Structure of 249562-06-9
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CAS No. : | 249562-06-9 |
Formula : | C14H20O2 |
M.W : | 220.31 |
SMILES Code : | C=CC(OC1(C)C2CC3CC(C2)CC1C3)=O |
MDL No. : | MFCD08704223 |
InChI Key : | YRPLSAWATHBYFB-UHFFFAOYSA-N |
Pubchem ID : | 11218292 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With triethylamine; In tetrahydrofuran; diethyl ether; | b. Synthesis of 2-methyl-2-adamantyl acrylate 2-methyl-2-adamantanol (33 g, 0.2 mol) and triethylamine (0.22 mol) were dissolved in 300 ml of THF and then acryloyl chloride (19g, 0.21 mol) was added slowly thereto using a dropping funnel. Then, the reaction was stirred at room temperature for about 12 hours. After completion of the reaction, excess THF was removed using a rotary evaporator and then the resultant product was poured into water. Then, the resultant product was neutralized with dilute sulfuric acid and extracted using diethyl ether and was then dried over magnesium sulfate. The diethyl ether removed crude product was vacuum-distilled to yield the desired product (yield: 80%). |
80% | With triethylamine; In tetrahydrofuran; diethyl ether; | b. Synthesis of 2-methyl-2-adamantyl acrylate 2-methyl-2-adamantanol (33 g, 0.2 mol) and triethylamine (0.22 mol) were dissolved in 300 ml of THF and then acryloyl chloride (19 g, 0.21 mol) was added slowly thereto using a dropping funnel. Then, the reaction was stirred at room temperature for about 12 hours. After completion of the reaction, excess THF was removed using a rotary evaporator and then the resultant product was poured into water. Then, the resultant product was neutralized with dilute sulfuric acid and extracted using diethyl ether and was then dried over magnesium sulfate. The diethyl ether removed crude product was vacuum-distilled to yield the desired product (yield: 80%). 1H-NMR (CDCl3; ppm): 6.3 (doublet), 6.1 (1H, dd), 5.7 (1H, d), 2.3 (2H, s), 1.5-2.1 (m) FT-IR (NaCl; cm-1): 2911, 2861, 1718, 1635, 1618, 1401, 1201 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 33 A reaction, a post-treatment and an analysis were conducted in the same manner as in Example 15 except that no anhydrous calcium sulfate was used and 3.0 g of Amberslist-15 was used as an acid catalyst and dehydrating agent. As a result, the yield of 2-methyl-2-adamantyl acrylate was 74%. | ||
With n-Undecane; at 60 - 125℃; under 1.0 Torr; for 1.16667h;Purification / work up; | In a similar reaction operation to that employed in Example 1, 2-methyleneadamantane was prepared. After it was cooled to 50 C. and 8 L of toluene was distilled off under reduced pressure, the residue was cooled to 0 C. An acrylate forming reaction was then carried out by adding 1070 g of acrylic acid and 83 g of boron trifluoride ethyl ether to it while stirring the resulting mixture for one hour. After the reaction mixture was washed with 6 L of a 10% aqueous sodium carbonate solution and 5 L of deionized water, toluene was distilled off at 70 C. under reduced pressure, whereby 1050 g of crude 2-methyladamantan-2-yl acrylate was obtained. The resulting product contained 86.8 wt. % of 2-methyladamantan-2-yl acrylate and 12.5 wt. % of 2-methyleneadamantane. The crude 2-methyladamantan-2-yl acrylate (100 g) thus obtained and 50 g of n-undecane were charged in a vacuum still and distilled at 60 C. and 1 mmHg, whereby 63.3 g was distilled off in 60 minutes. The fraction thus distilled off contained 87% of 2-methyleneadamantane together with undecane. The distillation temperature was raised to 85 C. and 3.5 g was distilled out in 10 minutes to decrease the amount of 2-methyleneadamantane to less than 1 wt. %. The residue in the still was then distilled at 125 C. and 1 mmHg to obtain the target compound, whereby 785 g of 2-methyladamantan-2-yl acrylate having a purity of 99.5 wt. % was obtained. The resulting product had a 2-methyleneadamantane content of 0.1 wt. %. | |
With n-Undecane; at 60 - 125℃; under 1.0 Torr; for 1.16667h;Purification / work up; | The crude 2-methyladamantan-2-yl methacrylate was distilled at 60 C. and 1 mmHg by using a vacuum still and 59 g was distilled off in 60 minutes. The fraction thus distilled off contained 87% of 2-methyleneadmanatane together with n-undecane. The distillation temperature was raised to 85 C. and 3.4 g was distilled out in 10 minutes to adjust the amount of 2-methyleneadamantane remaining in the residue in the still to less than 1 wt. %. The residue in the still was then distilled at 125 C. and 1 mmHg, whereby 79.1 g of 2-methyladamantan-2-yl methacrylate having a purity of 99.4 wt. % was obtained. The resulting product had a 2-methyleneadamantane content of 0.1 wt. %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.5% | With sodium hydroxide; sulfuric acid; In toluene; | EXAMPLE 2 Synthesis of 2-methyl-2-adamantyl Acrylate [MAAC] A 500 ml flask was flushed with nitrogen to displace the air with nitrogen, and was charged with 36.0 g (0.50 mol) of acrylic acid, 0.5 g (5 mmol) of sulfuric acid and 100 g of toluene. Separately 88.8 g (0.60 mol) of 2-methyleneadamantane, prepared by the same procedures as described in Reference Example 1, was dissolved in 100 g of toluene. The obtained solution of 2-methyleneadamantane in toluene was dropwise added to the content in the flask over a period of about 3 hours, while the content was maintained at a reaction temperature of about 20 C. Then the content was stirred for 5 hours at the same temperature. After completion of the reaction, the residual catalyst was neutralized by adding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, and the neutralized liquid was washed with an aqueous saturated sodium chloride solution. The thus-obtained organic phase was subjected to column chromatography, and further, analyzed by NMR and mass spectrometry. Thus, 100.7 g (yield: 91.5%) of the object 2-methyl-2-adamantyl acrylate was obtained. |
boron trifluoride diethyl etherate; at 0℃; for 1.0h;Product distribution / selectivity; | In a similar reaction operation to that employed in Example 1, 2-methyleneadamantane was prepared. After it was cooled to 50 C. and 8 L of toluene was distilled off under reduced pressure, the residue was cooled to 0 C. An acrylate forming reaction was then carried out by adding 1070 g of acrylic acid and 83 g of boron trifluoride ethyl ether to it while stirring the resulting mixture for one hour. After the reaction mixture was washed with 6 L of a 10% aqueous sodium carbonate solution and 5 L of deionized water, toluene was distilled off at 70 C. under reduced pressure, whereby 1050 g of crude 2-methyladamantan-2-yl acrylate was obtained. The resulting product contained 86.8 wt. % of 2-methyladamantan-2-yl acrylate and 12.5 wt. % of 2-methyleneadamantane. The crude 2-methyladamantan-2-yl acrylate (100 g) thus obtained and 50 g of n-undecane were charged in a vacuum still and distilled at 60 C. and 1 mmHg, whereby 63.3 g was distilled off in 60 minutes. The fraction thus distilled off contained 87% of 2-methyleneadamantane together with undecane. The distillation temperature was raised to 85 C. and 3.5 g was distilled out in 10 minutes to decrease the amount of 2-methyleneadamantane to less than 1 wt. %. The residue in the still was then distilled at 125 C. and 1 mmHg to obtain the target compound, whereby 785 g of 2-methyladamantan-2-yl acrylate having a purity of 99.5 wt. % was obtained. The resulting product had a 2-methyleneadamantane content of 0.1 wt. %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In tetrahydrofuran; diethyl ether; | c. Synthesis of 2-methyl-2-adamantyl 5-norbornene-2-carboxylate <strong>[249562-06-9]2-methyl-2-adamantyl acrylate</strong> (44 g, 0.2 mol) was dissolved in 250 ml of THF, cyclopentadiene (20 g, 0.3 mol) was added slowly thereto at 0C and then thereaction temperature was raised to about 50C. Then, the reaction was stirred for about 20 hours. After completion of the reaction, excess THF was removed using a rotary evaporator and then neutralized with dilute sulfuric acid. Then, the resultant product was extracted using diethyl ether and dried over magnesium sulfate. The obtained crude product was vacuum-distilled to yield the desired compound of viscous colorless liquid (yield: 90%) FIGS. 1 and 2 are NMR and FT-IR spectrums of the compound. |
90% | In tetrahydrofuran; diethyl ether; | c. Synthesis of 2-methyl-2-adamantyl 5-norbornene-2-carboxylate 20 <strong>[249562-06-9]2-methyl-2-adamantyl acrylate</strong> (44 g, 0.2 mol) was dissolved in 250 ml of THF, cyclopentadiene (20 g, 0.3 mol) was added slowly thereto at 0 C. and then the reaction temperature was raised to about 50 C. Then, the reaction was stirred for about 20 hours. After completion of the reaction, excess THF was removed using a rotary evaporator and then neutralized with dilute sulfuric acid. Then, the resultant product was extracted using diethyl ether and dried over magnesium sulfate. The obtained crude product was vacuum-distilled to yield the desired compound of viscous colorless liquid (yield: 90%) FIGS. 1 and 2are NMR and FT-IR spectrums of the compound. 1H-NMR (CDCl3; ppm): 6.2 (1H, m), 6.1 (1H, s), 5.9 (1H, m), 3.2 (1H, s), 2.9 (2H, m), 2.3-1.2 (m) FT-IR (NaCl; cm-1): 2910, 2861, 1725, 1334, 1270, 1189, 713 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,1,1,3,3-pentafluorobutane; dibenzoyl peroxide; In tetrahydrofuran; acetic acid methyl ester; at 50℃; under 10069.0 Torr; for 16.0h; | Synthesis of TFE/NB-F-OH/PinAc/HAdA/MAdA Pentapolymer A 4000 mL pressure vessel is charged with 695.4 g (2.398 mol) of NB-F-OH, 25.1 g (0.146 mol) of PinAc, 77.4 g (0.282 mol) of HAdA, 10.7 g (0.049 mol) of MAdA, 60.4 g (0.840 mol) of THF and 381.6 g (2.578 mol) of Solkane 365 mfc. The vessel is closed and heated to 50 C. under agitation at 100 rpm. The vessel is then charged with TFE until the reactor pressure reached 180 psig (1.24 MPa), at which point about 86 g (0.860 mol) of TFE is expected to be in the solution at that pressure and temperature. The monomer composition at the beginning of the run, then, is targeted to be 23% TFE, 64% NB-F-OH, 4% PinAc, 8% HadA, and 1% MAdA (mol %) and the reactor contained 1336 g of solution, including dissolved TFE. When the reaction temperature and pressure setpoints are reached, continuous flow of three solutions to the reactor is begun. Two of these solutions contained the monomers and chain transfer agent (THF) and the third contained the initiator. The first monomer solution contained 711.9 g (2.455 mol) of NB-F-OH, 51.6 g (0.717 mol) of THF and 125.4 g (0.847 mol) of Solkane 365mfc. This solution is metered into the reactor by means of an Isco series D high-pressure precision syringe pump at a constant rate of 1.054 g/min for 720 min. The second monomer solution contained 122.8 g (0.714 mol) of PinAc, 378.1 g (1.380 mol) of HAdA, 52.3 g (0.238 mol) of MAdA, 49.0 g (0.681 mol) of THF, 119.1 g (0.805 mol) of Solkane 365mfc and 171.4 g (2.301 mol) of methyl acetate to aid in dissolution of the monomers. This solution is metered in a second Isco series D high-pressure precision pump at a constant rate of 1.088 g/min for 720 min. The initiator solution contained 89.2 g (0.224 mol) of Perkadox 16N, 369.7 g (2.498 mol) of Solkane 365mfc and 518.9 g (7.012 mol) of methyl acetate. The initiator solution is metered into the reactor with an Isco series D high-pressure precision syringe pump at 35.49 g/min for six min, followed by a rate of 1.42 g/min for 480 min. TFE is supplied to the reactor over the course of 720 min by maintaining the reactor pressure at 180 psig (1.34 MPa). The calculated total amounts of ingredients added to the vessel after 720 min of reaction is 275.7 g (2.757 mol) of TFE, 1287.9 g (4.441 mol) of NB-F-OH, 132.3 g (0.769 mol) of PinAc, 407.5 g (1.487 mol) of HAdA, 56.4 g (0.256 mol) of MAdA, 146.2 g (2.031 mol) of THF, 922.9 g (6.236 mol) of Solkane 365mfc, 602.3 g (8.139 mol) of methyl acetate and 81.6 g (0.205 mol) of Perkadox 16N. The reaction temperature is held at 50 C., the pressure is maintained with TFE feed at 180 psig (1.34 MPa), and the agitation rate is 100 rpm over the course of the 720 min of reaction. After 720 min, the TFE feed is stopped and the reactor is held under agitation for 4 hr at 50 C. The vessel is then cooled rapidly to room temperature and vented to 1 atmosphere. The vessel contents are transferred to a container via blowcasing after adding an additional 400 ml of THF to reduce viscosity and aid in rinsing of the vessel. A 1073.4 g (890 ml) sample of the resultant polymer solution is metered into a 22-L agitated flask containing 16020 ml of n-heptane (18/1 volume ratio to polymer solution). After mixing for 30 min, the slurry is discharged across an in-line cloth filter. The wet precipitate on the filter weighed 497.8 g. A sample of this precipitate (478.7 g.) is redissolved with 765.9 ml of Solkane 365mfc and 480 ml of THF. The resultant solution is precipitated a second time into a vessel containing n-heptane at a volume ratio of 18/1 with the polymer solution. After mixing for 30 min, the slurry is discharged again across another in-line cloth filter. The filtrate is dried under vacuum with a nitrogen bleed at 70 C. for 16 hr to obtain 347 g of very fine, white powder. Gel permeation chromatography of the product indicated Mn=5130, Mw=9780 and Mw/Mn=1.91. A combination of 13C and 19F NMR analyses of the product resulted in a calculated polymer composition of 15 mol % TFE, 39 mol % NB-F-OH, 10 mol % PinAc, 30 mol % HAdA and 6 mol % MAdA. |
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