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HazMat fee for 500 gram (Estimated)
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USD 0.00
Limited Quantity
USD 15-60
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USD 80+
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Structure of 111-27-3 * 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] Bulletin de la Societe Chimique de France, 1936, vol. <5>3, p. 1065
[2] Journal of the Chemical Society [Section] C: Organic, 1966, p. 346 - 350
[3] Patent: US2006/84822, 2006, A1, . Location in patent: Page/Page column 7-8
[4] Patent: US2006/84822, 2006, A1, . Location in patent: Page/Page column 7-8
16
[ 111-27-3 ]
[ 503-38-8 ]
[ 6092-54-2 ]
Reference:
[1] Journal of the Chinese Chemical Society, 2000, vol. 47, # 1, p. 271 - 274
[2] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 8, p. 1716 - 1727
17
[ 127-19-5 ]
[ 111-27-3 ]
[ 1118-92-9 ]
Reference:
[1] Journal of the American Chemical Society, 2016, vol. 138, # 34, p. 10786 - 10789
[2] RSC Advances, 2013, vol. 3, # 33, p. 13702 - 13704
[3] Organic and Biomolecular Chemistry, 2016, vol. 14, # 39, p. 9215 - 9220
18
[ 124-63-0 ]
[ 111-27-3 ]
[ 16156-50-6 ]
Yield
Reaction Conditions
Operation in experiment
99%
With triethylamine In dichloromethane at 0 - 20℃;
General procedure: Alcohols (50 mmol, 1 equiv.) and 11.08 mL Et3N (80 mmol, 1.6 equiv.) was dissolved in 60 mL CH2Cl2, and the solution was cooleddown to 0 °C, then 4.33 mL methanesulfonyl chloride (56 mmol, 1.12 equiv.) was introduced by syringe successively. The mixture is stirredfor 30 min at 0 °C, and then stirred overnight at room temperature. The organic layer is washed successively with 1M hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and brine. The organic layer is dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by column chromatography with silica gel (EtOAc: petroleum=1: 2).
Reference:
[1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 41, p. 7753 - 7759
[2] Journal of the American Chemical Society, 1985, vol. 107, # 18, p. 5210 - 5219
[3] Journal of Fluorine Chemistry, 2018, vol. 214, p. 35 - 41
[4] Journal of the Electrochemical Society, 2010, vol. 157, # 9, p. F124-F129
[5] European Journal of Organic Chemistry, 2018, vol. 2018, # 35, p. 4850 - 4856
[6] Canadian Journal of Chemistry, 1956, vol. 34, p. 757,760
[7] Journal of the American Chemical Society, 1954, vol. 76, p. 2984,2986
[8] Journal of Medicinal Chemistry, 1990, vol. 33, # 10, p. 2807 - 2813
[9] Tetrahedron Letters, 1990, vol. 31, # 17, p. 2457 - 2460
[10] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1991, # 8, p. 1201 - 1208
[11] Synthetic Communications, 1984, vol. 14, # 5, p. 469 - 476
[12] Green Chemistry, 2009, vol. 11, # 12, p. 1955 - 1960
[13] Physical Chemistry Chemical Physics, 2009, vol. 11, # 39, p. 8939 - 8948
[14] Catalysis Communications, 2010, vol. 11, # 5, p. 470 - 475
[15] Tetrahedron Letters, 2017, vol. 58, # 1, p. 59 - 62
19
[ 112-30-1 ]
[ 111-27-3 ]
[ 3913-02-8 ]
[ 2425-77-6 ]
[ 21078-85-3 ]
[ 5333-42-6 ]
Yield
Reaction Conditions
Operation in experiment
8.4%
at 255℃; for 6 h; Dean-Stark; Inert atmosphere
General procedure: A 100 mL five-neck flask equipped with; a magnetic stirring-bar, a temperature probe, a nitrogen inlet, a condenser and a Dean-Stark system for separating the water formed by the reaction, was charged with 40 g of 1 -octanol, 0.6 g of granular potassium hydroxide (1 .5 wtpercent) and 0.4 g of copper-nickel catalyst comprised in a hydrotalcite (the Cu/Ni molar ratio was 2.5/7.5; and the total content of copper and nickel metals in the whole catalyst was 13percent by weight). The temperature was elevated under N2 flow (rate of 50 to 60 mL/min) up to the boiling point of the alcohol (195 9C). The time when the reaction mixture reached 190 to 200 QC (reflux) was designed as the point of initiation of the reaction. The highest temperature allowed for the reaction to be conducted was 225 QC. The reaction was terminated after 8 hours. Then, the liquid reaction mixture was cooled and centrifuged to remove the copper- nickel catalyst and the precipitated soap-type products (potassium carboxylates). The composition of the final reaction mixture was analysed by GC, as follow: 83.4percent 2-hexyl-1 - decanol; 5.3percent C16-non-Guerbet; 5.3percent C24-products; 2.1 percent 1 -octanol. (0223) The 1 -octanol conversion, 2-hexyl-1 -decanol (C16-Guerbet alcohol) product selectivity, C16- Guerbet (alcohol) product yield after 6 hours reaction and the C16-non-Guerbet (alcohol) (such as 2-hexyl-2-decenal, 2-hexyldecanal and 2-hexyl-2-decen-1 -ol) product yield after 6 hours reaction are shown in Table 1 . A purity of the final target product (2-hexyl-1 -decanol (C16-Guerbet alcohol)) was calculated considering the losses in the mass balance during the reaction (due to the formation of carboxylic salts and 1 -octanol evaporation) and subtracting the un reacted 1 -octanol. This value is a good agreement with the purity of the Cl 6-Guerbet estimated after distillation of the final reaction mixture.
General procedure: All the reactions were carried out in an autoclave reactor withan inner volume of 190 ml. A typical procedure of the reaction of CO2 + methanol with 2-cyanopyridine was as follows: 0.34 g of CeO2 catalyst, 0.64 g of methanol (20 mmol, Wako Pure Chemical Industries, 99.8percent min.), and 10.4 g of 2-cyanopyridine (100 mmol,Tokyo Chemical Industry Co., Ltd., 99.0percent min.) were put into the autoclave together with a spinner, and then, the reactor was purged and pressurized with CO2 (Shimakyu Co. Ltd., >99.5percent). Gas line was closed, and then, the reactor was heated to the reaction temperature. The time when the temperature reached the desired reaction temperature is defined as zero reaction time. The mixture was constantly stirred during the reaction. After the specific reaction time, the reactor was cooled to room temperature and the gas was collected. Ethanol (30 ml, Wako Pure Chemical Industries, 99.5percent min.) and 1-hexanol (0.2 ml, Tokyo ChemicalIndustry Co., Ltd., 98.0percent min.) were added to the liquid phase asa solvent and an internal standard substance for a quantitativeanalysis, respectively. Products in the liquid and gas phases were analyzed by using a gas chromatograph equipped with FID(Shimadzu GC-2014) and GC–MS (Shimadzu QP-2020) with a CP-Sil5 capillary column (length 50 m, i.d. 0.25 mm, film thickness0.25 μm). For the synthesis of various carbonates from CO2 and the corresponding alcohols, the procedures are the same as the case of the reaction of CO2 + methanol with 2-cyanopyridine. After the reaction time, 30 ml of ethanol or acetone (Wako Pure Chemical Industries,99.5percent min.) was added to the liquid phase as a solvent, and 0.2 ml of 1-hexanol or 1-propanol (Wako Pure Chemical Industries,99.5percent min.) was added to the liquid phase as an internal standard substance for a quantitative analysis. The products in the liquid and gas phases were analyzed by gas chromatography equippedwith an FID or quadrupole mass spectrometer (GC–MS) using a CP-Sil5 capillary column (length 50 m, i.d. 0.25 mm, film thickness 0.25 μm) or TC-WAX capillary column (length 30 m, i.d. 0.25 mm, film thickness 0.25 μm).
40%
at 130℃; for 288 h; Heating
Into a two-necked flask equipped with a condenser was inserted an injection tube which had connected thereto a glass ball filter (G2) (manufactured and sold by Vidrex Co., Ltd., Japan). Further, a stirrer was placed in the flask. Into the two-necked flask were charged 0.75 g of the above-obtained liquid (containing an organometal compound) and 41 g of n-hexanol. Then, introduction of a high purity carbon dioxide gas into the flask through the injection tube was started at a flow rate of 100 ml/min. The flask was heated using an oil bath (which was maintained at 130 °C) while stirring the contents of the flask and introducing a high purity carbon dioxide gas into the flask, thereby producing dihexyl carbonate. 288 hours after the start of the heating of the flask, the yield of dihexyl carbonate was 40 percent.
18%
at 120℃; for 100 h;
Production of dihexyl carbonate from dibutyltin dihexyloxide Into a 100-ml autoclave (manufactured and sold by Toyo Koatsu Co., Ltd., Japan) were charged about 2.2 g of an organometal compound containing about 5 mmol of dibutyltin dihexyloxide (wherein the organometal compound was contained in the above-obtained reaction mixture) and 25.5 g (250 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade). The autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 4 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 120 °C while stirring. Thereafter, carbon dioxide gas was gradually withdrawn from the autoclave through a purge line so as to adjust the internal pressure of the autoclave to 4 MPa. Then, a reaction was performed for 100 hours while maintaining the internal pressure of the autoclave at 4 MPa. After that period, the inside of the autoclave was cooled to about 30 °C, and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through a purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 18 percent.
17%
at 120℃; for 100 h;
Into a 100-ml autoclave (manufactured and sold by Toyo Koatsu Co., Ltd., Japan) were charged about 2.2 g of an organometal compound containing about 5 mmol of dibutyltin dihexyloxide (wherein the organometal compound was contained in the above-obtained reaction mixture) and 25.5 g (250 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade). The autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 4 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 120 °C while stirring. Thereafter, carbon dioxide gas was gradually withdrawn from the autoclave through a purge line so as to adjust the internal pressure of the autoclave to 4 MPa. Then, a reaction was performed for 100 hours while maintaining the internal pressure of the autoclave at 4 MPa. After that period, the inside of the autoclave was cooled to about 30 °C, and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through a purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 17 percent.
14%
at 180℃; for 6.16667 h;
Into the above-mentioned 200-ml autoclave containing the reaction mixture (containing an organometal compound having a hexyloxy group) was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade), and the autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 5 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 °C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 °C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of about 14 percent.
14%
at 180℃; for 6.16667 h;
Subsequently, the same procedures as in step (1) and step (2) were successively performed as follows. Step (1): Production of dihexyl carbonate from the organometal compound obtained in step (3) Into the above-mentioned autoclave in which step (3) was performed was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade), and the autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 5 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 °C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 °C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through the purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of about 14 percent.
Reference:
[1] Journal of Catalysis, 2014, vol. 318, p. 95 - 107
[2] Patent: EP1460056, 2004, A1, . Location in patent: Page 32
[3] Journal of the Chemical Society - Perkin Transactions 1, 1999, # 15, p. 2205 - 2208
[4] Patent: EP1460056, 2004, A1, . Location in patent: Page 29
[5] Patent: EP1460056, 2004, A1, . Location in patent: Page 29-30
[6] Patent: EP1460056, 2004, A1, . Location in patent: Page 27
[7] Patent: EP1460056, 2004, A1, . Location in patent: Page 28
21
[ 57-13-6 ]
[ 111-27-3 ]
[ 7523-15-1 ]
Yield
Reaction Conditions
Operation in experiment
92.3%
at 140 - 170℃; for 20 h;
The reaction apparatus was the same as in Example 1. Take 10g urea, 68g n-hexanol, 0.5g nickel acetate, 2g triphenylphosphine in a three-neck bottle, heat in 170 ° C oil bath, vacuum, system vacuum 10Kpa, system maintain 140 ° C, slightly boiling, stirring reflux Reaction for 20 hr.Gas chromatography analysis showed that the yield of di-n-hexyl carbonate was 92.3percent based on the amount of urea charged.
Reference:
[1] Patent: CN108358786, 2018, A, . Location in patent: Paragraph 0048
22
[ 111-27-3 ]
[ 7523-15-1 ]
Yield
Reaction Conditions
Operation in experiment
17%
for 0.5 h;
After step (1), 10 g of hexanol containing 1 percent by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 17 percent.
16%
for 0.5 h;
After step (1), 10 g of hexanol containing 1 percent by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 16 percent.
13%
at 150℃; for 0.5 h; Heating
After step (1), 10 g of hexanol containing 1 percent by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating in an oil bath at 150 °C and under a pressure of 1 KPa. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 13 percent.
13%
for 0.5 h;
After step (1), 10 g of hexanol containing 1 percent by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 13 percent.
This example describes the preparation of dihexyl carbonate from propylene carbonate and hexanol. Propylene carbonate (1.02 g; 10 mmol), hexanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2.
EXAMPLE 8 This example describes the preparation of dihexyl carbonate from propylene carbonate and hexanol. Propylene carbonate (1.02 g; 10 mmol), hexanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed = 30 rpm). The reaction was conducted at 170 C for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2.
General procedure: EC (10 mmol), alcohol (100 mmol), and catalyst (5 wtpercent of EC) were taken in a Teflon-lined stainless-steel autoclave placed in a rotating hydrothermal reactor (Hiro Co., Japan; rotation speed = 50 rpm). Reactions were conducted at 40–100°C for 0.5–6 h. After completion of the reaction, the autoclave was cooled to 25°C, and the catalyst was separated by centrifugation/filtration. The liquid product was analyzed and quantified by gas chromatography (GC, Varian 3800; CP-SIL 5 column; 50 m × 0.25 mm × 0.25 m). The influence of reaction parameters (reaction time, reaction temperature, catalyst amount, and type of alcohol) on product yield was investigated. For comparison, experiments were also conducted with PC instead of EC. Those runs were carried out at 80–170°C.
Reference:
[1] Journal of Molecular Catalysis A: Chemical, 2015, vol. 398, p. 42 - 49
27
[ 616-38-6 ]
[ 111-27-3 ]
[ 7523-15-1 ]
[ 39511-75-6 ]
Yield
Reaction Conditions
Operation in experiment
4 %Chromat.
at 80℃; for 6 h;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7.x.10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80° C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
5.1 %Chromat.
at 80℃; for 6 h;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7.x.10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80° C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
3.4 %Chromat.
at 80℃; for 6 h;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7.x.10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80° C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
23.5 %Chromat.
at 80℃; for 6 h;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7.x.10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80° C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
2.1 %Chromat.
at 80℃; for 6 h;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7.x.10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80° C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
Into the above-mentioned 200-ml autoclave containing the reaction mixture (containing an organometal compound having a hexyloxy group) was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade), and the autoclave was sealed. Then, from a carbon dioxide gas bomb which was connected to the autoclave through a SUS tube and a valve, carbon dioxide gas having a pressure of 5 MPa was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 °C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 °C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 14 percent.; Step (2) After step (1), 10 g of hexanol containing 1 percent of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 1 minute. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to a distillation under heating in an oil bath at 160 °C and under reduced pressure. By the distillation, hexanol, tributyltin hexyloxide and dihexyl carbonate were recovered as a distillate. The yield of dihexyl carbonate was 13 percent. It was found that the distillate contained about 2 mmol of tributyltin hexyloxide. On the other hand, a viscous liquid remained in the flask after completion of the distillation.
13%
at 180℃; for 6.16667 h;
The white solids obtained in step (2) and the residual viscous liquid which remained in the flask after the distillation performed in step (2), were charged into a 200-ml autoclave (manufactured and sold by Toyo Koatsu Co., Ltd., Japan). Further, 51.1 g (500 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade) was charged into the autoclave, and the autoclave was sealed. The atmosphere in the autoclave was purged with nitrogen gas. Then, stirring of the contents of the autoclave was started, and the internal temperature of the autoclave was elevated to 160 °C. Then, the stirring was continued for about 30 minutes. Thereafter, the purge line of the autoclave was opened, and water and hexanol were distilled off through the purge line over 4 hours while blowing a small amount of nitrogen gas into the bottom of the autoclave. After that period, there was almost no distillate any more. Then, the inside of the autoclave was cooled to about 30 °C, and there was obtained a reaction mixture. 1H-, 13C- and 119Sn-NMR analyses of the reaction mixture was performed. The NMR analyses showed that the reaction mixture contained about 40 mmol of 1,1,3,3-tetrabutyl-1,3-di-hexyloxy-distannoxane, about 7 mmol of dibutyltin dihexyloxide and about 4 mmol of tributyltin hexyloxide. After step (3), step (1) was performed as follows. Into the above-mentioned autoclave in which step (3) was performed was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade). The autoclave was sealed. Then, from a carbon dioxide gas bomb which was connected to the autoclave through a SUS tube and a valve, carbon dioxide gas having a pressure of 5 MPa was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 °C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 °C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through the purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 14 percent. After step (1), 10 g of hexanol containing 1 percent of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 1 minute. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to a distillation under heating in an oil bath at 160 °C and under reduced pressure. The resultant flask was subjected to distillation under heating and under reduced pressure. By the distillation, hexanol, tributyltin hexyloxide and dihexyl carbonate were recovered as a distillate. The yield of dihexyl carbonate was 13 percent. It was found that the distillate contained about 2 mmol of tributyltin hexyloxide.
Reference:
[1] Catalysis Science and Technology, 2015, vol. 5, # 4, p. 2238 - 2250
30
[ 105-58-8 ]
[ 111-27-3 ]
[ 7523-15-1 ]
Reference:
[1] Zhurnal Fizicheskoi Khimii, 1953, vol. 27, p. 790[2] Chem.Abstr., 1955, p. 2828
[3] Uchenye Zapiski, Kazanskii Gosudarstvennyi Universitet, 1952, vol. 112, # 4, p. 35,100
31
[ 6092-54-2 ]
[ 111-27-3 ]
[ 7523-15-1 ]
Reference:
[1] Journal of the Chemical Society, 1952, p. 514,540
32
[ 281-23-2 ]
[ 111-27-3 ]
[ 5001-18-3 ]
[ 99181-50-7 ]
Yield
Reaction Conditions
Operation in experiment
70%
With hydrogenchloride; sodium hydroxide; sodium hypochlorite In water; ethyl acetate
EXAMPLE 1 Into a 10-L five-necked jacketed flask equipped with a stirring device, a thermometer, a Dimroth condenser and a pH electrode, were charged 408 g (3 mol) of adamantane, 3000 mL of ethyl acetate, 20 g of ruthenium chloride n-hydrate (corresponding to 82 mmol of dihydrate) and 500 g of water. After heating to 46° C, the pH was adjusted to 4. Then, a 12percent aqueous solution of sodium hypochlorite was started to be added dropwise. The dropping speed was regulated so as to add 4120 g (7.5 mol) of the aqueous solution of sodium hypochlorite over 400 min as calculated from the reaction rate previously measured. The content of the free alkali in the aqueous solution of sodium hypochlorite was 0.5percent. The reaction was continued by maintaining the pH of the reaction system at 4.0 to 4.5 by adding a 5percent hydrochloric acid in an amount equivalent to the free alkali in the aqueous solution of sodium hypochlorite. During the reaction, the hypochlorite concentration in the water phase varied between 0.03 and 0.09 mmol/g. After the addition of the sodium hypochlorite was completed, 80 g of a 25 wt percent NaOH aqueous solution and 3000 mL of hexanol were added to separate the reaction mixture into the organic phase and the water phase. The gas chromatographic analysis on each phase showed that the conversion of adamantane was 100percent, the yield of 1-adanantanol was 9percent, the yield of 1,3-adamantanediol was 70percent, and the yield of 1,3,5-adamantanetriol was 14percent. The ruthenium catalyst was recovered as black precipitates by filtering the water phase.
Reference:
[1] Patent: US2002/40170, 2002, A1,
33
[ 281-23-2 ]
[ 111-27-3 ]
[ 5001-18-3 ]
[ 99181-50-7 ]
Reference:
[1] Patent: US2002/40170, 2002, A1,
34
[ 95-48-7 ]
[ 108-46-3 ]
[ 111-27-3 ]
[ 136-77-6 ]
Reference:
[1] Patent: US4108909, 1978, A,
35
[ 62-53-3 ]
[ 111-27-3 ]
[ 33228-45-4 ]
Reference:
[1] Journal of Experimental Medicine, 1934, vol. 59, p. 751,753,754
[2] Polish Journal of Chemistry, 1983, vol. 57, # 4/5/6, p. 593 - 596
[3] Molecular Crystals and Liquid Crystals (1969-1991), 1987, vol. 151, p. 233 - 242
36
[ 589-87-7 ]
[ 111-27-3 ]
[ 30752-19-3 ]
Reference:
[1] Journal of Organic Chemistry, 2008, vol. 73, # 19, p. 7814 - 7817
Reference:
[1] Chemical and Pharmaceutical Bulletin, 1994, vol. 42, # 3, p. 570 - 575
[2] Chemical and Pharmaceutical Bulletin, 1994, vol. 42, # 3, p. 576 - 579
39
[ 131986-59-9 ]
[ 111-27-3 ]
[ 131986-45-3 ]
Reference:
[1] Canadian Journal of Chemistry, 2010, vol. 88, # 12, p. 1222 - 1232
40
[ 1295502-53-2 ]
[ 111-27-3 ]
[ 1190978-94-9 ]
Reference:
[1] Journal of the American Chemical Society, 2017, vol. 139, # 35, p. 12175 - 12181
With triethylamine; In dichloromethane; at 0 - 20℃;
General procedure: Alcohols (50 mmol, 1 equiv.) and 11.08 mL Et3N (80 mmol, 1.6 equiv.) was dissolved in 60 mL CH2Cl2, and the solution was cooleddown to 0 C, then 4.33 mL methanesulfonyl chloride (56 mmol, 1.12 equiv.) was introduced by syringe successively. The mixture is stirredfor 30 min at 0 C, and then stirred overnight at room temperature. The organic layer is washed successively with 1M hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and brine. The organic layer is dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by column chromatography with silica gel (EtOAc: petroleum=1: 2).
88.1%
With triethylamine; In dichloromethane; at 10℃; for 3h;Large scale;
1-hexanol (1.2 kg, 11.70 mol), triethylamine (2.4 kg, 23.40 mol),Stir methylene chloride (12.0 L),MsCl (1.6 kg, 14.0 mol) was added dropwise while maintaining an internal temperature of 10 C. or less.After completion of the dropwise addition, the internal temperature was maintained at 10 C. or lower and stirred for 3 hours.After layer separation by adding 5 L of purified water, the separated organic layer was concentrated under reduced pressure to obtain the title compound (1.9 kg, 88.1%).
With triethylamine; In dichloromethane; for 2h;
General procedure: In a 50 mL round-bottomed flask, 3-phenylpropan-1-ol (0.136 ml 1 mmol) and triethylamine (0.140 ml, 3 mmol) were added to DCM (25 ml). The methanesulfonyl chloride (0.090 ml, 1.2 mmol) was added slowly and allowed to stir for 2 hours, After the completion of reaction, Add water and reaction mixture was extracted with DCM. Organic layer washed with brine and dried over Na2SO4 and concentrated in vacuo. The title compound was isolated using column chromatography (0-20% EtOAc: hexane) gave 0.192 mg 90% colorless oil.
With pyridine; at 0 - 20℃; for 24h;
General procedure: The synthesis of the AKGs was performed following the literature with some modifications (Baumann and Mangold 1964; Hanus et al. 2001; Appendino et al. 2003; Parkkari et al. 2006). LiAlH4 (550 mg, 14.5 mmol) was added slowly to a solution of the corresponding methyl ester (3.4 mmol) in anhydrous tetrahydrofuran (15 mL) at 0C and stirred for 1 h and was then left at 20C for 20 h. The reaction mixture was washed with NaOH (10%) followed by HCl (10%) and extracted with diethyl ether (3 × 20 mL); the extract was neutralized with saturated NaHCO3, dried under reduced pressure and purified by CC. The alcohol obtained was subsequently mesylated in absolute pyridine (4.5 mL, 55.6 mmol) at 0C by the addition of MsCl (880 mg, 7.65 mmol) and the solution was maintained for 24 h at 20C. After quenching the reaction with 5 mL of degasified water, the solution was extracted with diethyl ether (4 × 20 mL). The organic phase was washed with H2SO4 (2 N), neutralized, concentrated in vacuo, and the crude mesylate was purified by CC. KOH (127 mg, 2.26 mmol) was added to the chiral precursor (R)-solketal (283 mg, 2.14 mmol) in anhydrous toluene (2 mL). The reaction stirred at 50C for 1 h before the addition of metallic Na (3 mg, 0.15 mmol) followed by the mesylate dissolved in toluene (15 mL), and the resulting mixture was kept at 50C for 72 h. The reaction was quenched with HCl (10%) and extracted with ethyl ether (4 × 20 mL). The organic phase was neutralized, concentrated and purified by CC to give 1-O-alkyl-2,3-O-isopropylidene-sn-glycerol. This intermediate was deprotected in 5 mL of HCl:MeOH (1:10 v/v) and refluxed overnight. After the addition of H2O (10 mL) and extraction with diethyl ether (4 × 20 mL), the organic phase was neutralized, evaporatedto dryness in vacuo, and the residue was purified by CC to afford pure AKGs. Each step in the synthesis was monitored by TLC, and all CC steps were eluted with hexane-toluene-ethyl acetate (10:0:0-0:10:0-0:0:10) mixtures. The structures of the synthesised compounds were confirmed by 1H, 13C APT NMR with COSY, HMQC, HMBC and ESI-MS or HRESI-MS spectra along with the specific optical rotation.
With 2-Cyanopyridine; cerium(IV) oxide; at 109.84℃; under 37503.8 Torr; for 48.0h;Autoclave;
General procedure: All the reactions were carried out in an autoclave reactor withan inner volume of 190 ml. A typical procedure of the reaction of CO2 + methanol with 2-cyanopyridine was as follows: 0.34 g of CeO2 catalyst, 0.64 g of methanol (20 mmol, Wako Pure Chemical Industries, 99.8% min.), and 10.4 g of 2-cyanopyridine (100 mmol,Tokyo Chemical Industry Co., Ltd., 99.0% min.) were put into the autoclave together with a spinner, and then, the reactor was purged and pressurized with CO2 (Shimakyu Co. Ltd., >99.5%). Gas line was closed, and then, the reactor was heated to the reaction temperature. The time when the temperature reached the desired reaction temperature is defined as zero reaction time. The mixture was constantly stirred during the reaction. After the specific reaction time, the reactor was cooled to room temperature and the gas was collected. Ethanol (30 ml, Wako Pure Chemical Industries, 99.5% min.) and 1-hexanol (0.2 ml, Tokyo ChemicalIndustry Co., Ltd., 98.0% min.) were added to the liquid phase asa solvent and an internal standard substance for a quantitativeanalysis, respectively. Products in the liquid and gas phases were analyzed by using a gas chromatograph equipped with FID(Shimadzu GC-2014) and GC-MS (Shimadzu QP-2020) with a CP-Sil5 capillary column (length 50 m, i.d. 0.25 mm, film thickness0.25 mum). For the synthesis of various carbonates from CO2 and the corresponding alcohols, the procedures are the same as the case of the reaction of CO2 + methanol with 2-cyanopyridine. After the reaction time, 30 ml of ethanol or acetone (Wako Pure Chemical Industries,99.5% min.) was added to the liquid phase as a solvent, and 0.2 ml of 1-hexanol or 1-propanol (Wako Pure Chemical Industries,99.5% min.) was added to the liquid phase as an internal standard substance for a quantitative analysis. The products in the liquid and gas phases were analyzed by gas chromatography equippedwith an FID or quadrupole mass spectrometer (GC-MS) using a CP-Sil5 capillary column (length 50 m, i.d. 0.25 mm, film thickness 0.25 mum) or TC-WAX capillary column (length 30 m, i.d. 0.25 mm, film thickness 0.25 mum).
40%
dibutyltin dihexyloxide; 1,1,3,3-tetrabutyl-1,3-di-hexyloxy-di-stannoxane; at 130℃; for 288.0h;Heating;
Into a two-necked flask equipped with a condenser was inserted an injection tube which had connected thereto a glass ball filter (G2) (manufactured and sold by Vidrex Co., Ltd., Japan). Further, a stirrer was placed in the flask. Into the two-necked flask were charged 0.75 g of the above-obtained liquid (containing an organometal compound) and 41 g of n-hexanol. Then, introduction of a high purity carbon dioxide gas into the flask through the injection tube was started at a flow rate of 100 ml/min. The flask was heated using an oil bath (which was maintained at 130 C) while stirring the contents of the flask and introducing a high purity carbon dioxide gas into the flask, thereby producing dihexyl carbonate. 288 hours after the start of the heating of the flask, the yield of dihexyl carbonate was 40 %.
18%
dibutyltin dihexyloxide; 1,1,3,3-tetrabutyl-1,3-di-hexyloxy-di-stannoxane; at 120℃; under 30003 Torr; for 100.0h;
Production of dihexyl carbonate from dibutyltin dihexyloxide Into a 100-ml autoclave (manufactured and sold by Toyo Koatsu Co., Ltd., Japan) were charged about 2.2 g of an organometal compound containing about 5 mmol of dibutyltin dihexyloxide (wherein the organometal compound was contained in the above-obtained reaction mixture) and 25.5 g (250 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade). The autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 4 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 120 C while stirring. Thereafter, carbon dioxide gas was gradually withdrawn from the autoclave through a purge line so as to adjust the internal pressure of the autoclave to 4 MPa. Then, a reaction was performed for 100 hours while maintaining the internal pressure of the autoclave at 4 MPa. After that period, the inside of the autoclave was cooled to about 30 C, and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through a purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 18 %.
17%
at 120℃; under 30003 Torr; for 100.0h;
Into a 100-ml autoclave (manufactured and sold by Toyo Koatsu Co., Ltd., Japan) were charged about 2.2 g of an organometal compound containing about 5 mmol of dibutyltin dihexyloxide (wherein the organometal compound was contained in the above-obtained reaction mixture) and 25.5 g (250 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade). The autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 4 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 120 C while stirring. Thereafter, carbon dioxide gas was gradually withdrawn from the autoclave through a purge line so as to adjust the internal pressure of the autoclave to 4 MPa. Then, a reaction was performed for 100 hours while maintaining the internal pressure of the autoclave at 4 MPa. After that period, the inside of the autoclave was cooled to about 30 C, and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through a purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 17 %.
14%
1,1,3,3-tetrabutyl-1,3-di-hexyloxy-di-stannoxane; at 180℃; under 37503.8 - 56255.6 Torr; for 6.16667h;
Into the above-mentioned 200-ml autoclave containing the reaction mixture (containing an organometal compound having a hexyloxy group) was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade), and the autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 5 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of about 14 %.
14%
at 180℃; under 37503.8 - 56255.6 Torr; for 6.16667h;
Subsequently, the same procedures as in step (1) and step (2) were successively performed as follows. Step (1): Production of dihexyl carbonate from the organometal compound obtained in step (3) Into the above-mentioned autoclave in which step (3) was performed was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade), and the autoclave was sealed. Then, from a carbon dioxide gas bomb, carbon dioxide gas, the pressure of which was lowered to 5 MPa by means of a pressure regulator connected to the carbon dioxide gas bomb, was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through the purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of about 14 %.
5-amino-4-oxo-pentanoic acid hexyl ester; hydrochloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
Compound 4 was synthesized using modified published procedures [14,53]. Briefly, thionyl chloride (8.20g, 68.9mmol) was added dropwise to 1-hexanol (60.0mL, 48.8g, 475mmol) at 0C. After stirring for 10min the ice-bath was removed, and <strong>[5451-09-2]5-aminolevulinic acid hydrochloride</strong> (8.20g, 49.0mmol) was added. The reaction mixture was stirred at ambient temperature for 1h, followed by reflux at 80C. After 2h the reaction mixture was cooled down and ether (150mL) was added. The precipitate was filtered off and washed with ether (2×50mL). Extensive drying in vacuo gave colorless solid (10.6g, 42.1mmol, 86%). . 1H NMR (300MHz, DMSO-d6) delta 8.35 (s, 3H), 3.97 (t, J=6.7Hz, 2H), 3.92 (s, 2H), 2.78 (t, J=6.5Hz, 2H), 2.52 (t, J=6.5Hz, 2H), 1.61-1.43 (m, 2H), 1.37-1.14 (m, 2H), 1.05-0.73 (m, 1H). 13C NMR (75MHz, DMSO-d6) delta 203.33, 172.74, 64.77, 47.19, 34.94, 31.55, 28.72, 27.76, 25.68, 22.67, 14.58. LRMS, ESI: m/z 216.4 [M+H]+. HRMS: m/z calculated for C11H22NO3 216.1594 [M+H]+, observed 216.1597.
With thionyl chloride;
Next, the manufacturer performs a step of mixing and reacting the <strong>[5451-09-2]5-aminolevulinic acid hydrochloride</strong>, hexyl alcohol and thionyl chloride, finally, 5-aminolevulinic acid hexyl ester hydrochloride is prepared.
After step (1), 10 g of hexanol containing 1 % by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 17 %.
16%
In water; for 0.5h;
After step (1), 10 g of hexanol containing 1 % by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 16 %.
13%
In water; at 150℃; under 7.50075 Torr; for 0.5h;Heating;
After step (1), 10 g of hexanol containing 1 % by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating in an oil bath at 150 C and under a pressure of 1 KPa. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 13 %.
13%
In water; for 0.5h;
After step (1), 10 g of hexanol containing 1 % by weight of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 30 minutes. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to distillation under heating. By the distillation, hexanol and dihexyl carbonate were recovered. The yield of dihexyl carbonate was 13 %.
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7×10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80 C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
0.2%Chromat.; 5.1%Chromat.
di(n-butyl)tin oxide; at 80℃; for 6.0h;Conversion of starting material;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7×10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80 C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
0.1%Chromat.; 3.4%Chromat.
dibutyltin dilaurate; at 80℃; for 6.0h;Conversion of starting material;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7×10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80 C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
5.3%Chromat.; 23.5%Chromat.
ytterbium(III) acetyl acetonate; at 80℃; for 6.0h;Conversion of starting material;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7×10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80 C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
0.1%Chromat.; 2.1%Chromat.
magnesium carbonate; at 80℃; for 6.0h;Conversion of starting material;
Dimethyl carbonate (3.06 g) and 1-hexanol (6.94 g) in a molar ratio of 1:2 were mixed together with in each case a constant quantity (5.7×10-6 mol) of a catalyst (see Table 1) in a 20 ml rolled flange glass vessel, which was closed with a natural rubber septum including a gas outlet. If the catalyst used was present at room temperature in solid aggregate state, it was first dissolved in one of the educts. The reaction mixture was heated for 6 hours to 80 C., with stirring. After cooling to room temperature, analysis of the product spectrum was performed by gas chromatography, optionally coupled with mass spectrometric examination. The reaction product contents, namely methylhexyl carbonate or dihexyl carbonate, which can be taken as a measure of the activity of the transesterification catalyst used, were quantified by integration of the respective gas chromatograms
at 180℃; under 37503.8 - 56255.6 Torr; for 6.16667h;Product distribution / selectivity;
Into the above-mentioned 200-ml autoclave containing the reaction mixture (containing an organometal compound having a hexyloxy group) was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade), and the autoclave was sealed. Then, from a carbon dioxide gas bomb which was connected to the autoclave through a SUS tube and a valve, carbon dioxide gas having a pressure of 5 MPa was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 14 %.; Step (2) After step (1), 10 g of hexanol containing 1 % of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 1 minute. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to a distillation under heating in an oil bath at 160 C and under reduced pressure. By the distillation, hexanol, tributyltin hexyloxide and dihexyl carbonate were recovered as a distillate. The yield of dihexyl carbonate was 13 %. It was found that the distillate contained about 2 mmol of tributyltin hexyloxide. On the other hand, a viscous liquid remained in the flask after completion of the distillation.
13%
at 180℃; under 37503.8 - 56255.6 Torr; for 6.16667h;Product distribution / selectivity;
The white solids obtained in step (2) and the residual viscous liquid which remained in the flask after the distillation performed in step (2), were charged into a 200-ml autoclave (manufactured and sold by Toyo Koatsu Co., Ltd., Japan). Further, 51.1 g (500 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade) was charged into the autoclave, and the autoclave was sealed. The atmosphere in the autoclave was purged with nitrogen gas. Then, stirring of the contents of the autoclave was started, and the internal temperature of the autoclave was elevated to 160 C. Then, the stirring was continued for about 30 minutes. Thereafter, the purge line of the autoclave was opened, and water and hexanol were distilled off through the purge line over 4 hours while blowing a small amount of nitrogen gas into the bottom of the autoclave. After that period, there was almost no distillate any more. Then, the inside of the autoclave was cooled to about 30 C, and there was obtained a reaction mixture. 1H-, 13C- and 119Sn-NMR analyses of the reaction mixture was performed. The NMR analyses showed that the reaction mixture contained about 40 mmol of 1,1,3,3-tetrabutyl-1,3-di-hexyloxy-distannoxane, about 7 mmol of dibutyltin dihexyloxide and about 4 mmol of tributyltin hexyloxide. After step (3), step (1) was performed as follows. Into the above-mentioned autoclave in which step (3) was performed was charged 61.5 g (602 mmol) of hexanol (manufactured and sold by Aldrich, U.S.A.; a dehydrated grade). The autoclave was sealed. Then, from a carbon dioxide gas bomb which was connected to the autoclave through a SUS tube and a valve, carbon dioxide gas having a pressure of 5 MPa was introduced into the autoclave. Stirring of the contents of the autoclave was started. 10 Minutes after the start of the stirring, the valve of the carbon dioxide gas bomb was closed. Then, the internal temperature of the autoclave was elevated to 180 C while stirring. In this instant, the internal pressure of the autoclave was about 7.5 MPa. Then, a reaction was performed for 6 hours while maintaining the internal pressure of the autoclave at about 7.5 MPa. Thereafter, the inside of the autoclave was cooled to about 30 C and the internal pressure of the autoclave was returned to atmospheric pressure by gently purging the carbon dioxide gas through the purge line, and there was obtained a transparent reaction mixture. In the reaction mixture, dihexyl carbonate was obtained in a yield of 14 %. After step (1), 10 g of hexanol containing 1 % of water was gently added to the reaction mixture obtained in step (1), and the resultant mixture was stirred for about 1 minute. Then, the autoclave was opened, and it was found that the mixture in the autoclave had turned into a white slurry. The white slurry was subjected to filtration using a membrane filter (H020A142C, manufactured and sold by Advantec Toyo Kaisha, Ltd., Japan) to thereby obtain white solids and a filtrate. The white solids were washed 2 times with 20 ml of hexanol. The filtrate was transferred into a 1-liter eggplant-shaped flask and subjected to a distillation under heating in an oil bath at 160 C and under reduced pressure. The resultant flask was subjected to distillation under heating and under reduced pressure. By the distillation, hexanol, tributyltin hexyloxide and dihexyl carbonate were recovered as a distillate. The yield of dihexyl carbonate was 13 %. It was found that the distillate contained about 2 mmol of tributyltin hexyloxide.
4-[3,4-dihydro-1-methyl-2(1H)-isoquinolinyl]-N-(4-fluorophenyl)-5,6-dimethyl-2-pyrimidineamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium acetate;
EXAMPLE 14 2.65 g(27 mmole) of potassium acetate and 4.0 g(26.9 mmole) of <strong>[4965-09-7]1-methyl-1,2,3,4-tetrahydroisoquinoline</strong> were added to 85 ml of n-hexanol and then warmed to 80 C. 6.17 g(24.5 mmole) of 4-chloro-2-(4-fluorophenylamino)-5,6-dimethylpyrimidine was added thereto and then reacted at 140 C. for 28 hours under refluxing to prepare 5,6-dimethyl-2-(4-fluorophenylamino)-4-(1-methyl-1,2,3,4-tetrahydroisoquinolin-2-yl)pyrimidine. The reaction solution was cooled to room temperature, diluted with 20 ml of acetone and then added dropwise to 120 ml of water with stirring.
EXAMPLE VIII n-Hexanol (2.05 g., 20 mmol.) was reacted with bis(2,2,2-trifluoroethyl) carbonate (2.38 g., 10.5 mmol.) and sodium methoxide (5.4 mg., 0.10 mmol.) in 10 ml. of toluene, according to the procedure of Example II. Vpc analysis of the product showed clean formation of di-n-hexyl carbonate. No n-hexanol remained. Isolation of the product by evaporation of solvents gave a quantitative yield of the product, further characterized by spectral analysis. STR12
Fe-Zn double metal cyanide catalyst; at 170℃; for 8.0h;
This example describes the preparation of dihexyl carbonate from propylene carbonate and hexanol. Propylene carbonate (1.02 g; 10 mmol), hexanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170 C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2.
EXAMPLE 8 This example describes the preparation of dihexyl carbonate from propylene carbonate and hexanol. Propylene carbonate (1.02 g; 10 mmol), hexanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed = 30 rpm). The reaction was conducted at 170 C for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2.
platinum on carbon; In water; for 3h;Direct aqueous phase reforming;
Direct aqueous phase reforming (APR) experiments were conducted in 100-ml stirred reactors with draft-tube gas-induction impeller (Parr Series 4590). Reaction tests for direct bio-based feedstock aqueous phase reforming (APR) entailed filling the reactor with 60-grams of solvent (deionized water, or a mixture of DI water and isopropanol (IPA), and 3-3.5 grams of bio-based feedstock comprising biomass (bagasse, or pine sawdust)). One (1) gram of acetic acid was optionally charged to facilitate biomass hydrolysis.[0098] Bagasse was milled via a 1-mm grate. Dry, debarked Loblolly pine was ground via blender (Thomas Scientific of Swedesboro, NJ) and sieved to less than 30 mesh. Dry solids fraction was determined by vacuum drying at 80 °C to 82 °C. One gram of aqueous phase reforming catalyst (reduced 5percent Pt/C catalyst at 50percent moisture, or powdered 1.9percent Pt/A1203) was charged to the reactor, which was charged with 4200 kPa of hydrogen or nitrogen. To minimize degradation of hydrolysate to heavy ends, each reactor was typically heated with a staged temperature sequence of one hour at, 160 °C, 190 °C, 225 °C, and finally 250 °C, before leaving overnight at the final setpoint.[0099] Comparison tests were also conducted with glucose or sorbitol fed directly to the reaction in place of biomass, to simulate and quantify conversion of model hydrolysate to APR intermediates. Glucose is one of the sugars readily leached from biomass in hot water, while sorbitol is readily formed via hydrogenation of glucose, where platinum or other catalysts capable of hydrogenation are present.[00100] A batch reaction time of 20 hours under these conditions corresponds to a weight hourly space velocity (g-feed/g-catalyst/h) of about 3, for a comparable continuous flow reactor. A 0.5-micron sintered metal filter attached to a dip tube allowed liquid samples to be taken throughout the course of reaction, without loss of biomass or catalyst. Samples were analyzed by an HPLC method based on combined size and ion exclusionchromatography, to determine unreacted sorbitol, and amount of C3 and smaller polyols formed: glycerol (Gly), ethylene glycol (EG), and 1,2-propylene glycol (PG). Additional GC analysis via a moderate polarity DB-5 column were conducted to assess formation of C6 and lighter oxygenates (e.g., ketones, aldehydes, alcohols), as well as alkane and alkene products. A separate GC equipped with thermal conductivity and flame ionization (FID) detectors for refinery gas analysis, were used for detection of H2, C02, and light alkanes C1-C5. GC-mass spec was used to characterize select APR reaction product mixtures. Examples 1-3[00101] Batch APR reactions with sugar cane bagasse as biomass feed, and with a comparison of 25percent sorbitol as feed, were performed as described above. 1.7percent acetic acid was added to simulate catalysis of hydrolysis by recycle acid. Products formed from this concentration of acetic acid were subtracted from total product formation, to calculate the net production of liquid fuels from bagasse. This result shown in Table 1 shows the critical importance of concerted APR reaction with hydrolysis of biomass. In the absence of concerted aqueous phase reforming, the hydrolysate undergoes irreversible degradation (presumably to heavy ends), and cannot be reverted to liquid fuels upon subsequent APR and condensation. Converted reaction may be effected by direct inclusion of APR catalyst in the hydrolysis reactor, or via a pump around loop to recirculate liquid between a biomass contactor, and an APR catalytic reactor. Table 1: Direct APR of Biomass
General procedure: EC (10 mmol), alcohol (100 mmol), and catalyst (5 wt% of EC) were taken in a Teflon-lined stainless-steel autoclave placed in a rotating hydrothermal reactor (Hiro Co., Japan; rotation speed = 50 rpm). Reactions were conducted at 40-100C for 0.5-6 h. After completion of the reaction, the autoclave was cooled to 25C, and the catalyst was separated by centrifugation/filtration. The liquid product was analyzed and quantified by gas chromatography (GC, Varian 3800; CP-SIL 5 column; 50 m × 0.25 mm × 0.25 m). The influence of reaction parameters (reaction time, reaction temperature, catalyst amount, and type of alcohol) on product yield was investigated. For comparison, experiments were also conducted with PC instead of EC. Those runs were carried out at 80-170C.
2.3.1 Hexyl 5-amino-4-oxopentanoate 1 Hexyl 5-amino-4-oxopentanoate was synthesized according to published procedure [40] . Briefly, thionyl chloride (8.20 g, 68.9 mmol) was added dropwise to 1-hexanol (60.0 mL, 48.8 g, 475 mmol) in an ice-bath. After the solution was stirred for 10 min the ice-bath was removed, <strong>[5451-09-2]5-aminolevulinic acid hydrochloride</strong> (8.20 g, 49.0 mmol) was added. The reaction mixture was stirred at ambient temperature for 1 h, followed by reflux at 80 C for 2 h. After cooling down, ether (150 mL) was added and the precipitate filtered off and washed with ether (2 * 50 mL). Extensive drying in vacuo gave colorless solid (10.6 g, 42.1 mmol, 86%). 1H NMR (300 MHz, DMSO-d6) delta 8.35 (s, 3H), 3.97 (t, J = 6.7 Hz, 2H), 3.92 (s, 2H), 2.78 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.5 Hz, 2H), 1.61-1.43 (m, 2H), 1.37-1.14 (m, 2H), 1.05-0.73 (m, 1H). 13C NMR (75 MHz, DMSO-d6) delta 203.33, 172.74, 64.77, 47.19, 34.94, 31.55, 28.72, 27.76, 25.68, 22.67, 14.58. LRMS, ESI: m/z 216.4 [M + H]+. HRMS: m/z calculated for C11H22NO3 216.1594 [M]+, observed 216.1597.
With nitric acid; In dimethyl sulfoxide; at 60℃; for 16.0h;
1 ,3,4,6-tetrakis(hydroxymethyl)tetrahydroimidazo [4,5-d]imidazole-2,5(1H,3H)-dione (1 g, 3.8 mmol) in 2 ml of DM50 was dissolved. Then, 0.15 ml nitric acid (65%) and n-hexylalcohol (9.5 ml, 76.3 mmol) were added to the solution and the mixture was heated at 60 C. for 16 hours. After the reaction was over, the reaction liquid was cooled and iN NaOH was added around pH 7. Around 100 ml ethyl acetate was used to extract with mixture and the organic phase was washed by saturated NaC1(aq) solution for 2 times. After being dried by Na2SO4, the solvent was removed. The crude compound was purified by flash chromatography (Heptane/EtOAc). The product was obtained colorless viscous oil in 0.15 g, yield (%) ?H NMR (600 MHz, DMSO-d6): oe ppm) 5.50 (s, 2H), 4.73 (m, 8H), 3.36 (m, 8H), 1.46 (m, 8H), 1.24 (m, 26H), 0.85 (t, 12H)
hexyl 2,3-dihydro-1,4-benzodioxine-6-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With iron(III) chloride; ammonium persulfate; In tetrachloromethane; 1,2-dichloro-ethane; at 120℃; for 15h;
General procedure: 1a-j (0.0299 - 0.0532 g, 0.299 mmol, 1 eq.), 2a-d (0.0166 - 0.228 g, 0.224 mmol, 0.75 eq.), FeCl3 (0.0145 g, 0.0897 mmol, 0.3 eq.), (NH4)2S2O8 (0.1363 g, 0.598 mmol, 2 eq.), and DCE / CCl4 (0.75 mL, 1 / 1) were stirred in Schott culture tubes (H × diam. 160 mm × 16 mm) at 120 C for 3 h. Further, after adding a solution of 2a-d (0.055 - 0.0763, 0.0748 mmol, 0.25 eq.) and DCE / CCl4 (0.08 mL, 1 / 1), the reaction mixture was stirred at 120 C for 3 h (3 times at 3-hour intervals). Next it was stirred at 120 C for 12 h. The yields of 3a-f,a-d were determined by 1H NMR (CDCl3) after the filtration of the reaction mass through a thin pad (0.4 - 0.5 cm) of silica gel (0.015 - 0.040 mm) using 20 mL of DCM and evaporation of solvent in vacuum. Products 3c,b and 3d,a-d were isolated by gradient flash chromatography (eluent: petroleum ether / ethyl acetate).
With dmap; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide; In dichloromethane; N,N-dimethyl-formamide; at 20℃;
General procedure: Ester prodrugs of BEX and RA were synthesised by adding2.87 mmol of the desired alcohol to 0.287 mmol of BEX or RA. 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide (0.431 mmol) and 4-dimethylaminopyridine(0.057 mmol) were added, and dichloromethane(15 mL) was used as the solvent. The mixture was stirred magneticallyovernight at room temperature. Purification was performed by flashchromatography using a 200-400 mesh silica gel-packed glass columnsand hexane-ethyl acetate 50:2 (v/v) as the mobile phase. Specific detailsfor compounds that were obtained by different synthetic schemesare described in Supplementary Material 1
With nickel diacetate; triphenylphosphine; at 140 - 170℃; under 75.0075 Torr; for 20.0h;
The reaction apparatus was the same as in Example 1. Take 10g urea, 68g n-hexanol, 0.5g nickel acetate, 2g triphenylphosphine in a three-neck bottle, heat in 170 C oil bath, vacuum, system vacuum 10Kpa, system maintain 140 C, slightly boiling, stirring reflux Reaction for 20 hr.Gas chromatography analysis showed that the yield of di-n-hexyl carbonate was 92.3% based on the amount of urea charged.
With oxygen; sodium hydroxide; In water; at 20℃; for 3.0h;Irradiation;
General procedure: Purified chloroform (20 mL), phenol (0.941 g, 10 mmol) and sodium hydroxide aqueous solution (20 mL, 100 mmol) were added to the above-described reaction vessel, and the mixture was stirred to be mixed. Oxygen gas was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20 C. to cause bubbling, and a light was irradiated from the low pressure mercury lamp. After 3 hours, water and dichloromethane were added to the reaction mixture. An organic phase and a water phase were separated. The organic phase was dried by anhydrous sodium sulfate and then concentrated under reduced pressure at 70 C. to obtain a light orange solid (yield: 55%). The obtained solid was analyzed by 1H-NMR; as a result, it was confirmed that the target copolymer was generated.