Structure of 37830-90-3
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CAS No. : | 37830-90-3 |
Formula : | C5H6O3 |
M.W : | 114.10 |
SMILES Code : | CC1=C(OC(O1)=O)C |
MDL No. : | MFCD00135139 |
InChI Key : | QYIOFABFKUOIBV-UHFFFAOYSA-N |
Pubchem ID : | 142210 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-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 |
---|---|---|
66% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In benzene; at 110℃; for 2h;Inert atmosphere; | To a stirred solution of 4, 5-dimethyl-l, 3-dioxol-2-one (4.5 g, 39.4 mmol) in benzene (150 mL), were added NBS (15.44 g, 87 mmol) and AIBN (0.648 g, 3.94 mmol). The reaction mixture was stirred at 1 10 C for 2 h under nitrogen atmosphere and subsequently concentrated in vacuo. The residue was dissolved in ethyl acetate (200 mL). The solution was washed with water (2* 150 mL) and brine (100 mL), dried over anhydrous sodium sulphate and concentrated in vacuo to get the crude product as a light brownish oil, which was purified by CombiFlash chromatography (60-120 silica gel; 5- 55% ethyl acetate in pet. ether as eluent) to afford 4,5 -bis (bromomethyl)-l,3-dioxol-2- one (7 g, 66%) as a light yellowish oil. NMR (400 MHz, Chloroform-7) d ppm 4.22 (s, 4H). |
With N-Bromosuccinimide;2,2'-azobis(isobutyronitrile); In benzene; for 1h;Reflux; | NBS (19.58 g, 110 mmol) followed by AIBN (0.821 g, 5.00 mmol) were added to a stirred, room temperature mixture of 4,5-dimethyl-l,3-dioxol-2-one (5.70 g, 50 mmol) in benzene (300 mL) and the mixture was stirred at reflux for 1 h. Volatiles were removed.Chromatography over silicaeluting with 5-55% EtOAc/hexane afforded the desired product as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.8% | With N-Bromosuccinimide; In chloroform;Reflux; Large scale; | 5. 0kg adding the compound of formula (IV) in a reaction vessel, 8. 0kg N- bromosuccinimide (NBS), 0. 30kg of azobisisobutyronitrile was added as the reaction solvent chloroform 100L, stirring was warmed to 38 ° C, the reaction system to be stable, then slowly heated to reflux for 2-3 hours, the reaction was completed, cooled to room temperature, insolubles were removed by filtration, the filtrate was atmospheric recovery chloroform, 4 ° C refrigerated overnight and filtered again after crystallization the insoluble matter was removed, and then distilled under reduced pressure collecting ll ° C~120 ° C / 5mmHg fractions, the compound of formula (V) 8. 66kg, yield (mole) 938percent, purity 95.1percent.; |
92% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; at 77℃; for 6h; | Step III: 4-Bromomethyl-5-methyl~l,3-dioxol~2-one; A mixture of 4,5-dimethyl-l,3-dioxol-2-one (1.5 g, 0.013158 mol), NBS (2.34 g, 0.013158 mol) and benzoyl peroxide (0.089 g, 0.0003684 mol) in CCl4 (20 mL) was stirred at 77°C for 6 hrs (TLC monitoring: cyclohexane/AcOEt 6:4). The solution was treated with an aqueous solution OfNaHCO3 and extracted with CH2Cl2. The organic phase was dried over Na2SO4 and concentrated under reduced pressure to give 4-bromomethyl-5 -methyl- 1,3- dioxol-2-one (2.34 g). Yield: 92percent.1H-NMR (400 MHz, CDCl3, delta): 2.13 (s, 3H, CH3), 4.18 (s, 2H, CH2Br). |
73% | With N-Bromosuccinimide;azobisisobutyronitrile; In tetrachloromethane; | (1) Synthesis of 4-bromomethyl-5-methyl-1,3-dioxolen-2-one[the compound of formula (III) in which X is a bromine atom]: 3.42 g of 4,5-dimethyl-1,3-dioxolen-2-one (synthesised in accordance with Tetrahedron Letters, (1972), pages 1701-1704) was dissolved in 150 ml of carbon tetrachloride, and 5.34 g of N-bromosuccinimide and a catalytic amount of alpha,alpha'-azobisisobutyronitrile were added. The mixture was heated under reflux for 15 minutes. The reaction mixture was concentrated to half of its volume and the resulting insoluble matter was removed by filtration. Concentrating the filtrate gave a syrupy residue. The residue was distilled under reduced pressure to give a fraction boiling at 115° to 120° C./5 mm Hg which was 4.2 g (yield 73percent) of the captioned compound. |
58% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 78℃; for 0.333333h;Darkness; | Example 12: (5-Methyl-2-oxo-l,3-dioxol-4-yl)methyl 4-[(4-methoxyphenyl)amino]-6- (methylcarbamoy^quinoline-S-carboxylate. a) Preparation of the intermed 4-bromomethyl-5-methyl-2-oxo-l,3-dioxolene; To a solution of 4,5-dimethyl-l,3-dioxol-2-one (342 mg, 3.0 mmol) in carbon tetrachloride (10 mL) was added azobisisobutyronitrile (AIBN, 9.8 mg, 0.06 mmol) and iV-bromosuccinimide NBS (580 mg, 3.3 mmol). The reaction mixture was heated in the dark in a stem block at 78 C for 20 minutes. The mixture was cooled and evaporated almost into dryness. The mixture was filtered and the residue was evaporated to give a light yellow solid, which contained 20 percent starting material Yield: 450 mg (58percent). The mixture was used in the next step without further purifi- cation. |
49% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 2.5h;Heating / reflux; | To a solution of 4,5-dimethyl-1,3-dioxolene-2-one (TCI, 10 g, 88 mmol) and N- bromosuccinimide (Fluka, 15.69 g, 88 mmol) in carbon tetrachloride (250 mL) was added benzoyl peroxide (Acros, 500 mg, 2.1 mmol). The reaction mixture was then refluxed for 2.5 h after which time the volatiles were evaporated under vacuum. The resulting residue was triturated with some carbon tetrachloride, filtered and the solid cake was washed with carbon tetrachloride. The filtrate volatiles were removed under vacuum and the yellow oily residue was distilled under vacuum (2-5 torr) to give 4-bromomethyl-5-methyl-1,3-dioxolene-2-one 903 (8.35 g, b.p. 94-98 °C, 49percent) as a pale yellow oil. 1H NMR (CDCI3) 8 4.21 (s, 2H), 2.17 (s, 3H). |
With N-Bromosuccinimide; azobisisobutyronitrile; In tetrachloromethane; | PREPARATION 18 4-Carbo-(5-methyl-2-oxo-1,3-dioxol-4-ylmethoxy)methylpiperazine hydrochloric acid salt Combine <strong>[37830-90-3]4,5-dimethyl-1,3-dioxol-2-one</strong> (3.42 g, 30 mmol), N-bromosuccinimide (5.34 g, 30 mmol) and AIBN (500 mg, 3 mmol) in anhydrous carbon tetrachloride (100 mL). Heat at reflux. After 2 hours, cool and filter. Concentrate the filtrate to give 4-bromomethyl-5-methyl-1,3-dioxol-2-one (6.5 g, crude) as an oil, which can be used for the next step without further purification. | |
With N-Bromosuccinimide;azobisisobutyronitrile; In tetrachloromethane; | PREPARATION 2 Preparation of 4-bromomethyl-5-methyl-1,3-dioxole-2-one According to the method described in Liebigs. Ann. Chem., 1977, 27-32 4,5-dimethyl-1,3-dioxole-2-one (500 mg, 4.38 mmol) and N-bromosuccinimide (0.78 g, 4.38 mmol) were heated under reflux in dry carbon tetrachloride in the presence of alpha-alpha'-azobisisobutyronitrile (7.5 mg) for 20 minutes. The reaction mixture was concentrated under reduced pressure to half the volume, and the precipitated solid was filtered by suction. After removing the solvent from the filtrate, the residue was analyzed by gas chromatography. The obtained mixture (792 mg), contained 70percent of the desired title compound and used for the subsequent reactions. | |
With N-Bromosuccinimide; In tetrachloromethane; | PREPARATION 1 4-Bromomethyl-5-methyl-2-oxo-1,3-dioxole To a stirred solution of 3.0 g of <strong>[37830-90-3]4,5-dimethyl-2-oxo-1,3-dioxole</strong> in 100 ml of carbon tetrachloride was added 4.63 g of N-bromosuccinimide. The resulting solution was heated under reflux and irradiated for 15 minutes. The reaction mixture was cooled to 0°-5° C., filtered and evaporated to give the title product. The NMR spectrum (CDCl3) showed absorptions at 2.05 (5percent of starting material), 2.18 (3H, s), 4.30 (2H, s) and 4.35 (5percent of dibromo compound) ppm downfield from tetramethylsilane. The IR spectrum showed an absorption at 5.49 microns. | |
With N-Bromosuccinimide;azobisisobutyronitrile; In tetrachloromethane; | (1) 4-Bromomethyl-5-methyl-1,3-dioxolen-2-one [compound of formula (III) in which R is methyl and X is bromine] 3.42 g of 4,5-dimethyl-1,3-dioxolen-2-one [compound of formula (III') in which R is methyl, prepared in accordance with the procedure described in Tetrahedron Letters, pages 1701-1704, (1972)] was dissolved in 150 ml of carbon tetrachloride. To the solution were added 5.34 g of N-bromosuccinimide and a catalytic amount of alpha,alpha'-azobisisobutyronitrile. The mixture was heated under reflux for 15 minutes. The reaction mixture was cooled with ice, and the insoluble materials were removed by filtration. The filtrate was concentrated under reduced pressure to give a syrupy residue. The residue was distilled under reduced pressure, and a fraction having a boiling point of 115° to 120° C./5 mmHg was recovered. Thus, 4.2 g (yield 73percent) of the captioned compound having the following properties was obtained as a colorless liquid. Elemental analysis for C5 H5 BrO3: IR (neat) nu(cm-1): near 18 25 (carbonyl). NMR (CCl4) delta(ppm): 2.10 (3H, --CH3, s), 4.10 (2H, --CH2 Br, s). | |
With N-Bromosuccinimide; In tetrachloromethane; | PREPARATION 1 4-Bromomethyl-5-methyl-2-oxo-1,3-dioxole To a stirred solution of 3.0 g of <strong>[37830-90-3]4,5-dimethyl-2-oxo-1,3-dioxole</strong> in 100 ml of carbon tetrachloride was added 4.63 g of N-bromosuccinimide. The resulting solution was heated under reflux and irradiated for 15 minutes. The reaction mixture was cooled to 0°-5° C., filtered and evaporated to give the title product. The NMR spectrum (CDCl3) showed absorptions at 2.05 (5percent of starting material), 2.18 (3H, s), 4.30 (2H, s) and 4.35 (5percent of dibromo compound) ppm downfield from tetramethylsilane. The infrared spectrum showed an absorption at 5.49 microns. | |
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 2h;Reflux; | A mixture of <strong>[37830-90-3]4,5-dimethyl-1,3-dioxol-2-one</strong> (1.0 g, 8.8 mmol), benzoylperoxide (60 mg, 0.25 mmol) and N-bromosuccinimide (1.6 g, 9.0 mmol) in carbon tetrachloride (10 mL) was heated at reflux for 2 h. The solid was removed from the reaction mixture by filtration. The mother liquid was washed with sat. NaHCO3 and brine, dried over MgSO4 and concentrated. The crude product, 4-(bromomethyl)-5-methyl-1,3-dioxol-2-one, was obtained as a yellow oil (1.7 g) and was used without further purification in the next step. | |
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 80℃; for 2h; | To a solution of 16 grams 4,5-dimethyl-1, 3-dioxol-2-one in CC14 (250 mE) was added N135 (23.4 g,131.5 mmol) and AII3N (1.3 g, 7.88 mmol), then the reaction mixture was heated to 80° C. and stirred for 2 hrs. Monitored the starting material gone by TLC. The mixture was filtered and the filtrate was washed with water and brine, the organic phase was dried over Na2504 and concentrated to give crude product as a yellow oil which was used directly next step (25.3 g, yield 93percent). | |
With N-Bromosuccinimide;2,2'-azobis(isobutyronitrile); In tetrachloromethane; | Compound 20 was prepared following the steps disclosed in the literature (Sakamoto er a/., Chem. Pharm. Bull, 1984, 32, 2241). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuryl dichloride; In dichloromethane; | REFERENCE EXAMPLE 2 Preparation of 4-chloromethyl-5-methyl-1,3-dioxolene-2-one (II) To a solution of 75 g of 4,5-dimethyl-1,3-dioxolene-2-one (IV) in 750 ml of methylene chloride was added 97.6 g of sulfuryl chloride dropwise at 40°-42° C. over 2 hours. The mixture was stirred for 40 minutes at the same temperature and evaporated in vacuo to remove the solvent. NMR spectrometry of the resulting oil revealed that the product was 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one (III) containing a trace amount of unreacted 4,5-dimethyl-1,3-dioxolene-2-one (IV). This oil was heated at 90° C. with stirring for 2 hours without isolating 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one (III) and then distilled in vacuo. 75.4 g (corresponding to an overall yield from 4,5-dimethyl-1,3-dioxolene-2-one (IV) of 77percent) of 4-chloromethyl-5-methyl-1,3-dioxolene-2-one (II) having the physicochemical properties described in Reference Example 1 was obtained. | |
326 g | With N-chloro-succinimide; dibenzoyl peroxide; at 90℃; for 5.5h;Large scale; | 4725 g of dichloroethane was added to the DMDO that was stirred up.1012.5g N-chlorosuccinimideAnd 45g benzoyl peroxide,Reaction temperature 90°C, reaction time 5.5h,The crude product obtained DMDO-Cl 382.5g, a yield of 85.00percent; Step 3: Distillation: The DMDO-Cl crude product at -0.1MPa vacuum,Distilled at 110°C to produce 326g of DMDO-ClThe purity by gas chromatography was 99.06percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuryl dichloride; In dichloromethane; | EXAMPLE 1 Preparation of 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one (III) To a solution of 50 g of 4,5-dimethyl-1,3-dioxolene-2-one (IV)(Synthesised by the method described in Tetrahedron Letters, 1701-1704 (1972)) in 350 ml of methylene chloride was added 65 g of sulfuryl chloride dropwise over 1 hour at 40°-42° C. The mixture was stirred for one hour at the same temperature and then evaporated in vacuo to remove the solvent. The resulting residue was distilled in vacuo to obtain 42.1 g (65percent of theory) of 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one (III) as a colorless oil. B.p. 45°-48° C./2 mmHg. IR(CHCl3)nu(cm-1): 1820, near 1695 etc. NMR(CDCl3, delta(ppm)): 2.19(3H, s, CH3), STR5 | |
With thionyl chloride; In dichloromethane; for 4.5h;Reflux; | Example 1The feeding substance than the molar amount of the: DMDO: sulfonyl chloride to 1 : 1.3. The organic solvent is dichloromethane, the quality of the organic solvent with DMDO volume ratio is 1:7. Solid free radical scavenging agent is methyl hydroquinone, DMDO the quality of the amount of 1percent.To is provided with a magnetic stirring, constant pressure dropping funnel, reflux condensation tube, thermometer and is provided with a tail gas absorption device 500 ml flask to three in 350 ml dichloromethane, 50gDMDO, under stirring backflow state, slowly dropping 77g sulfonyl chloride, dropping time is approximately 2.5h, heat preservation after dropping 2h, rotary evaporation to remove the solvent. Furthermore, added to the bottoms of 0.5g methyl hydroquinone, for 90 °C conditions, stirring rearrangement 5h, obtaining a reaction crude. Analysis of the purity of crude 92.33percent, the crude in 2mmHg the vacuum degree of the vacuum distillation, to obtain the target product 52.8g, to yield 81.1percent, purity of 97.87percent. | |
With sulfuryl dichloride; In dichloromethane; at 40℃; for 2h; | Add 50.0 g of <strong>[37830-90-3]4,5-dimethyl-1,3-dioxol-2-one</strong> to a 1 L four-necked flask.530 g of dichloromethane, stirred and dissolved, and heated to reflux, when the internal temperature is not lower than 40 ° C,A mixture of 65 g (1.1 equivalents) of sulfonyl chloride and 132 g of dichloromethane was added dropwise.The internal temperature of the control is not lower than 40 °C, and the mixture is kept warm for 2 hours after the dropwise addition.The temperature was then raised to 85 ° C while distilling off the dichloromethane. When it reaches 85 ° C, it is rearranged for 2 to 3 hours.At room temperature, crude DMDO-Cl was obtained with a GC purity of 85percent to 90percent.Add 30 ml of isopropanol to the above crude product, stir and cool to -10 ° C ~ -5 ° C,Crystallization 0 ~ 1h, suction filtration, rinse with isopropanol down to -5 ° C,Obtained white crystals 53.3g (yield 81.9percent, GC purity 99.3percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 6 Example 5 was repeated using the same molar quantity of 2,3-butanediol in place of ethylene glycol, and the reaction mixture was heated to 120° C. for thirty minutes, then to 150° C. for an additional thirty minutes. A yield of 8.0 g distilled 4,5-dimethyl-1,3-dioxol-2-one was obtained, 88 percent of the theoretical amount. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2,2'-azobis(isobutyronitrile); In benzene; at 20℃; for 0.5h;Heating / reflux; | (1) 2.08 g of <strong>[37830-90-3]4,5-dimethyl-1,3-dioxol-2-one</strong> was dissolved in 24 mL of benzene, to which 3.25 g of N-bromosuccinimide and 86 mg of 2,2'-azobis(isobutyronitrile) were added at room temperature, and this mixture was stirred for 30 minutes while heating it under reflux. The reaction mixture was cooled to room temperature, and consequently, a solution of 4-bromomethyl-5-methyl-1,3-dioxol-2-one in benzene was obtained.(2) 3.00 g of methyl 3-(5-[4-(cyclopentyloxy)-2-hydroxybenzoyl]-2-[3-(methoxymethoxy)-1,2-benzisoxazol-6-yl]methoxy}phenyl) propanoate was dissolved in 15 mL of methanol and 15 mL of tetrahydrofuran, to which a solution of 1.08 g of potassium hydroxide in 4.5 mL of water was added, and this mixture was stirred for one hour at room temperature, and then the solvent was distilled out under reduced pressure. The resultant residue was dissolved in 40 mL of N,N-dimethylformamide, to which 3.60 g of potassium carbonate was added. Then, the benzene solution prepared in (1) was added thereto, and was stirred for one hour at room temperature. The reaction mixture was poured into a mixture of ethyl acetate and water, and adjusted to pH 7 with 6M hydrochloric acid, and then the organic phase was separated therefrom. After the resultant organic phase was washed with water and a saturated sodium chloride solution successively, the washed phase was dried over anhydrous sodium sulfate, and the solvent was distilled out under reduced pressure. The resultant residue was purified by silica gel column chromatography [eluent; toluene:ethyl acetate=5:1] to yield 1.58 g of (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl 3-(5-[4-(cyclopentyloxy)-2-hydroxybenzoyl]-2-[3-(methoxymethoxy)-1,2-benzisoxazol-6-yl]methoxy}phenyl) propanoate as yellow oil. NMR(400MHz,CDCl3) delta value: 1.5-2.0(8H,m), 2.16(3H,s), 2.75(2H,t,J=7.6Hz), 3.10(2H,t,J=7.6Hz), 3.65(3H,s), 4.5-5.0(3H,m), 5.33(2H,s), 5.57(2H,s), 6.37(1H,dd,J=8.8,2.4Hz), 6.47(1H,d,J=2.4Hz), 6.95(1H,d,J=8.4Hz), 7.35(1H,dd,J=8.4,1.2Hz), 7.4-7.6(4H,m), 7.72(1H,d,J=8.0Hz), 12.67(1H,s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With selenium(IV) oxide; In 1,4-dioxane; | Example 26 Preparation of 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene A mixture of <strong>[37830-90-3]4,5-dimethyl-2-oxo-1,3-dioxole</strong>ne (1 mmol) and selenium dioxide (2.5 mmol) in dioxane was heated at reflux for 1 h. Evaporation, extraction and chromatography gave 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene as a yellow oil. TLC: Rf=0.5, 5percent MeOH-dichloromethane. | |
With selenium(IV) oxide; In 1,4-dioxane; | Example 17 Preparation of 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene A solution of <strong>[37830-90-3]4,5-dimethyl-2-oxo-1,3-dioxole</strong>ne (1 mmol) and selenium dioxide (2.5 mmol) in dioxane was heated at reflux for 1 h. Evaporation, extraction and chromatography gave 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene as a yellow oil. TLC: Rf=0.5, 5percent MeOH-dichloromethane. | |
With selenium(IV) oxide; In 1,4-dioxane; for 1h;Heating / reflux; | [01658] A solution of <strong>[37830-90-3]4,5-dimethyl-2-oxo-1,3-dioxole</strong>ne (1 mmole) and selenium dioxide (2.5 mmole) in dioxane was heated at reflux for 1 h. Evaporation, extraction and chromatography gave 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene as a yellow oil. TLC: RPf=0.5, 5percent MeOH-dichloromethane. [01659] A solution of 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene (1 mmole) in DMF was treated with tert-butyldimethylsilane (1.2 mmole) and imidazole (2.2 mmole) at 25 C. for 24 h. Extraction and chromatography gave 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-oxo-1,3-dioxolene. [01660] A solution of 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-oxo-1,3-dioxolene (1 mmole) and Lawesson's reagent (1.2 mmole) in toluene was heated to 120 C. for 12 h. Extraction and chromatography gave 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-thio-1,3-dioxolene. [01661] A solution of 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-thio-1,3-dioxolene in methanolic hydrogen chloride was stirred at 0 C. for 1 h and 25 C. for 12 h. Extraction and chromatography gave 5-methyl-4-hydroxymethyl-2-thio-1,3-dioxolene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With N-Bromosuccinimide; In tetrachloromethane; | Example 9 Synthesis of 4-bromomethyl-5-methyl-1,3-dioxol-2-one A mixture of <strong>[37830-90-3]4,5-dimethyl-1,3-dioxol-2-one</strong> (15.0 g, 0.132 mol), a,a-azobisisobutyronitrile (AIBN) (1.08 g, 0.0066 mol) and N-bromosuccinimide (23.4 g, 0.132 mol) in freshly distilled carbon tetrachloride (350 mL) was refluxed under nitrogen for 16 h. The mixture was concentrated to one-half the initial volume, cooled in an ice bath and the white solid was filtered off. Concentration of the filtrate (CCl4 solution) in a rotavap under reduced pressure gave 4-bromomethyl-5-methyl-1,3-dioxol-2-one as a pale brown liquid in 90percent yield (25 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With N-Bromosuccinimide; In tetrachloromethane; | 1-bromomethyl-2-methylvinylene carbonate A mixture of <strong>[37830-90-3]dimethylvinylene carbonate</strong> (11.4 g, 100 mmol), N-bromosuccinimide (17.8 g, 100 mmol) and 2,2'-azobisisobutyronitrile (250 mg) in carbon tetrachloride (400 mL) was stirred at reflux for 4 hours. Aqueous workup followed by vacuum distillation (110-112° C., 3.5 mm Hg) gave the desired compound (9.26 g, 48percent). |
With N-Bromosuccinimide; In tetrachloromethane; | EXAMPLE 2 Preparation of 4-bromomethyl-5-methyl-1,3-dioxolene-2-one STR13 4,5-Dimethyl-1,3-dioxolene-2-one (11.4 g) was mixed with N-bromosuccinimide (19.6 g) and 2,2-azobis(2-methylpropionitrile) (0.5 g) in freshly distilled carbon tetrachloride (350 mL) and refluxed for 6 hours under an argon atmosphere. The reaction mixture was cooled in an ice bath after reflux and the precipitate formed was filtered off. The tiltrate was washed with water and brine, and dried over sodium sulfate. The solvent was evaporated to yield a yellow oil (20.54 g) which was distilled to obtain the pure monobromomethyl compound as a light yellow oil (11.86 g, 54percent), bp 93° C. at 0.45 mm; 1 H NMR (CDCl3) delta2.15 (s, 3H), 4.21 (S, 2H); IR (film) 1820, 1728, 1392, 1201, 1236, 768 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | In dichloromethane; N,N-dimethyl-aniline; toluene; | A. 4,5-Dimethyl-1,3-dioxole-2-one To 3-hydroxy-2-butanone (17.62 g, 0.2 mol, 1.0 eq.) and N,N-dimethylaniline (25.4 g, 0.21 mol, 1.05 eq.) in methylene chloride (200 mL) at 0° C., a solution of phosgene in toluene (1.93M, 109 mL, 0.21 mol, 1.05 eq.) was added. The reaction was stirred at 0° C. for 15 minutes and then at room temperature for four days. Solvents of the reaction were distilled out until the bath temperature reached 1600C. The mixture was cooled to room temperature, diluted with ether, washed with 1N hydrochloric acid and saturated sodium chloride. The organic liquid was dried (magnesium sulfate) and concentrated. The residue was recrystallized (ether/hexane) to afford the title compound as a white solid (12.64 g, 55percent). |
3.53 g (25%) | In dichloromethane; N,N-dimethyl-aniline; | PREPARATION 2 4,5-Dimethyl-2-oxo-1,3-dioxole A solution of phosgene (12.18 g) in cold dichloromethane was added dropwise to a cold solution of 3-hydroxy-2-butanone (10.83 g) and 16.38 g of N,N-dimethylaniline in 50 ml dichloromethane. The resulting green solution was stirred 2 hours at 0°-5° C. The solution was then evaporated to give an oil which was heated at 160°-190° C. for 30 minutes. The cooled reaction mixture was partitioned between water and ether. The separated aqueous layer was further extracted with ether and the combined organic extracts were dried and concentrated. The residue was triturated with pentane to give 3.53 g (25percent) of a white crystalline solid, m.p. 76°-78° C. The NMR spectrum of the product (CDCl3) showed an absorption at 2.05 (s) ppm downfield from tetramethylsilane. The mass spectrum showed peaks at m/e 114, 56 and 43 (100percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.7% | The autoclave with the agitation was filled with carbon dioxide gas,After the addition of the solid base catalyst sodium carbonate and potassium bicarbonate,5 kg of raw materials 3-hydroxy-2-butanone into the reactor,Control the reactor temperature at 30 ± 2 ,After stirring for 5 hours, 3-hydroxy-2-butanone was enolated,3-hydroxy-2-butanone for enolysis,The feed quality ratio is:3-hydroxy-2-butanone: sodium carbonate: potassium bicarbonate = 100: 0.5: 0.5.3-hydroxy-2-butanone,To the high pressure reactor supplementation of esterification catalyst potassium methoxide,Sodium ethoxide,among them,Feed quality ratio: 3-hydroxy-2-butanone: potassium methoxide: sodium ethoxide = 100: 0.5: 0.5.Closed reactor,So that sodium methoxide,The sodium ethoxide composition is evenly distributed in a high pressure reactor,And then bubbling carbon dioxide gas from the reaction liquid level,To the kettle pressure to 3.5MPa,The reaction temperature was controlled at 40 ± 2 ° C.During the insulation process,When the reaction is carried out for a period of time,The pressure inside the reactor is reduced,When the pressure inside the kettle is no longer reduced,Supplemented with carbon dioxide to 3.5MPa,And then adjust the temperature again to 40 ± 2 to continue the esterification reaction,Repeat the above operation,Until the temperature inside the reactor after the pressure did not decline so far,The unreacted 3-hydroxy-2-butanone was recovered.Adjust the reactor temperature to room temperature,Eliminate unreacted carbon dioxide to atmospheric pressure,To the reaction vessel was added 10 L of dichloroethane,The reaction solution containing 4,5-dimethyl-1,3-dioxol-2-one was taken out,The reaction solution was washed with distilled water to remove the aqueous phase to remove the catalyst,Until the reaction solution is neutral,After drying the reaction solution with anhydrous magnesium sulfate,After drying, the desiccant is removed by filtration,The filtrate is distilled to recover dichloroethane,The residue was cooled to 0-5 ° C,The crude solid was collected by centrifugation.The crude product was recrystallized from a mass of petroleum ether as a crystallization solvent to give the product 4,5-dimethyl-1,3-dioxol-2-one as white crystals,The single crystal yield of the white crystal was 48.23percentPurity 99.7percentTotal 3133.4g.In the same manner as in Example 13, prior to the addition of dichloroethane to the autoclave,The unreacted 3-hydroxy-2-butanone was recovered in the reaction solution,And re-as a raw material,And supplemented with fresh 3-hydroxy-2-butanone starting material to 5 kg,The rest is operated as in Example 13,The above-mentioned operation was repeated by recovering the recovered 3-hydroxy-2-butanone as a starting material,Continuous batch preparation,A total of 5248.2 g of white crystals of product 4,5-dimethyl-1,3-dioxol-2-one were obtained,The total yield reached 80.7percentPurity of 99.6percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
450 g | In N,N-dimethyl-aniline; at 15℃; for 5.5h; | Add 500 g of acetoin to the three bottle with stirring.1000gN,N-dimethylaniline, 3250g dichloroethane,Then add 1000 g of methyl chloroformate uniformly.The reaction temperature is controlled at 15°C and the reaction time is 5.5h. After completion of the reaction solution stripped to give DMDO 450g; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
850 g | In dichloromethane; N,N-dimethyl-aniline; at 12℃; for 6h; | 1000 g acetoin was added to the reactor while stirring.2000gN,N-dimethylaniline,4000g dichloromethane,Then, 1500 g of ethyl chloroformate was added dropwise.The reaction temperature is controlled at 12°C and the reaction time is 6h.After the reaction was completed, DMDO 850g was desolvated; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
190 g | In dichloromethane; N,N-dimethyl-aniline; at 20℃; for 0.5h; | Add 200 g of acetoin to the three-mouth bottle while stirring.600gN,N-dimethylaniline,2000g dichloromethane,Then 600 g of propyl chloroformate is added dropwise,The reaction temperature is controlled at 20°C and the reaction time is 0.5h.Upon completion of the reaction, DMDO 190g was desolvated; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With triethylamine; at 0 - 20℃; for 1.0h;Inert atmosphere; | 4,5-Dimethyl vinylene carbonate (86 mg, 1 mmol) and triethylamine (10 mg, 0.1 mmol) were mixed. The system was purged with nitrogen, and <strong>[83706-98-3](Z)-4,4,4-trifluoro-2-buten-1-ol</strong> (126 mg, 1 mmol) was dropwise added at 0 C. The solution was returned to room temperature and stirred for one hour, whereby 158 mg (yield: 66%) of the target product represented by the following formula was obtained. |
Tags: 37830-90-3 synthesis path| 37830-90-3 SDS| 37830-90-3 COA| 37830-90-3 purity| 37830-90-3 application| 37830-90-3 NMR| 37830-90-3 COA| 37830-90-3 structure
A146976 [80841-78-7]
4-(Chloromethyl)-5-methyl-1,3-dioxol-2-one
Similarity: 0.78
A146976 [80841-78-7]
4-(Chloromethyl)-5-methyl-1,3-dioxol-2-one
Similarity: 0.78
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