtained.
22
phosphoric acid mono-(2-methoxy-propyl ester)[ No CAS ]
The distillate of example 2 was dewatered by means of azeotropic distillation using a distillation column having an inner diameter of 25 mm and a filling with stainless steel coils. The column had a separation efficiency of 25 theoretical stages and was equipped with external electric heating to compensate heat loss. The distillate of example 2 was fed continuously at a rate of 150 g/h to the 3rd theoretical stage (counted from the top) of said column. Additionally benzene was fed to the top of the column. The reboiler was heated to obtain 1235 g/h distillate. The distillate was condensed and transferred to a phase separation vessel, in that it separated to a benzene phase and an aqueous phase. The benzene phase was again fed to the top of the column and the aqueous phase was removed at a rate of 115 g/h. Simultaneously, a bottom product was removed at a rate of 35 g/h. The content of organic compounds of the bottom product was analyzed via gc-analysis. The water content was determined by Karl-Fischer-Titration.
Yield
Reaction Conditions
Operation in experiment
pH 11;Heating / reflux; Distillation;Purification / work up;
Example 1 was repeated with the difference, that the pH-value of the aqueous composition was adjusted to 11 by adding sodium hydroxide prior to feeding said aqueous composition to the distillation column. After establishing equilibrium in the distillation column, the distillate had a composition as indicated in table 3.
Yield
Reaction Conditions
Operation in experiment
pH 3;Heating / reflux; Distillation;Purification / work up;
The aqueous composition used for the process of separating 1-methoxy- 2-propanol and 2-methoxy-l-propanol is a waste water stream obtained from a process of producing propylene oxide from propylene and hydrogen peroxide in the presence of methanol. The composition is given in table 1. The pH-value is 3. The aqueous composition of table 1 was continuously fed to the 7th plate (counted from the top) of a bubble-cap column having 13 plates in total. The feed rate was 307 g/h. The reboiler was heated so that at a reflux rate of 1,0, 84 g/h distillate was obtained at the top of the column. Additionally 223 g/h of bottom product was obtained. After establishing equilibrium in the distillation column, the distillate had a composition as indicated in table 2. Table 2: composition of the distillate of example 1 Component percent by weight 1-methoxy-2-propanol 13,8 2-methoxy-l-propanol 9,19 1,2-propane diol < 0,01 formic acid 0,22 acetic acid < 0,01 propionic acid < 0,01 dimethoxymethane < 0,01 2-propanol < 0,01 water rest The amount of 1-methoxy-2-propanol and 2-methoxy-l-propanol could significantly be increased by the pre-distillation step. The amount of formic acid was decreased, and acetic acid and propionic acid were nearly completely removed.
Yield
Reaction Conditions
Operation in experiment
Distillation;Purification / work up;
The bottom product of example 3 was fed continuously to the middle of a glass column with a length of 3000 mm packed with 3 mm stainless steel coils at a feed rate of 55 [G/H.] Heating was adjusted to obtain 33 g/h distillate at a reflux ratio of 6,2. Simultaneously, 22 g/h of bottom product were removed from the distillation column. The obtained 1-methoxy-2-propanol is essentially free of water and only a trace of 2-methoxy-l-propanol was present.
The aqueous composition used for the process of separating 1-methoxy-2-propanol and 2-methoxy-1-propanol is a waste water stream obtained from a process of producing propylene oxide from propylene and hydrogen peroxide in the presence of methanol. The composition is given in table 1. The pH-value is 3. The aqueous composition of table 1 was continuously fed to the 7th plate (counted from the top) of a bubble-cap column having 13 plates in total. The feed rate was 307 g/h. The reboiler was heated so that at a reflux rate of 1,0, 84 g/h distillate was obtained at the top of the column. Additionally 223 g/h of bottom product was obtained. After establishing equilibrium in the distillation column, the distillate had a composition as indicated in table 2. The amount of 1-methoxy-2-propanol and 2-methoxy-1-propanol could significantly be increased by the pre-distillation step. The amount of formic acid was decreased, and acetic acid and propionic acid were nearly completely removed. Example 2 [0047] Example 1 was repeated with the difference, that the pH-value of the aqueous composition was adjusted to 11 by adding sodium hydroxide prior to feeding said aqueous composition to the distillation column. After establishing equilibrium in the distillation column, the distillate had a composition as indicated in table 3. Again, the amount of 1-methoxy-2-propanol and 2-methoxy-1-propanol could significantly be increased by pre-distillation. Formic acid, acetic acid and propionic acid were not detectable in the distillate. Example 3 [0049] The distillate of example 2 was dewatered by means of azeotropic distillation using a distillation column having an inner diameter of 25 mm and a packing with stainless steel coils. The column had a separation efficiency of 25 theoretical stages and was equipped with external electric heating to compensate heat loss. The distillate of example 2 was fed continuously at a rate of 150 g/h to the 3rd theoretical stage (counted from the top) of said column. Additionally benzene was fed to the top of the column. The reboiler was heated to obtain 1235 g/h distillate. The distillate was condensed and transferred to a phase separation vessel, in that it separated to a benzene phase and an aqueous phase. The benzene phase was again fed to the top of the column and the aqueous phase was removed at a rate of 115 g/h. Simultaneously, a bottom product was removed at a rate of 35 g/h. [0050] The content of organic compounds of the bottom product was analyzed via gc-analysis. The water content was determined by Karl-Fischer-Titration. Table 4 shows that the bottom product was a mixture of 1-methoxy-2-propanol and 2-methoxy-1-propanol with a very low content of water. Other impurities could not be detected. Example 4 [0052] The bottom product of example 3 was fed continuously to the middle of a glass column with a length of 3000 mm packed with 3 mm stainless steel coils at a feed rate of 55 g/h. Heating was adjusted to obtain 33 g/h distillate at a reflux ratio of 6,2. Simultaneously, 22 g/h of bottom product were removed from the distillation column. Table 5 shows that the amount of 1-methoxy-2-propanol was increased to 99 percent by weight. The obtained 1-methoxy-2-propanol is essentially free of water and only a trace of 2-methoxy-1-propanol was present.
With hydrogen;2percent Ru on activated carbon; at 140℃; under 30003 Torr;Product distribution / selectivity;
The Comparative Example was repeated with the exception that the bottom product obtained in the pre-evaporator stage was directed to a trickle-bed reactor for continuous hydrogenation. The hydrogenation reactor had an interior volume of 150 ml and was filled with a hydrogenation catalyst in form of extrudates with 2.3 mm diameter comprising 2% Ru on activated carbon (The catalyst was prepared according to the incipient wetness method using RuCl3, ?Preparation of Catalyst?, Demon, B. et al., Elsevier, Amsterdam, 1976, page 13). The hydrogenation was performed at 140 C. and 40 barabs at a hydrogen flow rate of 10 ml/h. The hydrogenated product was continuously removed and had a pH of 9. The pH was reduced to be below 7 by adding sulfuric acid prior to entering the final distillation step according to the comparative example. [0072] After 500 h running the epoxidation process the cooling temperature in the reaction step was 42 C. and the H2O2 conversion was still 96% at a catalyst selectivity of 96%. The propene oxide stream contained 0.07% acetaldehyde, 20 ppm methylformate and 10 ppm dimethoxymethane. [0073] As can be seen from the comparison of both examples the activity of the epoxidation catalyst even after 500 h running the process was only very marginally reduced if the solvent stream was hydrogenated prior to recycling the solvent to the reaction stage. In contrast thereto without hydrogenating the solvent stream a considerable reduction in catalyst performance is observed, which requires a gradual increase in the reaction temperature in order to maintain a constant hydrgen peroxide conversion. The effect on product quality is even more dramatic. Thus it is shown that hydrogenation of the solvent stream to be recycled to the epoxidation process leads to considerably reduced catalyst deactivation and improved product quality. ; EXAMPLE 2 [0074] The epoxidation reaction was performed as described for the Comparative Example. The bottom product obtained in the pre-evaporation was analyzed and subjected to the hydrogenation as described for Example 1. [0075] The composition of the hydrogenation feed and product are given in Table 1. Apart from hydrogen peroxide, the feed stream was free of other peroxy compounds.
33
[ 1589-47-5 ]
[ 98-59-9 ]
[ 99861-96-8 ]
Yield
Reaction Conditions
Operation in experiment
91%
With pyridine; In dichloromethane; at 20℃;Cooling with ice;
Cool a solution of 2-methoxypropan-i -i (1.0 g, 11,1 mmoi) in pyridine (12,5 mL) and DCM (19 niL) in an ice water bath and add 4-methy1benzenesuifonyi chloride(2.54 g, i3,3 mrnol). Stir the mixture overnight while allowing the temperature to rise slowly to ambient temperature. Quench the reaction with water (40 niL) and EtOAc (50 mL). Separate the phases and extract the aqueous phase twice with additional EtOAc (50 mL). Wash the combined organic solutions with saturated aqueous ammonium chloride and saturated NaC1. Dry the organics over anhydrous magnesium sulfate. Filter andconcentrate the filtrate to give the title comrn pound 2,71 g (91%) as a colorless oil. MS (mlz): 245 (M+1).
56%
With 2,6-dimethylpyridine; In dichloromethane; at 20℃; for 72h;
To a stirred solution of 2-methoxy-propan-1-ol (1.70 g, 18.86mmol) in dichloromethane (20 ml) was added 2,6-lutidine (4.38ml, 37.9mmol) followed by para-toluenesulphonyl chloride (4320mg, 22.6mmol) portion-wise. The reaction mixture was stirred at room temperature for 72 hours. Solvents were evaporated in vacuo, then ethyl acetate (100 ml) and saturated citric acid (aqueous) (100 ml) were added. The layers were separated and the organic extract was washed with further saturated citric acid (aqueous) (2 x 40 ml). The organic extract was then washed with saturated sodium bicarbonate (aqueous solution) (50 ml) then dried over anhydrous MgSO4 (s), filtered and evaporated in vacuo to afford crude title compound (4.51 g, 56%). Material was taken on without further purification.1H-NMR (CDCI3): 1.08 (d, 3H), 2.42 (d, 3H), 3.26 (s, 3H)1 3.94 (s, 2H), 7.32 (d, 2H), 7.77 (d, 2H).
In pyridine; at 0 - 20℃; for 19h;
Step 1: To a solution of <strong>[1589-47-5]2-methoxypropanol</strong> (1.73 g, 19.2 mmol, prepared by LiAlH4 reduction of methyl 2-methoxypropionate) in pyridine (6 ml) at 0 C. add dropwise toluenesulfonyl chloride (4.57 g, 24.0 mmol) in pyridine (12 ml). Stir 1 h, allow to warm to RT, and stir 18 h. Partition between water and CH2Cl2, wash with 1N HCl, and dry (MgSO4). Concentrate to obtain the tosylate as a yellow oil.
With pyridine; at 20℃; for 5h;Cooling with ice bath;
Production Example 6-22-Methoxypropyl 4-methylbenzenesulfonate To dichloromethane (30 mL) mixture of <strong>[1589-47-5]2-methoxypropan-1-ol</strong> (1.6 g, 17.8 mmol) and pyridine (20.0 mL), was added p-toluenesulfonyl chloride (4.07 g, 21.4 mmol) while stirring on ice, and the mixture was stirred at room temperature for five hours. To the mixture, were added water and ethyl acetate. After thoroughly shaking the mixture, the organic layer was separated, and the organic layer was washed with brine and dried over anhydrous magnesium sulfate. The mixture was filtered, and the solvent in the filtrate was then distilled off under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of n-heptane and ethyl acetate: n-heptane/ethyl acetate=2/1) to obtain the title compound (3.12 g, 12.8 mmol).1H-NMR (CDCl3) delta: 1.12 (d, J=6.0 Hz, 3H), 2.45 (s, 3H), 3.29 (s, 3H), 3.49-3.59 (m, 1H), 3.95 (d, J=5.2 Hz, 2H), 7.32-7.36 (m, 2H), 7.76-7.81 (m, 2H).
With dihydrogen peroxide;titanium silicate; In methanol; at 59℃; under 18751.9 Torr;Product distribution / selectivity;
A titanium-silicate catalyst was employed in all examples. The titanium-silicate powder was shaped into 2 mm extrudates using a silica sol as binder in accordance with example 5 in EP-A 1 138 387. The H2O2 employed was prepared according to the anthraquinone process as a 40 wt-% aqueous solution. [0067] Epoxidation is carried out continuously in a reaction tube of 300 ml volume, a diameter of 10 mm and a length of 4 m. The equipment is furthermore comprised of three containers for liquids and relevant pumps and a liquid separating vessel. The three containers for liquids comprised methanol, the 40% H2O2 and propene. The 40% H2O2 was adjusted with ammonia to a pH of 4.5. The reaction temperature is controlled via an aqueous cooling liquid circulating in a cooling jacket whereby the cooling liquid temperature is controlled by a thermostat. The reactor pressure was 25 bar absolute. Mass flow of the feeding pumps was adjusted to result in a propene feed concentration of 21.5 wt-%, a methanol feed concentration of 57 wt-% and an H2O2 feed concentration of 9.4 wt-%. The reactor was operated in down-flow operation mode. [0068] The cooling jacket temperature was 41 C., the total mass flow was 0.35 kg/h and the maximum temperature was 59 C. Product output was determined by gas chromatography and the H2O2 conversion by titration. The catalyst selectivity was calculated on the basis of gas chromatographical analysis of the propene oxygenates as the ratio of the amount of propene oxide formed relative to the amount of all propene oxygenates formed. Initial H2O2 conversion was 96% at a catalyst selectivity of 96%. [0069] The reaction mixture obtained from the reaction after release of pressure was separated in the pre-evaporation stage into an overhead product containing propene, propane, propene oxide and methanol, and a bottom product containing methanol, propylene glycol monomethyl ethers, propylene glycol, water and high boiling point compounds and non-converted hydrogen peroxide. A liquid condensate that contains propene oxide and methanol as well as propene and propane dissolved therein was obtained from the vapour state overhead product. The uncondensed stream, which substantially consisted of propene and propane, was returned to the epoxidation reaction. The propene and propane dissolved in the condensate were stripped from the latter in the C3 stripper and returned in the vapour state together with the stream to the partial condensation stage. The stream, which consisted substantially of propene oxide and methanol and had been freed from propene and propane, was separated in an extractive distillation in which water was fed in as extraction agent immediately underneath the head of the column, into a propene oxide crude product that consisted initially of more than 99.5%, of propene oxide, and into a bottom product that consisted substantially of methanol and water, the water content being less than 20%. The bottom product was returned as solvent to the epoxidation reaction. [0070] The bottom product obtained in the pre-evaporator was separated in a distillation stage at a pressure of 2 bars abs. using a continuously running column having 35 stages at a reflux ratio of 2 for recovering methanol, into an overhead product that consisted of more than 95% of methanol, and into a bottom product consisting of propylene glycol monomethyl ethers, propylene glycol, water, high boiling point compounds and only traces of hydrogen peroxide. The overhead product was continuously returned as solvent to the epoxidation reaction. After 500 h running the epoxidation process the cooling temperature in the reaction step had to be increased to 50 C. to maintain the conversion constant at 95% and the catalyst selectivity dropped to 90%. The propene oxide stream contained 2% acetaldehyde, 0.5% methylformate and 0.2% dimethoxymethane.
With ammonia; dihydrogen peroxide;titanium-silicate catalyst; In water; at 50℃; under 18751.9 Torr;pH 4.5;Continuously procces;Product distribution / selectivity;
A titanium-silicate catalyst was employed in all examples. The titanium-silicate powder was shaped into 2 mm extrudates using a silica sol as binder in accordance with example 5 in EP-A 1 138 387. The H2O2 employed was prepared according to the anthraquinone process as a 40 wt-% aqueous solution. Epoxidation is carried out continuously in a reaction tube of 300 ml volume, a diameter of 10 mm and a length of 4 m. The equipment is furthermore comprised of three containers for liquids and relevant pumps and a liquid separating vessel. The three containers for liquids comprised methanol, the 40% H2O2 and propene. The 40% H2O2 was adjusted with ammonia to a pH of 4.5. The reaction temperature is controlled via an aqueous cooling liquid circulating in a cooling jacket whereby the cooling liquid temperature is controlled by a thermostat. The reactor pressure was 25 bar absolute. Mass flow of the feeding pumps was adjusted to result in a propene feed concentration of 21.5 wt-%, a methanol feed concentration of 57 wt-% and an H2O2 feed concentration of 9.4 wt-%. The reactor was operated in down-flow operation mode. The cooling jacket temperature was 41 C, the total mass flow was 0.35 kg/h and the maximum temperature was 59C. Product output was determined by gas chromatography and the H2O2 conversion by titration. The catalyst selectivity was calculated on the basis of gas chromatographical analysis of the propene oxygenates as the ratio of the amount of propene oxide formed relative to the amount of all propene oxygenates formed. Initial H2O2 conversion was 96% at a catalyst selectivity of 96%. The reaction mixture obtained from the reaction after release of pressure was separated in the pre-evaporation stage into an overhead product containing propene, propane, propene oxide and methanol, and a bottom product containing methanol, propylene glycol monomethyl ethers, propylene glycol, water and high boiling point compounds and non-converted hydrogen peroxide. A liquid condensate that contains propene oxide and methanol as well as propene and propane dissolved therein was obtained from the vapour state overhead product. The uncondensed stream, which substantially consisted of propene and propane, was returned to the epoxidation reaction. The propene and propane dissolved in the condensate were stripped from the latter in the C3 stripper and returned in the vapour state together with the stream to the partial condensation stage. The stream, which consisted substantially of propene oxide and methanol and had been freed from propene and propane, was separated in an extractive distillation in which water was fed in as extraction agent immediately underneath the head of the column, into a propene oxide crude product that consisted initially of more than 99.5%, of propene oxide, and into a bottom product that consisted substantially of methanol and water, the water content being less than 20%. The bottom product was returned as solvent to the epoxidation reaction. The bottom product obtained in the pre-evaporator was separated in a distillation stage at a pressure of 2 bars abs. using a continuously running column having 35 stages at a reflux ratio of 2 for recovering methanol, into an overhead product that consisted of more than 95% of methanol, and into a bottom product consisting of propylene glycol monomethyl ethers, propylene glycol, water, high boiling point compounds and only traces of hydrogen peroxide. The overhead product was continuously returned as solvent to the epoxidation reaction. After 500 h running the epoxidation process the cooling temperature in the reaction step had to be increased to 50C to maintain the conversion constant at 95% and the catalyst selectivity dropped to 90%. The propene oxide stream contained 2% acetaldehyde, 0.5% methylformate and 0.2% dimethoxymethane.
With hydrogen; dihydrogen peroxide;1% Pd/C; In water; at 140℃; under 30003 Torr;pH 9;Continuously procces;Product distribution / selectivity;
Comparative Example was repeated with the exception that the bottom product obtained in the pre-evaporator stage was directed to a trickle-bed reactor for continuous hydrogenation. The hydrogenation reactor had an interior volume of 150 ml and was filled with a hydrogenation catalyst in form of extrudates with 2.3 mm diameter comprising 2% Ru on activated carbon (The catalyst was prepared according to the incipient wetness method using RuCl3, "Preparation of Catalyst", Demon, B. et al., Elsevier, Amsterdam, 1976, page 13). The hydrogenation was performed at 140 C and 40 barabs at a hydrogen flow rate of 10 ml/h. The hydrogenated product was continuously removed and had a pH of 9. The pH was reduced to be below 7 by adding sulfuric acid prior to entering the final distillation step according to the comparative example.
With ammonia; dihydrogen peroxide;titanium-silicate catalyst; In water; at 41 - 59℃; under 18751.9 Torr;pH 4.5;Continuously procces;Product distribution / selectivity;
A titanium-silicate catalyst was employed in all examples. The titanium-silicate powder was shaped into 2 mm extrudates using a silica sol as binder in accordance with example 5 in EP-A 1 138 387. The H2O2 employed was prepared according to the anthraquinone process as a 40 wt-% aqueous solution. Epoxidation is carried out continuously in a reaction tube of 300 ml volume, a diameter of 10 mm and a length of 4 m. The equipment is furthermore comprised of three containers for liquids and relevant pumps and a liquid separating vessel. The three containers for liquids comprised methanol, the 40% H2O2 and propene. The 40% H2O2 was adjusted with ammonia to a pH of 4.5. The reaction temperature is controlled via an aqueous cooling liquid circulating in a cooling jacket whereby the cooling liquid temperature is controlled by a thermostat. The reactor pressure was 25 bar absolute. Mass flow of the feeding pumps was adjusted to result in a propene feed concentration of 21.5 wt-%, a methanol feed concentration of 57 wt-% and an H2O2 feed concentration of 9.4 wt-%. The reactor was operated in down-flow operation mode. The cooling jacket temperature was 41 C, the total mass flow was 0.35 kg/h and the maximum temperature was 59C. Product output was determined by gas chromatography and the H2O2 conversion by titration. The catalyst selectivity was calculated on the basis of gas chromatographical analysis of the propene oxygenates as the ratio of the amount of propene oxide formed relative to the amount of all propene oxygenates formed. Initial H2O2 conversion was 96% at a catalyst selectivity of 96%. The reaction mixture obtained from the reaction after release of pressure was separated in the pre-evaporation stage into an overhead product containing propene, propane, propene oxide and methanol, and a bottom product containing methanol, propylene glycol monomethyl ethers, propylene glycol, water and high boiling point compounds and non-converted hydrogen peroxide. A liquid condensate that contains propene oxide and methanol as well as propene and propane dissolved therein was obtained from the vapour state overhead product. The uncondensed stream, which substantially consisted of propene and propane, was returned to the epoxidation reaction. The propene and propane dissolved in the condensate were stripped from the latter in the C3 stripper and returned in the vapour state together with the stream to the partial condensation stage. The stream, which consisted substantially of propene oxide and methanol and had been freed from propene and propane, was separated in an extractive distillation in which water was fed in as extraction agent immediately underneath the head of the column, into a propene oxide crude product that consisted initially of more than 99.5%, of propene oxide, and into a bottom product that consisted substantially of methanol and water, the water content being less than 20%. The bottom product was returned as solvent to the epoxidation reaction. The bottom product obtained in the pre-evaporator was separated in a distillation stage at a pressure of 2 bars abs. using a continuously running column having 35 stages at a reflux ratio of 2 for recovering methanol, into an overhead product that consisted of more than 95% of methanol, and into a bottom product consisting of propylene glycol monomethyl ethers, propylene glycol, water, high boiling point compounds and only traces of hydrogen peroxide. The overhead product was continuously returned as solvent to the epoxidation reaction. After 500 h running the epoxidation process the cooling temperature in the reaction step had to be increased to 50C to maintain the conversion constant at 95% and the catalyst selectivity dropped to 90%. The propene oxide stream contained 2% acetaldehyde, 0.5% methylformate and 0.2% dimethoxymethane.
With water; hydrogen; oxygen;Pd-Bi/TiO2; tegafur; at 60℃; under 16274.9 Torr; for 18h;pH 6;aqueous ammonium phosphate buffer;Product distribution / selectivity;
EXAMPLE 2; Epoxidation Reactions; A 300 cc stainless steel reactor is charged with the supported noble metal catalyst (0.07 g of 1A, 1B, or 1C), TS-1 powder (0.63 g), methanol (100 g), and a buffer solution (13 g of 0.1 M aqueous ammonium phosphate, pH=6). The reactor is then charged to 300 psig with a feed consisting of 2% hydrogen, 4% oxygen, 5% propylene, 0.5% methane and the balance nitrogen (volume %) for runs utilizing a 2:1 O2:H2 ratio or a feed consisting of 4% hydrogen, 4% oxygen, 5% propylene, 0.5% methane and the balance nitrogen (volume %) for runs utilizing a 1:1 O2:H2 ratio. The pressure in the reactor is maintained at 300 psig via a backpressure regulator with the feed gases passed continuously through the reactor at 1600 cc/min (measured at 23 C. and one atmosphere pressure). In order to maintain a constant solvent level in the reactor during the run, the oxygen, nitrogen and propylene feeds are passed through a two-liter stainless steel vessel (saturator) preceding the reactor, containing 1.5 liters of methanol. The reactor is stirred at 1500 rpm. The reaction mixture is heated to 60 C. and the gaseous effluent is analyzed by an online GC every hour and the liquid analyzed by offline GC at the end of the 18 hour run. Propylene oxide and equivalents (?POE?), which include propylene oxide (?PO?), propylene glycol (?PG?), and propylene glycol methyl ethers (PMs), are produced during the reaction, in addition to propane formed by the hydrogenation of propylene.The epoxidation results (see Table 1) show that mixed catalyst comprising TS-1 and either Pd-Bi/TiO2 or Pd-Au-Bi/TiO2 show a significant increase in propylene selectivity resulting from reduced propane make, as compared to mixtures of TS-1 and Pd-Au/TiO2.
With water; hydrogen; oxygen;Pd-Au/TiO2; tegafur; at 60℃; under 16274.9 Torr; for 18h;pH 6;aqueous ammonium phosphate buffer;Product distribution / selectivity;
EXAMPLE 2; Epoxidation Reactions; A 300 cc stainless steel reactor is charged with the supported noble metal catalyst (0.07 g of 1A, 1B, or 1C), TS-1 powder (0.63 g), methanol (100 g), and a buffer solution (13 g of 0.1 M aqueous ammonium phosphate, pH=6). The reactor is then charged to 300 psig with a feed consisting of 2% hydrogen, 4% oxygen, 5% propylene, 0.5% methane and the balance nitrogen (volume %) for runs utilizing a 2:1 O2:H2 ratio or a feed consisting of 4% hydrogen, 4% oxygen, 5% propylene, 0.5% methane and the balance nitrogen (volume %) for runs utilizing a 1:1 O2:H2 ratio. The pressure in the reactor is maintained at 300 psig via a backpressure regulator with the feed gases passed continuously through the reactor at 1600 cc/min (measured at 23 C. and one atmosphere pressure). In order to maintain a constant solvent level in the reactor during the run, the oxygen, nitrogen and propylene feeds are passed through a two-liter stainless steel vessel (saturator) preceding the reactor, containing 1.5 liters of methanol. The reactor is stirred at 1500 rpm. The reaction mixture is heated to 60 C. and the gaseous effluent is analyzed by an online GC every hour and the liquid analyzed by offline GC at the end of the 18 hour run. Propylene oxide and equivalents (?POE?), which include propylene oxide (?PO?), propylene glycol (?PG?), and propylene glycol methyl ethers (PMs), are produced during the reaction, in addition to propane formed by the hydrogenation of propylene.The epoxidation results (see Table 1) show that mixed catalyst comprising TS-1 and either Pd-Bi/TiO2 or Pd-Au-Bi/TiO2 show a significant increase in propylene selectivity resulting from reduced propane make, as compared to mixtures of TS-1 and Pd-Au/TiO2.
With water; hydrogen; oxygen;Pd-Bi-Au/TiO2; tegafur; at 60℃; under 16274.9 Torr; for 18h;pH 6;aqueous ammonium phosphate buffer;Product distribution / selectivity;
EXAMPLE 2; Epoxidation Reactions; A 300 cc stainless steel reactor is charged with the supported noble metal catalyst (0.07 g of 1A, 1B, or 1C), TS-1 powder (0.63 g), methanol (100 g), and a buffer solution (13 g of 0.1 M aqueous ammonium phosphate, pH=6). The reactor is then charged to 300 psig with a feed consisting of 2% hydrogen, 4% oxygen, 5% propylene, 0.5% methane and the balance nitrogen (volume %) for runs utilizing a 2:1 O2:H2 ratio or a feed consisting of 4% hydrogen, 4% oxygen, 5% propylene, 0.5% methane and the balance nitrogen (volume %) for runs utilizing a 1:1 O2:H2 ratio. The pressure in the reactor is maintained at 300 psig via a backpressure regulator with the feed gases passed continuously through the reactor at 1600 cc/min (measured at 23 C. and one atmosphere pressure). In order to maintain a constant solvent level in the reactor during the run, the oxygen, nitrogen and propylene feeds are passed through a two-liter stainless steel vessel (saturator) preceding the reactor, containing 1.5 liters of methanol. The reactor is stirred at 1500 rpm. The reaction mixture is heated to 60 C. and the gaseous effluent is analyzed by an online GC every hour and the liquid analyzed by offline GC at the end of the 18 hour run. Propylene oxide and equivalents (?POE?), which include propylene oxide (?PO?), propylene glycol (?PG?), and propylene glycol methyl ethers (PMs), are produced during the reaction, in addition to propane formed by the hydrogenation of propylene.The epoxidation results (see Table 1) show that mixed catalyst comprising TS-1 and either Pd-Bi/TiO2 or Pd-Au-Bi/TiO2 show a significant increase in propylene selectivity resulting from reduced propane make, as compared to mixtures of TS-1 and Pd-Au/TiO2.
11.8%Chromat.
With ammonium acetate; hydrogen; oxygen; at 60℃; under 56255.6 Torr; for 12h;Autoclave; Supercritical conditions;Catalytic behavior;
General procedure: PO synthesis reaction from propylene in presence of ex situ H2O2, as oxidizing agent, were performed in a 3 mL round bottom glass reactor in which the stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of TS-1 catalyst (2.5 mg), methanol (1.2 g), and propylene (9 mmol) were added, followed by the addition of the oxidant, 35% wt H2O2 in water (0.4 mmol). Then, the mixture was heated at 60C, and the reaction was monitored for 5 h. The experiments for the direct synthesis of PO with in situ generated H2O2 were carried out in a 15 mL stainless steel reactor which contained a relief valve, for safety. The stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of catalyst (15 mg), acidity inhibitor (ammonium acetate, 0.01 g) and co-solvent (0.2 gof different co-solvents) were added to the reactor, followed by the addition of propylene (2 mmol) and CO2, reaching carbon dioxide vapor pressure (>55 bar). Oxygen and hydrogen were added to the reactor by means of high pressure burettes, and then the reactor was heated up to desired temperature (ranging from room temperature to 80C, according each experiment). The reaction experiments were carried out for 5 h, unless otherwise stated. At the end of the reaction, the reactor was cooled down and the pressure was slowly released by venting, accumulating the gaseous mixture in an inert gas sampling bag. 3-pentanone was used forrecovering any product that could be retained on the reactor walls. The amount of formed products, i.e., propylene oxide, acetone, propionaldehyde, acrolein, isopropanol, 1-methoxy-2-propanol (MP1), 2-methoxy-1-propanol (MP2), propylene glycol (PG) and propylene carbonate were analyzed using a Shimadzu Gas chro-matograph GC-2010 Plus provided with FID detector and 20 m length, 0.10 mm ID, 0.10 m df. Permabond FFAP column. The amounts of propane and unreacted propylene, oxygen and hydrogen were analyzed using a Bruker 450-GC which contains two different independent channels. The first one is provided with a thermal conductivity detector (TCD) and three different columns: Hayesep N (0.5 m length), Hayesep Q (1.5 m length) and molsieve 13× (1.2 m length), using argon as carrier. The second one is provided with two different flame ionization detectors (FID) and three different columns: capillary column CP-Wax (1 m length and 0.32 mm ID), CP-Porabond Q (25 m length and 0.32 mm ID) and CP-Wax (5 m length and 0.32 mm ID).
EXAMPLES 6-7 These examples demonstrate that the integrated process of this invention, which uses a "crude" (unpurified) oxidant mixture obtained by air oxidation of an aryl-substituted secondary alcohol, provides epoxide yields equivalent to those obtained using purified hydrogen peroxide diluted in a "clean" alcohol/ketone reaction medium. A 300 ml glass-lined autoclave equipped with a Teflon stir shaft and blade and thermowell was charged with methanol (25 ml) and "TS-1" titanium silicalite catalyst (0.73g), followed by liquid propylene (16 mL; 0.20 mole). The autoclave was heated to 37 C. by means of an external coil attached to a circulating bath. A crude oxidant mixture (100 mL) obtained by air oxidation of alpha-methyl benzyl alcohol and containing 5.15 weight percent hydrogen peroxide was charged to an Isco pump and added to the contents of the autoclave over a 1 hour period. The reaction mixture exothermed to 45 C. and was stirred at this temperature for an additional 2 hours after addition was completed. The pressure dropped from 120 psia to ca. 42 psia during the reaction. The external heating cord was replaced with an ice bath and the liquid contents of the autoclave cooled to 20 C. The autoclave was vented and the head removed for product sampling. The reaction product was analyzed by iodometric titration (residual hydrogen peroxide) and gas chromatography (organic products). The results are shown in Table I below (Example 6). Epoxide selectivity with respect to olefin was over 99%, with no detectable amount of propylene glycol and less than 1% of 2-methoxy-1-propanol and 1-methoxy-2-propanol being produced.
4-[4-(2-chloro-4-bromophenoxy)phenoxy]2-pentenoic acid[ No CAS ]
[ 1589-47-5 ]
[ 72325-98-5 ]
Yield
Reaction Conditions
Operation in experiment
91.3%
With thionyl chloride;
Preparation 4-3 2-Methoxypropyl 4-[4-(4-bromo-2-chlorophenoxy)phenoxy](2)-pentenoate A mixture of 14.2 g of 4-[4-(4-bromo-2-chlorophenoxy)phenoxy]2-pentenoic acid and 25 ml of thionyl chloride was refluxed for 6 hours to react them. Excess of thionyl chloride was distilled off from the reaction mixture and 15 ml of <strong>[1589-47-5]2-methoxypropyl alcohol</strong> was added to the residue of the acid chloride. After the addition, the mixture was gradually heated to react them at 60 C. for 5 hours and excess of <strong>[1589-47-5]2-methoxypropyl alcohol</strong> was distilled off under a reduced pressure to obtain 17.2 g of an orange viscous liquid having ND20: 1.5210 (yield: 91.3%).
With hydrogen; oxygen;Pd/TS-1; In water; at 60℃; under 16274.9 Torr;pH 6;ammonium phosphate buffer;Product distribution / selectivity;
An ammonium phosphate buffer solution (0.1 M, pH 6) is prepared as follows. Ammonium dihydrogen phosphate (11.5 g) is dissolved in deionized water (900 g). Aqueous ammonium hydroxide (30 wt. % NH4OH) is added to the solution until the pH reads 6 via a pH meter. The volume of the solution is then increased to exactly 1000 mL with additional deionized water. A 300-mL stainless steel reactor is charged with Catalyst A (0.7 g), the buffer solution prepared above (13 g), and methanol (100 g). The reactor is then charged to 300 psig with a feed gas consisting of 2 volume percent (vol. %) hydrogen, 4 vol. % oxygen, 5 vol. % propylene, 0.5 vol. % methane, and the balance nitrogen. The pressure in the reactor is maintained at 300 psig via a back pressure regulator with the feed gases passed continuously through the reactor at 1600 mL/min (measured at 23 C. and 1 atmosphere pressure). In order to maintain a constant solvent level in the reactor during the run, the oxygen, nitrogen and propylene feeds are passed through a 2-L stainless steel vessel (saturator) preceding the reactor containing 1.5 L of methanol. The reaction mixture is heated to 60 C. while it is stirred at 1500 rpm. The gaseous effluent is analyzed by an online gas chromatograph (GC) every hour and the liquid analyzed by offline GC at the end of the 18 h run. The products formed include propylene oxide (PO), propane, and derivatives of propylene oxide such as propylene glycol, propylene glycol monomethyl ethers, dipropylene glycol, and dipropylene glycol methyl ethers. The catalyst productivity is 0.37 g POE/g cat/h. Propylene to POE selectivity is 68%. Propylene to propane selectivity is 32%. The catalyst productivity is defined as the grams of PO formed (including PO which is subsequently reacted to form PO derivatives) per gram of catalysts (Pd/TS-1) per hour. POE (mole)=moles of PO+moles of PO units in the PO derivatives. PO/POE=(moles of PO)/(moles of POE)×100. Propylene to POE selectivity=(moles of POE)/(moles of propane formed+moles of POE)×100. Propylene to propane selectivity=(moles of propane formed)/(moles of propane formed+moles of POE)×100.
poly(benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-methacrylic acid-co-2-methoxypropanol)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
V-65; at 65℃; for 10h;
-Synthesis of Resin P-1-; 70.0 g of <strong>[2495-37-6]benzyl methacrylate</strong>, 13.0 g of methacrylic acid, 17.0 g of 2-hydroxyethyl methacrylate, and 600 g of 2-methoxypropanol were placed in a three-neck flask which was attached with a stirrer, a reflux condenser tube, and thermometer. The mixture was mixed with a catalytic quantity of a polymerization initiator (trade name: V-65, made by Wako Pure Chemical Industries, Inc.), and was stirred for 10 hours at 65 C. in a nitrogen stream. The resin solution obtained was dripped into 20 L of ion-exchange water with vigorous stirring, and a white powder was obtained. The white powder was dried at 40 C. for 24 hours in a vacuum, and 145 g of resin P-1 was obtained. The molecular weight was measured by GPC, which showed the weight average molecular weight Mw=28,000, and number average molecular weight Mn=11,000.
With sodium hydride; In tetrahydrofuran; mineral oil; for 24h;Reflux;
A solution of 2-fiuoro-5-chlorobenzoic acid (2.9g, 16.6mmol) and 2-methoxypropanol (4.5g, 50mmol) in anhydrous THF (125ml) was treated portionwise with NaH (60% dispersion in mineral oil, 5.0g, 125mmol). The resulting mixture was stirred at reflux for 24hrs.The reaction was cooled to RT, diluted with EtOAc and acidified with 2M HC1. The organics were separated, dried and concentrated to give an oil. Columnchromatography (Si02; 1 :0?1 : 1 PE:EtOAc) gave the title compound (1.42g, 5.8mmol) NMR (CDCls) delta 8.16 (IH, d, J2.8), 7.49 (IH, dd, J 8.8, 2.8), 7.00 (IH, d, J 8.8), 4.35 (2H, m), 3.57 (2H, m), 3.39 (3H, s), 2.17 (2H, m)
With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; potassium chloride; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
62.9%; 14.4%; 12.5%
With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; potassium bromide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
44.1%; 6.7%; 5.8%
With potassium bromide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
41.7%; 29.8%; 23%
With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; potassium chloride; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
35.9%; 7.8%; 7.8%
With potassium chloride; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
With lithium iodide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
With dihydrogen peroxide; In methanol; at 60℃; under 60006 Torr; for 5h;Autoclave;
The experiments for the direct synthesis of PO with in situgenerated H2O2were carried out in a 15 mL stainless steel auto-clave coated with a Teflon beaker and with a relief valve, forsafety. The stirring was driven by a Teflon-coated magnetic stirrer.Known amounts of catalyst (15 mg), acidity inhibitor (ammoniumacetate, 0.01 g) and co-solvent (0.2 g of MeOH or a 50/50 mixtureof MeOH/H2O) were added to the reactor, followed by the additionof propylene (2 mmol) and CO2. Known amounts of oxygen andfinally hydrogen were then added to the reactor, which was thenheated up until the desired temperature, the critical point (73.8 barand 31C) being surpassed. The reaction experiments were carriedout for 5 h, unless otherwise stated. After that time, the reactorwas cooled down using a mixture of acetone and ice, and thepressure was slowly released by venting, recovering the gaseousmixture in an inert gas sampling bag. 3-pentanone was used forrecovering any product that could be in the walls of the reactor,avoiding the employment of acetone because could be a possibleby-product
With lithium bromide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
With polyethylene glycol (MW=4000); at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure;
General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min.
With hydrogenchloride; In water; at 120℃; for 72h;
EXAMPLE 1 Commercially available PGME containing both <strong>[1589-47-5]2-methoxypropan-1-ol</strong> and 1-methoxypropan-2-ol was added to a flask, followed by 1 mol % of trimethylacetic anhydride, and an acid catalyst. The reaction was heated to 120 C. and allowed to stir under mild reflux conditions for 72 hours, prior to fractional distillation of the reagent through a Vigreux column packed with glass beads. All distillate collected before a steady reading of 119-121 C. in the distillation head was discarded, and the subsequent fraction was collected for analysis, until a sudden temperature change was noted. Subsequently, the distillate was analyzed against a standard of >99% pure <strong>[1589-47-5]2-methoxypropan-1-ol</strong> by gas chromatography using an Agilent 6890 gas chromatograph, equipped with a flame ionization detector, an Agilent 122-1334 DB-624 60m×0.53 mm column with helium as the carrier gas (1.5 mL/min), a 1.0 muL injection volume, an injector split ratio of 10:1, and an initial oven temperature of 40 C., a temperature ramp of 2 C./min to 80 C. with an 8 min. hold time followed by a a temperature ramp of 20 C./min to 200 C. with a 5 min. hold time. The results are reported in Table 1. The Control sample was the commercially available PGME itself.
EXAMPLE 2 To a 250 mL round bottomed flask containing a stir bar is added 100 g PGME (1.11 mol, 1.0 equiv) as a mixture of approximately 99.88% of 1-methoxypropan-2-ol (PM-2) and 0.12% of <strong>[1589-47-5]2-methoxypropan-1-ol</strong> (beta-isomer, PM-1). Benzoic anhydride (2.5 g, 11.1 mmol, 0.01 equiv) is next added to the flask, followed by concentrated sulfuric acid (10.9 g, 111.0 mmol, 0.1 equiv). A reflux condenser is affixed to the reaction and it is left to stir for 36 hours in an oil bath set to 115 C. At the end of this interval, the reflux condenser is removed and a vacuum-jacketed Vigreux column filled with glass beads 1 mm in diameter is attached. Atop this, a short path distillation head is placed with a 100 mL receiving flask. The temperature of the oil bath is increased to 130 C., and the first distillate fraction is collected as the major product, within a temperature range of 118-120 C. Analysis of this material indicates that it consists of starting material isomer PM-2 and is substantially free of isomer PM-1. This process is illustrated by the following reaction scheme.
With hydrogenchloride; In water; at 115℃; for 36h;Reflux;
EXAMPLE 2 To a 250 mL round bottomed flask containing a stir bar is added 100 g PGME (1.11 mol, 1.0 equiv) as a mixture of approximately 99.88% of 1-methoxypropan-2-ol (PM-2) and 0.12% of <strong>[1589-47-5]2-methoxypropan-1-ol</strong> (beta-isomer, PM-1). Benzoic anhydride (2.5 g, 11.1 mmol, 0.01 equiv) is next added to the flask, followed by concentrated sulfuric acid (10.9 g, 111.0 mmol, 0.1 equiv). A reflux condenser is affixed to the reaction and it is left to stir for 36 hours in an oil bath set to 115 C. At the end of this interval, the reflux condenser is removed and a vacuum-jacketed Vigreux column filled with glass beads 1 mm in diameter is attached. Atop this, a short path distillation head is placed with a 100 mL receiving flask. The temperature of the oil bath is increased to 130 C., and the first distillate fraction is collected as the major product, within a temperature range of 118-120 C. Analysis of this material indicates that it consists of starting material isomer PM-2 and is substantially free of isomer PM-1. This process is illustrated by the following reaction scheme. EXAMPLE 4 The procedure of Example 2 is repeated except that he benzoic anhydride is replaced with 1-pyrenecarboxylic acid (5.4 g, 22.2 mmol, 0.02 equiv), and the sulfuric acid catalyst is replaced with 12.1N aqueous hydrochloric acid (9.2 mL, 111.0 mmol, 0.1 equiv). Analysis of the distillate indicates that it is isomer PM-2 and is substantially free of isomer PM-1. This process is illustrated by the following reaction scheme.
EXAMPLE 6 (urified PGME Sample 3 from Example 1, containing 9 ppm of the beta-isomer (<strong>[1589-47-5]2-methoxypropan-1-ol</strong>), is acylated with acetic acid (1.2 molar equivalents) at a temperature of 80 to 150 C. in the presence of an acid catalyst (0.05 to 1 wt %), such as hydrochloric acid, to provide PGMEA having ?9 ppm of the beta-isomer (2-methoxypropan-1-acetate).
With 1-butyl-3-methylimidazolium hydrogen sulfate; cyclohexane; at 75 - 150℃; for 4h;
In a thermometer, distillation column,Condenser, water separator 1000ml glass four-necked flask,270 g of <strong>[1589-47-5]2-methoxy-1-propanol</strong> was added,Acetic acid 360g, <strong>[1589-47-5]2-methoxy-1-propanol</strong> and acetic acid molar ratio of 1: 2,Acidic ionic liquid catalystThe amount of 1-butyl-3-methylimidazolium hydrogen sulfate was 6.3g,The dehydrating agent cyclohexane was 122 g,The temperature was raised and the reaction was kept in boiling (75-150 C)Reflux separation, 4h reaction is over,The reaction mixture was weighed and analyzed by gas chromatography to determine the content of <strong>[1589-47-5]2-methoxy-1-propanol</strong> acetate in the reaction solution,The calculated reaction yield was 97.9%.
EXAMPLE 6 (urified PGME Sample 3 from Example 1, containing 9 ppm of the beta-isomer (<strong>[1589-47-5]2-methoxypropan-1-ol</strong>), is acylated with acetic acid (1.2 molar equivalents) at a temperature of 80 to 150 C. in the presence of an acid catalyst (0.05 to 1 wt %), such as hydrochloric acid, to provide PGMEA having ?9 ppm of the beta-isomer (2-methoxypropan-1-acetate). EXAMPLE 7 The procedure of Example 6 is repeated except that the acetic acid is replaced with acetic anhydride (0.65 molar equivalents) and the acid catalyst is phosphoric acid.
With ammonium acetate; hydrogen; oxygen; at 60℃; under 56255.6 Torr; for 7h;Autoclave; Supercritical conditions;Catalytic behavior;
General procedure: PO synthesis reaction from propylene in presence of ex situ H2O2, as oxidizing agent, were performed in a 3 mL round bottom glass reactor in which the stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of TS-1 catalyst (2.5 mg), methanol (1.2 g), and propylene (9 mmol) were added, followed by the addition of the oxidant, 35% wt H2O2 in water (0.4 mmol). Then, the mixture was heated at 60C, and the reaction was monitored for 5 h. The experiments for the direct synthesis of PO with in situ generated H2O2 were carried out in a 15 mL stainless steel reactor which contained a relief valve, for safety. The stirring was driven by a Teflon-coated magnetic stirrer. Known amounts of catalyst (15 mg), acidity inhibitor (ammonium acetate, 0.01 g) and co-solvent (0.2 gof different co-solvents) were added to the reactor, followed by the addition of propylene (2 mmol) and CO2, reaching carbon dioxide vapor pressure (>55 bar). Oxygen and hydrogen were added to the reactor by means of high pressure burettes, and then the reactor was heated up to desired temperature (ranging from room temperature to 80C, according each experiment). The reaction experiments were carried out for 5 h, unless otherwise stated. At the end of the reaction, the reactor was cooled down and the pressure was slowly released by venting, accumulating the gaseous mixture in an inert gas sampling bag. 3-pentanone was used forrecovering any product that could be retained on the reactor walls. The amount of formed products, i.e., propylene oxide, acetone, propionaldehyde, acrolein, isopropanol, 1-methoxy-2-propanol (MP1), 2-methoxy-1-propanol (MP2), propylene glycol (PG) and propylene carbonate were analyzed using a Shimadzu Gas chro-matograph GC-2010 Plus provided with FID detector and 20 m length, 0.10 mm ID, 0.10 m df. Permabond FFAP column. The amounts of propane and unreacted propylene, oxygen and hydrogen were analyzed using a Bruker 450-GC which contains two different independent channels. The first one is provided with a thermal conductivity detector (TCD) and three different columns: Hayesep N (0.5 m length), Hayesep Q (1.5 m length) and molsieve 13× (1.2 m length), using argon as carrier. The second one is provided with two different flame ionization detectors (FID) and three different columns: capillary column CP-Wax (1 m length and 0.32 mm ID), CP-Porabond Q (25 m length and 0.32 mm ID) and CP-Wax (5 m length and 0.32 mm ID).
With carbon dioxide; In methanol; at 200℃; under 20686.5 - 97743.6 Torr; for 5h;Sealed tube;
Experimental condition (MeOH, DMC, C02). A 250 cc Hastelloy pressure vessel was charged with 10 g of propylene glycol (PG, 131 mmol), 50 g of dimethyl carbonate (DMC, 550 mol, 4.2 eq.) and 50 g of MeOH. The vessel was then sealed tightly and affixed to the reactor apparatus, purged x3 with 400 psi of C02, then saturated with CO2 until the pressure remained steady at 400 psi (methanol absorbs considerably amounts of C02). While stirring at 700 rpm, the vessel was heated to 200C,where the reaction persisted for 5 h; the maximum pressure attained was 1890 psi at this temperature. After that time, the solution was cooled to ambient temperature, gas released, and stirring halted. The resultant brownish solution was then analyzed by GC/MS (70C initial temp, hold for 4 mm, then 10C per minute until 300C, hold for 10 mm). The resultant chromatogram (Figure 1 2A) revealed a small signal at 2.72 mm with m/z of 76.0 (unreacted PG), and two prominent signals at 2.126,2.159 mm bothwith m/z of 90.0, consistent with the monomethylether isomers of PG. Figures 12B and 12C show the mass spectrum of the PG-monoethyl ether isomers A or B.[0058] GC/MS analysis using a HP Innowax column and following inlet and oven temperatureramps: Inlet - 60C initial, hold for 1 mm, ramp 5C per mm until 100C, no hold, ramp 60C per mm until 250C; Oven - 70C initial, hold for 5 mm, ramp 10C per mm until l5OoC, no hold, ramp 20Cper minute until 240 mm, no hold. The results are presented in Figures 13A-13D.[0059] FIG. 13A, is a gas chromatogram of the mixed mono- and di-methyl ether products of PG etherification according to an embodiment of the present process. FIG. 13B is the mass spectrum corresponding to the signal at 13.52 minutes in the gas chromatogram detailed in Figure 13A, andspecifying unreacted propylene glycol. FIG 1 3C is the mass spectrum corresponding to the signal at2.502 minutes in the gas chromatogram detailed in Figire 13A, and denoting PG dimethyl ether (1,2-dimethoxypropane). FIG 13D is a mass spectrum corresponding to the signal at 3.158 minutes in the gas chromatogram detailed in Figure 1 3A, and represents isomers of PG monomethyl ether (1-methoxypropan-2-ol and 2-methoxypropan-1 -ol).[0060] Both the chromatograms and corresponding spectra reveal clearly a high rate of conversion ofPG to the preponderant monomethyl ethers, which did not separate, as well as a significant amount ofthe dimethyl ethers. The control experiment (no C02) manifested only unreacted PG.
heptafluoro-2-methoxypropionic acid 2-methoxypropyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
>= 95%
With titanium(IV) tetraethanolate; In diethylene glycol dimethyl ether; at -5 - 80℃; under 11251.1 Torr; for 8h;Autoclave;
Accurately weigh 200ml of polar aprotic organic solvent diethylene glycol dimethyl ether, procatalyst 4g titanium tetraethoxide, 200g of <strong>[1589-47-5]2-methoxypropanol</strong>, add to 1L stainless steel autoclave reactor, replace with nitrogen, vacuum Under stirring, maintain the temperature for about 30 minutes at 25 C.The temperature was lowered to -5 C to 0 C, and 500 g of perfluoro-2-methoxypropionyl fluoride was continuously added at a rate of 5 ml/min to 30 ml/min.The temperature was started to be esterified, the temperature was maintained at 80 C, and the pressure was ? 1.5 MPa.After the reaction for 8 h, 600 g of the product was collected.Upon analysis, the product was heptafluoro-2-methoxypropionic acid-5-methoxypropyl ester with a purity of >99%.The reaction yield of this step is ?95%.
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