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CAS No. : | 3047-32-3 | MDL No. : | MFCD00190143 |
Formula : | C6H12O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UNMJLQGKEDTEKJ-UHFFFAOYSA-N |
M.W : | 116.16 | Pubchem ID : | 76444 |
Synonyms : |
|
Num. heavy atoms : | 8 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 30.83 |
TPSA : | 29.46 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.88 cm/s |
Log Po/w (iLOGP) : | 1.6 |
Log Po/w (XLOGP3) : | 0.18 |
Log Po/w (WLOGP) : | 0.41 |
Log Po/w (MLOGP) : | 0.21 |
Log Po/w (SILICOS-IT) : | 1.38 |
Consensus Log Po/w : | 0.76 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.54 |
Solubility : | 33.4 mg/ml ; 0.287 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.36 |
Solubility : | 51.1 mg/ml ; 0.44 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -1.01 |
Solubility : | 11.4 mg/ml ; 0.0984 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.35 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H227-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
64.7% | With potassium hydroxide; Diethyl carbonate In ethanol for 2 h; Reflux | 100g, diethyl carbonate 132g, potassium hydroxide 0.25g, bottle and ethanol 10 ml is added during the reaction. After heating at reflux for 2 hours, under atmospheric pressure, 150 °C by distillation in the greater part of the solvent is removed, a crude product is obtained. Furthermore, in a vacuum distillation is, for the purification of the crude product is obtained. 120 °C and 0.1torr compd. a1 (colorless liquid) is under a pressure, which is collected by the yield 64.7percent. Next, 82g compd. a1,pyridine 111g, and dichlomethane 400 ml bottles which are added to the reaction. The mixture is stirred under nitrogen, then cooled to 5° C -0 °C. 4-bromobenzoyl chloride in 200 ml of dichlomethane soln.of, 0 ° C-5 ° C during the reaction of the drop in the bottle. After completion of the addition, reaction bottle is warmed to room temperature, the stirring time is 8, the bottle 500 ml of water is added during the reaction, which is 5 min. The organic layer is collected, 100 ml of the water layer is extracted using dichlomethane 2 times. The organic layer is collected, in order to adjust the pH value to 7 in about 100 ml of the salt water. Next, an organic layer is collected, 20g is 30 minutes of drying with anhydrous sodium sulfate, then filtered. In order to obtain compd. a2, somas conc. under reduced pressure, the petroleum ether and ethyl acetate (9:1) [...] purified by using a flat, it is further chilled in ethanol recrystallization, 68.7percent yield. The purity of compd. a2 (gas chromatography (GC) analysis by a) is, at 98.109percent, and, the melting point (mp) compd. a2,50.63 ° C-52.56 ° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; | EXAMPLE 1 3-Ethyl-3-hydroxymethyloxetane Into a 150 mL round bottom flask fitted with a magnetic stirrer, thermometer, condenser, distillation head and receiver were placed a mixture of 67.0 g (0.5 mol) trimethylolpropane, 59.0 g (0.5 mol) of diethyl carbonate and 0.05 g of potassium hydroxide dissolved in 2 mL of absolute alcohol. The mixture was refluxed until the pot temperature was below 105° C. and then distilled keeping the head temperature at 76°-78° C. Distillation was continued until the pot temperature was 145° C. Then, the pressure was reduced gradually to 15 mm Hg maintaining the pot temperature at 140°-150° C. Upon heating above 180° C., carbon dioxide evolution was rapid and most of the product distilled at 100°-160° C. Redistillation through an efficient column gave 43.9 g of 3-ethyl-3-hydroxymethyloxetane (yield: 76percent, b.p.:114°-115° C. at 16 mm Hg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With hydrogen bromide; In tetrahydrofuran; water; at 25℃; for 5h; | Example 2: Synthesis of ethyl vinyl sulfone carbonate monomer Ethyl vinyl sulfone carbonate monomer (VSEC) was also synthesized in four steps (Scheme 2). To a stirred solution of 3-ethyl-3-oxetanemethanol (5.8 g, 50 mmol) in THF (100 mL) was dropwise added HBr (40percent, 20 mL). The reaction mixture was allowed to warm to 25 °C and stirred for 5 h. The reaction mixture was then diluted with H20 (150 mL) and extracted with diethyl ether (4 chi 150 mL). The organic phase was dried over anhydrous MgS04 and concentrated to give the desired product (bromo-diol) as a white solid (8.82 g, 90percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.3% | With pyridinium chlorochromate; In dichloromethane; at 20℃; for 5h; | Step 1 3-Ethyloxetane-3-carbaldehyde A solution of (3-ethyloxetan-3-yl)methanol (5.0 g, 43.0 mmol) in 60 ml of dichloromethane was added dropwise to a mixture of pyridinium chlorochromate (14.85 g, 68.9 mmol) and celite (4.30 g) in 200 ml of dichloromethane. The reaction medium was stirred at ambient temperature for 5 hours. The reaction medium was filtered on 70 g of silica and eluted with dichloromethane. The organic phases were combined and concentrated. 4.0 g of the expected product were obtained in the form of a pale green oil. Yield=82.3percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
SI-100L;Reactivity; | Examples 11-18 and Comparative Examples 2-3 (a stability test of oxetane); 10g of each of 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane (HBOX) synthesized in Example 1, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane (HPROX) synthesized in Example 4, 3-ethyl-3-(2-hydroxyethyloxyethyl)oxymethyloxetane (HEOEOX) synthesized in Example 6, 3-ethyl-3-(2,3-dihydroxypropyl)oxymethyloxetane (DHPOX) synthesized in Example 7 and 3-ethyl-3-hydroxymethyloxetane (hereinafter, referred to as EHO) which is a publicly known compound, was charged into a glass sample tube of an inner volume of 30 ml, and a cationic polymerization catalyst (SI-100L or SI-110L manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.) (0.1 g) was added into the tube. The content of the tube was intimately mixed and left at room temperature. A state of each oxetane in each elapsed time was visually observed. The results are shown in Table 2. | |
SI-110L;Reactivity; | Examples 11-18 and Comparative Examples 2-3 (a stability test of oxetane); 10g of each of 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane (HBOX) synthesized in Example 1, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane (HPROX) synthesized in Example 4, 3-ethyl-3-(2-hydroxyethyloxyethyl)oxymethyloxetane (HEOEOX) synthesized in Example 6, 3-ethyl-3-(2,3-dihydroxypropyl)oxymethyloxetane (DHPOX) synthesized in Example 7 and 3-ethyl-3-hydroxymethyloxetane (hereinafter, referred to as EHO) which is a publicly known compound, was charged into a glass sample tube of an inner volume of 30 ml, and a cationic polymerization catalyst (SI-100L or SI-110L manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.) (0.1 g) was added into the tube. The content of the tube was intimately mixed and left at room temperature. A state of each oxetane in each elapsed time was visually observed. The results are shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Examples of compounds of the general formula (1) are:3-methyl-3-hydroxymethyloxetane,3-ethyl-3-hydroxymethyloxetane,3-propyl-3-hydroxymethyloxetane,3-butyl-3-hydroxymethyloxetane,3-pentyl-3-hydroxymethyloxetane,3-hexyl-3-hydroxymethyloxetane,3-heptyl-3-hydroxymethyloxetane, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C27H33O3S(1+)*F6P(1-);UV-irradiation;Reactivity; | A composition is prepared by mixing the following components:; 81.80 parts of 3,4-epoxycyclohexylmethyl carboxylate (CYRACURE.(R). UVR 6105, provided by Dow Chemical); 11.73 parts of 3-ethyl-3-hydroxymethyl-oxetane (CYRACU RE.(R). UVR 6000, provided byDow Chemical); 5.92 parts of epsilon-caprolactone triol (Tone Polyol 301 , provided by Dow Chemical); 0.56 parts of a silicon surface additive (Byk 307, provided by BYK); 100.0 parts overprint varnish, flexo ink basic formulation; 3percent of the compound of example 2 is stirred into said formulation, which then is applied with a 4mum wire bar onto an aluminum film of 85mum thickness.Curing is effected by moving the sample on a conveyor belt under a 1x120 W/cm medium pressure mercury lamp (IST) fitted with an aluminum reflector. Curing is determined by dry- rub resistance with Tela.(TM). tissue paper. The belt speed is varied by 10 m/min steps. The higher the reactivity of the photoinitiator, the faster the belt can be moved to achieve a cured coating. With the described composition a cured coating is achieved at a conveyor belt speed of 180 m/min.To measure the yellowing of such a sample, the above formulation with 3percent of compound 2 is applied (30mum) on a Q-panel (white polyester base coat) and cured on a conveyor belt under a 200 W/cm medium pressure mercury lamp (IST) with a speed of 20 m/min. The b* value is measured directly after curing: 2.3. Then the sample is irradiated for 16 hours under a fluorescent tube (TLK 40/05) and the b* value is measured again: it is unchanged at 2.3. | |
With C33H39O3S(1+)*F6P(1-);UV-irradiation;Reactivity; | A composition is prepared by mixing the following components:; 81.80 parts of 3,4-epoxycyclohexylmethyl carboxylate (CYRACURE.(R). UVR 6105, provided by Dow Chemical); 11.73 parts of 3-ethyl-3-hydroxymethyl-oxetane (CYRACU RE.(R). UVR 6000, provided byDow Chemical); 5.92 parts of epsilon-caprolactone triol (Tone Polyol 301 , provided by Dow Chemical); 0.56 parts of a silicon surface additive (Byk 307, provided by BYK); 100.0 parts overprint varnish, flexo ink basic formulation; 3percent of the compound of example 2 is stirred into said formulation, which then is applied with a 4mum wire bar onto an aluminum film of 85mum thickness.Curing is effected by moving the sample on a conveyor belt under a 1x120 W/cm medium pressure mercury lamp (IST) fitted with an aluminum reflector. Curing is determined by dry- rub resistance with Tela.(TM). tissue paper. The belt speed is varied by 10 m/min steps. The higher the reactivity of the photoinitiator, the faster the belt can be moved to achieve a cured coating. With the described composition a cured coating is achieved at a conveyor belt speed of 180 m/min.To measure the yellowing of such a sample, the above formulation with 3percent of compound 2 is applied (30mum) on a Q-panel (white polyester base coat) and cured on a conveyor belt under a 200 W/cm medium pressure mercury lamp (IST) with a speed of 20 m/min. The b* value is measured directly after curing: 2.3. Then the sample is irradiated for 16 hours under a fluorescent tube (TLK 40/05) and the b* value is measured again: it is unchanged at 2.3. | |
With C51H51O3S(1+)*F6P(1-);UV-irradiation;Reactivity; | A composition is prepared by mixing the following components:; 81.80 parts of 3,4-epoxycyclohexylmethyl carboxylate (CYRACURE.(R). UVR 6105, provided by Dow Chemical); 11.73 parts of 3-ethyl-3-hydroxymethyl-oxetane (CYRACU RE.(R). UVR 6000, provided byDow Chemical); 5.92 parts of epsilon-caprolactone triol (Tone Polyol 301 , provided by Dow Chemical); 0.56 parts of a silicon surface additive (Byk 307, provided by BYK); 100.0 parts overprint varnish, flexo ink basic formulation; 3percent of the compound of example 2 is stirred into said formulation, which then is applied with a 4mum wire bar onto an aluminum film of 85mum thickness.Curing is effected by moving the sample on a conveyor belt under a 1x120 W/cm medium pressure mercury lamp (IST) fitted with an aluminum reflector. Curing is determined by dry- rub resistance with Tela.(TM). tissue paper. The belt speed is varied by 10 m/min steps. The higher the reactivity of the photoinitiator, the faster the belt can be moved to achieve a cured coating. With the described composition a cured coating is achieved at a conveyor belt speed of 180 m/min.To measure the yellowing of such a sample, the above formulation with 3percent of compound 2 is applied (30mum) on a Q-panel (white polyester base coat) and cured on a conveyor belt under a 200 W/cm medium pressure mercury lamp (IST) with a speed of 20 m/min. The b* value is measured directly after curing: 2.3. Then the sample is irradiated for 16 hours under a fluorescent tube (TLK 40/05) and the b* value is measured again: it is unchanged at 2.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With sodium hydroxide; tetrabutylammomium bromide; In hexane; water; at 80℃; for 6h; | Into a 2 L egg plant type flask were charged 46.3 g (0.40 mol) of 3-hydroxymethyl-3-ethyloxetane (product name: OXT-101 manufactured by Toagosei Co., Ltd.), 250.3 g (1.16 mol) of 1,4-dibromobutane (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 275 ml of hexane. 500 ml of a 33 percent sodium hydroxide aqueous solution containing 2 g of tetra-n-butylammonium bromide (reagent, manufactured by Tokyo Kasei Kogyo Co. , Ltd.) was added to the mixture and vigorously stirred for 5 hours. After the mixture was refluxed at a temperature of 80 °C for one hour, 500 ml of deionized water was added thereto so as to separate the mixture into an organic phase and an aqueous phase. The aqueous phase was extracted three times with 160 ml of hexane. After the organic phase and the extracted phase were dried over magnesium sulfate, the solvent was distilled out in a vacuum. The resulting transparent liquid was distilled in a vacuum thereby obtaining 44.5 g (0.18 mol) of 3-[(4-bromobutoxy)methyl]-3-ethyloxetane as a distillate at 109 °C/532 Pa (yield: 44percent, identified with 1H-NMR). In a 300 ml three neck flask, 5.2 g (31 mmol) of ethyl p-hydroxybenzoate, 4.7 g (34 mmol) of potassium carbonate anhydride, and 7.8 g (31 mmol) of the 3-[(4-bromobutoxy)methyl]-3-ethyloxetane were dissolved in 50 ml of dimethylformamide. After the solution remained turbid was heated to a temperature of 80 °C and stirred for 4 hours, the solvent was completely distilled out in a vacuum. To the resulting yellow oily substance were added 15 ml of a 7 percent sodium hydroxide aqueous solution and 15 ml of methanol. The mixture was refluxed for two and half hours. 1 N (normality) of hydrochloric acid was added to the mixture such that the pH is adjusted to about 3. The resulting white precipitate was filtered and dried in a vacuum thereby obtaining 8.6 g (28 mmol)of 4-[7-(3-ethyl-3-oxetanyl)-1,6-dioxaheptyl)benzoic acid (yield: 89percent, identified with 1H-NMR). The resulting compound was no more purified and used in the following reaction. Into a 100 ml three neck flask were charged 1.1 g (9.6 mmol) of methanesulfonyl chloride, 0.1 g of nitrobenzene, and 10 ml of tetrahydrofuran. To the mixture was added a solution obtained by dissolving 3.1 g (10 mmol) of the 4-[7-(3-ethyl-3-oxetanyl)-1,6-dioxaheptyl]benzoic acid in 1.3 g (10 mmol) of diisopropylethylamine and 10 ml of tetrahydrofuran, while the mixture was cooled with ice. The mixture was stirred for 2 hours after the temperature thereof had been returned to ordinary temperature. To the mixture were added a solution obtained by dissolving 0.54 g (4.8 mmol) of hydroquinone in 8 ml of tetrahydrofuran, 0.3 g of dimethylaminopyridine, and 1.0 g of triethylamine. The mixture was refluxed for 3 hours. After the mixture was cooled, the resulting white precipitate was recrystallized from methanol thereby obtaining 1.9 g (2.8 mmol) of the intended liquid crystalline oxetane compound 1 represented by the following formula (yield: 55 percent, identified with 1H-NMR).[Liquid crystalline oxetane compound 1] The 1H-NMR spectrum of the resulting liquid crystalline oxetane compound 1 is shown in Fig. 1. The phase behavior and phase transition temperature of the resulting liquid crystalline oxetane compound were as follows:[Liquid crystal phase behavior and phase transition temperature] C-65 °C-Nm-94 °C-Iso |
With sodium hydroxide;tetrabutylammomium bromide; In hexane; water; at 20℃; for 6h;Heating / reflux; | [Reference Example 2 (synthesis of intermediate compound 2 having an oxetanyl group)]; In accordance with Scheme 2 below, an intermediate compound 2 having an oxetanyl group was synthesized. [Show Image] Intermediate Compound 2 having an oxetanyl group | |
With sodium hydroxide; tetrabutylammomium bromide; In hexane; water; at 20℃; for 6h;Heating / reflux; | In accordance with Scheme 2 below, an acrylic compound having an oxetanyl group (acrylic compound 2) was synthesized using 3-ethyl-3-hydroxymethyloxetane (OXT-101, manufactured by Toagosei Co., Ltd). The 1H-NMR spectrum of the acrylic compound 2 is shown in Fig. 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With triethylamine; In dichloromethane; at 25℃; for 2h;Inert atmosphere;Product distribution / selectivity; | In a nitrogen atmosphere, 3-ethyl-3-oxetanemethanol (100 g), methylene chloride (1000 g), and triethylamine (113 g) were placed in a four-necked flask, followed by stirring at room temperature (25° C.). To this, was added dropwise methanesulfonyl chloride (108 g) over one hour. After dropwise addition, the mixture was subjected to a reaction at room temperature (25° C.) for one hour. The resulting reaction mixture was combined with 400 g of ion-exchanged water, separated into two liquid layers, from which the methylene chloride layer was recovered, concentrated, elded 3-ethyl-3-methanesulfonyloxymethyloxetane (170 g, in a yield of 99percent). |
95% | With triethylamine; In toluene; at 5 - 20℃; for 6h; | Reference Example 1 (Synthesis of 3-ethyl-3-methanesulfonyloxymethyloxetane) After adding 3-ethyl-3-hydroxymethyloxetane (465 g (4.0 mol)), triethylamine (486 g (4.8 mol)) and toluene (1,840 ml) to a glass flask having an inner volume of 5,000 ml equipped with a stirrer, a thermometer and a dropping funnel, while keeping the liquid temperature at 5-10°C, methanesulfonyl chloride (504 g (4.4 mol)) was gradually added to react at the same temperature for 3 hours and at room temperature for 3 hours with stirring. After the completion of the reaction, an aqueous saturated sodium bicarbonate solution (930 ml) was added to the reaction solution and a liquid separation was performed. Subsequently an aqueous layer was extracted with toluene (930 ml), an extract was combined with a previously extracted organic layer, and the combined liquid was washed with water (465 ml). A resultant organic layer was concentrated under reduced pressure to give, as a brown liquid, 3-ethyl-3-methanesulfonyloxymethyloxetane (777 g) having a purity of 95percent (a value measured by 1H-NMR) (an isolated yield based on 3-ethyl-3-hydroxymethyloxetane: 95percent). The physical properties of 3-ethyl-3-methanesulfonylmethyloxetane were as follows. CI-MS(m/e); 195 (M+1) 1H-NMR (CDCl3, delta (ppm)); 0.94 (3H, t), 1.81 (2H, q), 3.07 (3H, s), 4.38 (2H, s), 4.42-4.48 (4H, m) |
93% | With triethylamine; In dichloromethane; at 0 - 20℃; for 2h; | (3-Ethyloxetan-3-yl)methanol (64.0 mg, 0.552 mmol) and triethylamine (111 mg, 1.10 mmol) were dissolved in methylene chloride (20 mL), and methanesulfonyl chloride (94.9 mg, 0.829 mmol) was then added under the condition of 0° C. The reaction solution was stirred at room temperature for 2 hours, and then diluted by adding methylene chloride (20 mL), followed by washing with saturated sodium bicarbonate solution (20 mL*2). The organic phases were dried over anhydrous sodium sulfate, and then filtered. The filtrate was concentrated under reduced pressure, and then separated and purified by silica gel column chromatography (4:1 petroleum ether/ethyl acetate, Rf-0.5) to give (3-ethyloxetan-3-yl)methyl methanesulfonate (100 mg, colorless oil) with a yield of 93percent. MS-ESI calculated value: [M+H]+ 195; measured value: 195. |
With triethylamine; | [Reference Example 1 (synthesis of intermediate compound 1 having an oxetanyl group)]; In accordance with Scheme 1 below, an intermediate compound 1 having an oxetanyl group was synthesized using 3-ethyl-3-hydroxymethyloxetane (OXT-101, manufactured by Toagosei Co., Ltd.) as the raw material. [Show Image] Intermediate Compound 1 having an oxetanyl group | |
With triethylamine; In diethyl ether; for 1h; | Into a 300 ml three neck flask were charged 25.4 g of 2,3-dihydropyran (reagent, manufactured by Tokyo Kasei Kogyo Co. , Ltd.), 41.4 g of p-hydroxybenzoic acid (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 3.7 g of pyridinium p-toluenesulfonate (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.). The mixture was dissolved after addition of 20 ml of methylene chloride and 80 ml of absolute ether. After the mixture was vigorously stirred for about 3 hours, it was extracted 3 times with 70 ml of a 10 percent sodium hydroxide aqueous solution. The resulting extracted solution was neutralized with 1 N of hydrochloric acid until the pH is made to 6. The resulting precipitate was filtered and dried in a vacuum thereby obtaining 57.4 g of crude p-tetrahydropyranyloxy benzoic acid. Into a 500 ml three neck flask equipped with a mechanical stirrer, a dropping funnel, and a Dimroth condenser were charged 5.73 g of methanesulfonyl chloride, 0.6 g of nitrobenzene, and 20 g of tetrahydrofuran. To the mixture was added a solution obtained by dissolving 11.1 g of the crude p-tetrahydropyranyloxy benzoic acid in 6.46 g disopropylethylamine and 50 g of tetrahydrofuran through the dropping funnel while the mixture was cooled with ice. After the mixture was stirred for one hour while cooled with ice, to the mixture while cooled with ice was added a solution obtained by dissolving 12.2 g of p-octyloxyphenol (reagent manufactured by Kanto Kagaku) in 6.67 g of triethylamine and 50 g of tetrahydrofuran. The mixture was refluxed for one hour. The reaction solution was cooled and then extracted with diethylether. After the organic phase was washed 3 times with 1 N of hydrochloric acid and once with a sodium chloride solution, the solvent was distilled out in a vacuum. To the resulting oily product were added 20 ml of tetrahydrofuran and 20 ml of 1 N of hydrochloric acid. The mixture was refluxed for one hour. 50 ml of methylene chloride was added to the resulting reaction solution so as to separate the organic phase therefrom. After the organic phase was washed with 1 N of hydrochloric acid and a sodium chloride aqueous solution and then dried over magnesium sulfate anhydride, it was filtered. The solvent was distilled out in a vacuum. The resulting crude p-hydroxybenzoic acid-p-octyloxyphenol ester was recrystallized from ethylacetate/hexane thereby obtaining 5.13 g of crude p-hydroxybenzoic acid-p-octyloxyphenol ester. The resulting compound was identified with 1H-NMR. Into a 200 ml three neck flask equipped with a dropping funnel and a Dimroth condenser were charged 20 g of 3-ethyl-3-hydroxymethyl-oxetane (product name : OXT-101 manufactured by Toagosei Co., Ltd.), 17.4 g of triethylamine, and 50 ml of diethylether. The mixture was cooled in an ice bath. 25 ml of a solution obtained by dissolving 19.7 g of methanesulfonyl chloride in diethylether was slowly added to the mixture through the dropping funnel. After the ice bath was removed and the mixture was stirred for one hour, the precipitated amine salt was filtered out. The remaining reaction solution was concentrated in a vacuum thereby obtaining crude mesilate. Into a 200 ml three neck flask equipped with a mechanical stirrer and a Dimroth condenser was charged the crude mesilate and were added thereto 23.8 g of p-hydroxybenzoic acid ethyl ester (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 29.7 g of potassium carbonate (first grade reagent manufactured by Wako Pure Chemical Industries,Ltd). Lastly, dimethylformamide was added such that the total amount was made 180 ml. The mixture was heated to a temperature of 100 °C and stirred with the mechanical stirrer for 4 hours. After the mixture was then cooled to room temperature and the precipitated salt was filtered out, the solvent was distilled out in a vacuum therefrom and dried in a vacuum thereby obtaining a crude ester compound. Into a 200 ml egg plant type flask equipped with a Dimroth condenser were charged the crude ester compound and 50 ml (61.4 g) of a 18.5 percent potassium hydroxide aqueous solution. The mixture was refluxed for 3 hours. The resulting reaction solution was poured into 700 ml of ice water in a 2 L beaker so as to be made a transparent solution. The solution was added with stirred to 40 ml (65.8 g) of a 39 percent sodium hydrogen sulfate aqueous solution. As a result, deposit was precipitated and thus filtered thereby obtaining crude p-(3-ethyl-3-oxetanyl)-methoxybenzoic acid. The resulting crude crystal was recrystallized from water/acetonitrile and dried in a vacuum thereby obtaining 29.3 g of p-(3-ethyl-3-oxetanyl)-methoxybenzoic acid. Into a 200 ml three neck flask equipped with a mechanical stirrer, a dropping funnel, and a Dimroth condenser were charged 1.72 g of methanesulfonyl chloride, 0.2 g of nitrobenzene, and 10 ml of tetrahydrofuran. The mixture was cooled in an ice bath. After through the dropping funnel was added slowly a solution obtained by dissolving 3.5... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In accordance with Scheme 5 below, an acrylic compound 5 having an oxetanyl group (acrylic compound 5)was synthesized. The 1H-NMR spectrum of the acrylic compound 5 is shown in Fig. 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
dibutyltin(II) dilaurate; In ethyl acetate; at 55℃; for 4h; | Example 1: Preparation of compound represented by formula (2); Into a 100 mL four-necked flask, 10.0 g of 2-acryloyloxyethyl isocyanate (manufactured by SHOWA DENKO K. K. (70.9 mmol), 8.24 g of 3-ethyl-3-hydroxymethyloxetane (manufactured by UBE INDUSTRIES, LTD., product name: Ethanacol EHO) (70. 9mmol), 0.04 g of dibutyltin dilaurate (manufactured by TOKYO KASEI KOGYO CO. , LTD. ) and 44.5 g of ethyl acetate were charged. A thermometer and a condenser were equipped to the flask, and the flask was heated to 55 °C in an oil bath. Stirring was performed by using a magnetic stirrer. After 4 hours'reaction, disappearance of absorption of isocyanate group was confirmed by using an infrared spectrophotometer (manufactured by JASCO Corporation, product code : FT-IR/8000 (hereinafter, simply referred to as"FT-IR")), and the reaction solution was washed with demineralized water twice and then the organic layer was dried over anhydrous magnesium sulfate. Further, ethyl acetate was removed by using an evaporator and a vacuum pump to thereby obtain 14.68 g of a crude product having a purity of 94.9 percent. 5.0 g of the crude product was subjected to purification through column chromatography with silica gel (manufactured by Wako Pure Chemical Industries, Ltd. , product name: Wakogel C-200) and solvent composed of n-hexane : ethyl acetate=2: 1 (volume ratio) and then condensed. Subsequently, the product was subjected to high-performance liquid chromatography (hereinafter, simply referred to as"LC"), to thereby obtain a purified product having a purity of 98.0 percent. The obtained product was subjected to 13C-NMR spectrum measurement by using magnetic nuclear resonance analyzer (manufacturedbyJEOL, productcode : JNM-AL400) (hereinafter, referred to as"NMR") in heavy chloroform. The resulting 13C-NMR chart is shown in Fig. 1. In attribution of the peaks in the chart, the purified product was confirmed to be represented by formula (2). The peaks in the chart of Fig. 1 and attributions are shown below. 9. 0ppm : carbon atom in methyl group at 10, 27. 7ppm: carbon atom in methylene group at 9 41. 0ppm : carbon atom in methylene group at 5 43. 5ppm : quaternary carbon atom at 8 64.4ppm : carbon atom in methylene group at 4 67.6ppm : carbon atom in methylene group at 7 78.6ppm : carbon atom in methylene groups at 11 and 12 128. 7ppm: carbon atom at 1 132.3ppm : carbon atom at 2 157.2ppm : carbon atom in carbonyl group at 6 166.8ppm : carbon atom in carbonyl group at 3 |
Yield | Reaction Conditions | Operation in experiment |
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dibutyltin(II) dilaurate; In ethyl acetate; at 55℃; for 6h; | Example 2: Preparation of compound represented by formula (3); Into a 200 mL four-necked flask, 17. 15 g of 2-methacryloyloxyethyl isocyanate (product name: karenz MOI, manufactured by SHOWA DENKO K. K. (111 mmol), 12.85 g of 3-ethyl-3-hydroxymethyloxetane (111 mmol), 0.06 g of dibutyltin dilaurate and 70. 0 g of ethyl acetate were charged. A thermometer and a condenser were equipped to the flask, and the flask was heated to 55 °C in an oil bath. Stirring was performed by using a magnetic stirrer. After 6 hours'reaction, disappearance of absorption of isocyanate group was confirmed by using an FT-IR, and the reaction solution was washed with demineralized water twice and then the organic layer was dried over anhydrous magnesium sulfate. Further, ethyl acetate was removed by using an evaporator and a vacuum pump to thereby obtain 28.06 g of a crude product having a purity of 94.9 percent. 5.0 g of the obtained crude product was purified in the same manner as in Example 1 to thereby obtain a purified product having a purity of 98. 3 percent. The purified product was subjected to 13C-NMR measurement. The resulting 13C-NE chart was shown in Fig. 2. In attribution of the peaks in the chart, the purified product was confirmed to be represented by formula (3). The peaks in the chart of Fig. 2 and attributions are shown below. 8. 1ppm : carbon atom in methyl group at 11 18.3ppm : carbon atom in methyl group at 3, 26.8ppm : carbon atom in methylene group at 10, 40.2ppm : carbon atom in methylene group at 6, 42.7ppm : quaternary carbon atom at 9, 63.6ppm : carbon atom in methylene group at 5, 66.7ppm : carbon atom in methylene group at 8, 77.7ppm : carbon atom in methylene groups at 12 and 13, 125. 9ppm: carbon atom at 1, 135. 7ppm: carbon atom at 2, 156. 3ppm: carbon atom at carbonyl group at 7, 1 67. lppm : carbon atom at carbonyl group at 4. |
Yield | Reaction Conditions | Operation in experiment |
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55% | With sodium hydroxide; tetrabutylammomium bromide; In hexane; water; for 5h;Heating / reflux; | To a solution consisting of sodium hydroxide (50 percent in water, 50 g), hexane (50 ml) and tetrabutylamonium bromide (0.7 g) was added 3- ethyl-3-oxetanemethanol (5.0 g, 43.0 mmol) and 1,6-dibromohexane (30 g, 122.9 mmol). This mixture was heated at reflux for 5 h. After cooling to room temperature, the resulting mixture was diluted with water (100 ml) and extracted with ethyl acetate (3 x 100 ml). The extracts were combined and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography, eluting with petrol / ethyl acetate (9 : 1 ), to give a colourless oil (6.65 g, 55percent). 1H NMR (300 MHz, CDCl3) : No. (ppm) 4.44 (d, J = 5.8 Hz, 2H, OCH2), 4.37 (d, J = 5.8 Hz, 2H, OCH@), 3.52 (s, 2H, OCH2), 3.46 (t, J = 6.4 Hz, 2H, OCH@), 3.40 (t, J = 6.8 Hz 2H, BrCH@), 1.35-1.91 (m, 10H, CH2), 0.88 (t, J = 7.5 Hz, 6H, CH3) ; 13C NMR (75 MHz, CDCI3): No. (ppm) 78.5 (OCH2), 73.4 (OCH2), 71.3 (OCH2), 43.4 (quat. ), 33.8 (CH2), 32.7 (CH2), 29.3 (CH2), 27.9 (CH2) 26.8 (CH2), 25.4 (CH2), 8.2 (CH3). MS (m/e): 279 (MH+, 0.1 percent)0281 (MH+ , 0.1 percent), 248 (3), 250 (3), 83 (89), 55 (100), 41 (86) |
60 g | 50 g of 3-ethyloxetanylmethanol and 172 g of sodium hydroxide were added to 500 ml of DMF, The mixture was stirred at 50 °C DEG under a nitrogen atmosphere. Then, 158 g of 1,6-dibromohexane Was added dropwise. After the addition, the mixture was stirred for 6 hours at 80 DEG 50 °C . After cooling to room temperature, 500 ml of water and 500 ml of toluene were added to separate the organic layer. The obtained organic layer was washed with saturated aqueous sodium hydrogencarbonate and water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure. The residue was purified by vacuum distillation, 60 g of a colorless liquid (ex-4) was obtained |
Yield | Reaction Conditions | Operation in experiment |
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With dibutyltin dilaurate; at 60℃; for 4h; | A 500 mL flask was charged with m-tetramethylxylene diisocyanate (24.43 g, 0.1 mol). The reaction vessel was placed under N2 blanket and equipped with an overhead stirrer and condenser. Two drops of dibutyl tin dilaurate were charged to the mixture and the mixture was heated to 60°C. 3-Ethyl-3-(hydroxymethyl) oxetane (23.20 g, 0.2 mol) was placed in the addition funnel. Stirring was continued and the temperature was kept at 60°C by dropwise exothermic addition from the addition funnel over a period of 20 minutes. The reaction was monitored by FT-IR analysis for the consumption of isocyanate (peak at 2258 cm-1). The reaction was completed after four hours. After this interval, the reaction mixture was dissolved into dichloromethane (150 mL). Silica gel (50 g) was added. The organics were filtered and the solvent was removed in vacuo (60°C, 0.3 mm Hg) to afford a white solid with a melting point of 71°C. The NMR for this compound is shown in Figure 1. |
Yield | Reaction Conditions | Operation in experiment |
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With dmap; triethylamine; In dichloromethane; at 0 - 10℃; for 24h; | The initial charge was added to a 500-mL 4-neck round bottom flask: 3-ethyl-3-(hydroxymethyl) oxetane (40 g, 0.344 mol), triethylamine (34.809 g, 0.344 mol), dimethylaminopyridine (4.203 g, 0.034 mol) and dichloromethane (300 mL). The reaction vessel was equipped with an overhead mixer and condenser. Stirring was continued until the mixture became homogeneous. The temperature was kept between 0° and 10°C. 1,3,5-Benzenetricarbonyl trichloride (30.442 g, 0.115 mol) was dissolved into dichloromethane (100 mL) and the mixture was charged to the flask dropwise over a period of one hour. The reaction was monitored by FT-IR analysis for the consumption of carbonyl group in acid chloride (peak at 1801 cm-1) and the formation of ester group in product (peak at 1736 cm-1). The reaction was completed after 24 hours. The reaction mixture was washed with water (5 x 50 mL). The organics were dried over MgSO4, filtered, and the solvent was evaporated off at bath temperature of 50°C. Product was mixed with ethyl acetate (300 mL) and temperature was reduced below -30°C by dry ice. An insoluble white solid (product) precipitated out. Product was filtered and washed with hexane (3 x 30 mL) to afford a white solid with a melting point of 97°C. The NMR for this compound is shown in Figure 4. |
Yield | Reaction Conditions | Operation in experiment |
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With dmap; triethylamine; In dichloromethane; at 0 - 10℃; for 24h; | The initial charge was added to a 500-mL 4-neck round bottom flask: 3-ethyl-3-(hydroxymethyl) oxetane (40 g, 0.344 mol), triethylamine (34.809 g, 0.344 mol), dimethylaminopyridine (4.203 g, 0.034 mol) and dichloromethane (300 mL). The reaction vessel was equipped with an overhead mixer and condenser. Stirring was continued until the mixture became homogeneous. The temperature was kept between 0° and 10°C. Terephthaloyl chloride (35.0 g, 0.172 mol) was dissolved into dichloromethane (100 mL) and the mixture was charged to the flask by dropwise addition over a period of one hour. The reaction was monitored by FT-IR analysis for the consumption of carbonyl group in acid chloride (peak at 1801 cm-1) and the formation of ester group in product (peak at 1736 cm-1). The reaction was completed after 24 hours. The reaction mixture was washed with water (5 x 50 mL). The organics were dried over MgSO4, filtered, and the solvent was evaporated off at bath temperature of 50°C. Product was mixed with ethyl acetate (300 mL) and the temperature was reduced below -30°C by dry ice. An insoluble white solid (product) precipitated out. Product was filtered and washed with hexane (3 x 30 mL) to afford a white solid with a melting point of 79°C. The NMR for this compound is shown in Figure 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With dmap; triethylamine; In dichloromethane; at 0 - 10℃; for 24h; | The initial charge was added to a 500-mL 4-neck round bottom flask: 3-ethyl-3-(hydroxymethyl) oxetane (25.76 g, 0.222 mol), triethylamine (22.464 g, 0.222 mol), dimethylaminopyridine (2.712 g, 0.022 mol) and dichloromethane (180 mL). The reaction vessel was equipped with an overhead mixer and condenser. Stirring was continued until the mixture became homogeneous. The temperature was kept between 0° and 10°C. Azelaoyl chloride (25 g, 0.111 mol) was charged dropwise to the flask over a period of one hour. The reaction was monitored by FT-IR analysis for the consumption of carbonyl group in acid chloride (peak at 1801 cm-1) and the formation of ester group in product (peak at 1736 cm-1). The reaction was completed after 24 hours. The reaction mixture was washed with water (5 x 50 mL). The organics were dried over MgSO4, filtered, and the solvent was evaporated off at bath temperature of 50°C. Product was then dissolved in 50/50 hexane and ethyl acetate mixture (250 mL) and silica gel (8 g) was added. Silica gel was filtered out and the solvent was removed in vacuo (60°C, 0.3 mm Hg) to afford a clear yellow liquid (31 g, 0.081 mol, 67percent) with a viscosity of less than 100 mPa.s at room temperature. The NMR for this compound is shown in Figure 2. |
Yield | Reaction Conditions | Operation in experiment |
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EXAMPLE 5 A: Preparation of 3-ethyl-3-hydroxymethyl oxetane This oxetane was prepared as described by J. B. Pattison, J. Am. Chem. Soc., 79 (1957), p. 3455 and J. V. Crivello et al., J. M. S.-Pure Appl. Chem., A30 (1993), p. 189. Trimethylol propane (1023.6 g, 7.63 moles), diethyl carbonate (901.3 g, 7.63 moles), and potassium hydroxide (0.77 g) were weighed into a 5-l three-neck flask. The reaction mixture was heated to reflux temperature (123° C). After the reaction temperature had been lowered to 105° C., the distilling off of ethanol was started. The reaction temperature was increased to 150° C. On conclusion of the distillation vacuum (15 mbar) was used to remove the remaining ethanol and diethyl carbonate from the reaction mixture. Next, the reaction mixture was heated to 220° C. Gas formation was observed, and under reduced pressure (40 mbar) at 130° C. a clear oil came over which was identified as 3-ethyl-3-hydroxymethyl oxetane. The yield was 698.0 g (79percent); 1H NMR (CDCl3) d (ppm): 0.9 (t, 3H); 1.7 (q, 2H); 3.1 (t, 1H); 3.7 (d, 2H); 4.4 (dd, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; | EXAMPLE 6 A: Preparation of 3-ethyl-3-hydroxymethyl oxetane Trimethylol propane (1489 g, 11.1 moles), dimethyl carbonate (1201 g, 13.3 moles), and potassium hydroxide (5.38 g) were weighed into a 5-l three-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a heating jacket, and a thermometer. The reaction mixture was heated to reflux temperature (86° C.) and kept at reflux for 2 hours. The temperature lowered to 80° C. Subsequently, the temperature of the reaction mixture was increased to 155° C. in 6 hours. On conclusion of the distillation 890 g distillate were obtained containing mostly methanol and dimethyl carbonate in a ratio of 60 to 40. The temperature was lowered to 120° C. and under vacuum (200-40 mbar) the remaining ethanol and dimethyl carbonate was removed from the reaction mixture (about 14 g). Next, the reaction mixture was gradual heated to 180° C. Under a stream of CO2 and reduced pressure (60-40 mbar) a clear oil came over which was identified as 3-ethyl-3-hydroxymethyl oxetane. The yield was 860 g. |
Yield | Reaction Conditions | Operation in experiment |
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With triethylamine; In tetrahydrofuran; water; acryloyl chloride; | EXAMPLE 9 A: Preparation of 3-ethyloxetan-3-yl methyl acrylate The synthesis was carried out as described by P. G. Gassman et al., Chem. Comm., (1989), p. 837. The reaction was carried out under a nitrogen atmosphere. To a mixture of 3-ethyl-3-hydroxymethyl oxetane (170.6 g, 1.50 moles) and triethyl amine (153.8 g, 1.52 moles) in tetrahydrofuran (500 g) cooled in an ice bath acryloyl chloride (137.5 g, 1.52 moles) was added dropwise. The reaction mixture was stirred for one hour at room temperature. To the reaction mixture 500 g of water were added. The organic layer was separated from the aqueous layer. The aqueous layer was extracted with diethyl ether (2*500 ml). The combined organic layers were dried with a saturated NaCl solution and magnesium sulphate. Following filtration of the ether layer the volatile organic compounds were removed under vacuum using a rotary vacuum evaporator. The residue was distilled under vacuum. 3-ethyloxetan-3-yl methyl acrylate was isolated at 122° C./19 mbar as a clear oil. The yield was: 200.4 g, (80percent). 1H NMR (CDCl3) d (ppm): 0.92 (t, 3H); 1.80 (q, 2H); 4.30 (s, 2H); 4.48 (dd, 4H); 5.88 (d, 1H); 6.18 (dd, 1H); 6.45 (d, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium hydroxide; In tetrabutylammomium bromide; water; allyl bromide; | EXAMPLE 2 3-Ethyl-3-allyloxymethyloxetane To a solution of 23.2 g (0.2 mol) of 3-ethyl-3-hydroxymethyloxetane in 48.4 g (0.4 mol) of allylbromide and 50 g of a 50 wt percent aqueous solution of potassium hydroxide in a 300 mL round bottom flask equipped with a magnetic stirrer was added 1.0 g of tetra-n-butylammonium bromide with vigorous stirring at 0° C. After 24 hrs, 100 mL of dichlorometane and 100 mL of water were added to the reaction mixture. The organic phase was washed with water twice, dried over magnesium sulfate, filtered and the solvent removed on a rotary evaporator. The residue was purified by distillation under vacuum, giving 28.6 g of 3-ethyl-3-allyloxymethyloxetane (yield 92percent, b.p.:55° C. at 1.5 mm Hg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; In dichloromethane; | (ii) Nicotinyl chloride hydrochloride (8.9 gm.) was added to a stirred solution of 3-ethyl-3-hydroxymethyloxetane (5.8 gm.) and dry pyridine (20 ml.) in dry dichloromethane (150 ml.) at 0°. The mixture was stirred at room temperature for 4 days and poured into aqueous sodium carbonate solution. The aqueous mixture was extracted with dichloromethane. The extracts were washed with water and dried over anhydrous magnesium sulphate. The solvent was removed in vacuo. The residue was purified by chromatography on silica eluding with 5percent triethylamine in dichloromethane. (3-Ethyloxetan-3-yl)methyl 3-pyridinecarboxylate was obtained as a pale yellow oil (7.0 gm.). Gas liquid chromatography (g.l.c.): OV210 at 170° produced one peak. Nuclear magnetic resonance spectrum (NMR) was as follows: 1 H (p.p.m. from TMS in CDCl3, integral, number of peaks, JHz): 8.20, 1H, m; 7.20, 1H, m; 4.50, 6H, m; 1.80, 2H, m; 1.00, 3H, m. Infrared spectrum (1R) (liquid film); 1735 cm-1. Mass Spectrum: Chemical ionisation M+1 222. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64.7% | With potassium hydroxide; Diethyl carbonate; In ethanol; for 2h;Reflux; | 100g, diethyl carbonate 132g, potassium hydroxide 0.25g, bottle and ethanol 10 ml is added during the reaction. After heating at reflux for 2 hours, under atmospheric pressure, 150 °C by distillation in the greater part of the solvent is removed, a crude product is obtained. Furthermore, in a vacuum distillation is, for the purification of the crude product is obtained. 120 °C and 0.1torr compd. a1 (colorless liquid) is under a pressure, which is collected by the yield 64.7percent. Next, 82g compd. a1,pyridine 111g, and dichlomethane 400 ml bottles which are added to the reaction. The mixture is stirred under nitrogen, then cooled to 5° C -0 °C. 4-bromobenzoyl chloride in 200 ml of dichlomethane soln.of, 0 ° C-5 ° C during the reaction of the drop in the bottle. After completion of the addition, reaction bottle is warmed to room temperature, the stirring time is 8, the bottle 500 ml of water is added during the reaction, which is 5 min. The organic layer is collected, 100 ml of the water layer is extracted using dichlomethane 2 times. The organic layer is collected, in order to adjust the pH value to 7 in about 100 ml of the salt water. Next, an organic layer is collected, 20g is 30 minutes of drying with anhydrous sodium sulfate, then filtered. In order to obtain compd. a2, somas conc. under reduced pressure, the petroleum ether and ethyl acetate (9:1) [...] purified by using a flat, it is further chilled in ethanol recrystallization, 68.7percent yield. The purity of compd. a2 (gas chromatography (GC) analysis by a) is, at 98.109percent, and, the melting point (mp) compd. a2,50.63 ° C-52.56 ° C. |
3-Ethyl-3-hydroxymethyloxetane was prepared from 2,2-dihydroxymethylbutan-1-ol in an analogous manner. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Reference Example 3 (Synthesis of 3-ethyl-3-p-toluenesulfonyloxymethyloxetane) After adding p-toluene sulfonyl chloride (229 g (1.2 mol)), benzyltriethylammonium chloride (17.1 g (75 mmol)) and toluene (450 ml) to a glass flask of an inner volume of 2,000 ml equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, while keeping the liquid temperature below 5°C, a 35percent aqueous sodium hydroxide solution (200 g (1.75 mol)) was gradually added. While keeping the liquid temperature below 10°C, 3-ethyl-3-hydroxymethyloxetane (116.2 g (1.0 mol)) was dropwise added to perform the reaction at the same temperature for 1 hour and at room temperature for 5 hours. After the completion of the reaction, toluene (150 ml) and water (250 ml) were added to a reaction solution and a liquid separation was performed. After washing a resultant organic layer with water (250 ml) twice, a magnesium sulphate was added so that the organic layer was dried. After the completion of drying, the organic layer was filtered and a resultant filtrate was concentrated under reduced pressure to give, as a colorless liquid, 3-ethyl-3-p-toluene sulfonyloxymethyloxetane having a purity of 90percent (a value measured by 1H-NMR) (285 g) (an isolated yield based on 3-ethyl-3-hydroxymethyloxetane standard: 95percent). The physical properties of 3-ethyl-3-p-toluenesulfonyloxymethyloxetane were as follows. CI-MS (m/e); 271 (M+1) 1H-NMR (CDCl3, delta (ppm)); 0.82 (3H, t), 1.74 (2H, q), 2.45 (3H, s), 4.17 (2H, s), 4.29-4.37 (4H, m), 7.35-7.39 (2H, m), 7.79-7.83 (2H, m) | |
90% | With sodium hydroxide;tetramethylammonium bromide; In water; toluene; at 5 - 20℃; for 17.5h; | (Synthesis of 2-(3-oxetanyl)butyltosylate); Into a 2000 ml three-neck flask having a thermometer, a cooler, a stirring device, and a dripping funnel, 190.65 g (1.0 mol) of p-toluene sulfonate chloride, 32.24 g (0.1 mol) of tetramethylammonium bromide, and 400 ml of toluene were poured and cooled to 5°C with stirring in an ice bath. After pouring 116.16 g (1.0 mmol) of 3-ethyl-hydroxymethyloxetane into the three-neck flask, 130 ml of a 35wtpercent sodium hydroxide solution was dripped into the three-neck flask in 30 minutes. After the dripping, stirring was continued for 1 hour at the same temperature and then for 16 hours at a room temperature. After the reaction, 800 ml of water was poured into the flask followed by violent stirring. The mixture was left to stand to separate a water phase from an organic phase. The organic phase was washed with 400 ml of water and then dried with anhydrous magnesium sulfate over night. Then, the magnesium sulfate was removed by filtration, and the filtrate was concentrated. The thus-obtained crude product was separated and purified by silica gel column chromatography (eluting solution: hexane/ethyl acetate) to obtain a desired substance, i.e. 243.3 g (yield: 90percent) of 2-(3-oxetanyl)butyltosylate. |
90% | With sodium hydroxide; tetramethylammonium bromide; In water; toluene; at 5 - 20℃; for 17.5h; | Synthesis of 2-(3-oxetanyl)butyltosylate; Into a 2000 ml three-neck flask having a thermometer, a cooler, a stirring device, and a dripping funnel, 190.65 g (1.0 mol) of p-toluene sulfonate chloride, 32.24 g (0.1 mol) of tetramethylammonium bromide, and 400 ml of toluene were poured and cooled to 5° C. with stirring in an ice bath. After pouring 116.16 g (1.0 mmol) of 3-ethyl-hydroxymethyloxetane into the three-neck flask, 130 ml of a 35 wt percent sodium hydroxide solution was dripped into the three-neck flask in 30 minutes. After the dripping, stirring was continued for 1 hour at the same temperature and then for 16 hours at a room temperature. After the reaction, 800 ml of water was poured into the flask followed by violent stirring. The mixture was left to stand to separate a water phase from an organic phase. The organic phase was washed with 400 ml of water and then dried with anhydrous magnesium sulfate over night. Then, the magnesium sulfate was removed by filtration, and the filtrate was concentrated. The thus-obtained crude product was separated and purified by silica gel column chromatography (eluting solution: hexane/ethyl acetate) to obtain a desired substance, i.e. 243.3 g (yield: 90percent) of 2-(3-oxetanyl)butyltosylate. |
90% | With sodium hydroxide;tetramethylammonium bromide; In water; toluene; at 5 - 20℃; for 17.5h; | Synthesis of 2-(3-oxetanyl)butyltosylate Into a 2000 ml three-neck flask having a thermometer, a cooler, a stirring device, and a dripping funnel, 190.65 g (1.0 mol) of p-toluene sulfonate chloride, 32.24 g (0.1 mol) of tetramethylammonium bromide, and 400 ml of toluene were poured and cooled to 5°C with stirring in an ice bath. After pouring 116.16 g (1.0 mmol) of 3-ethyl-hydroxymethyloxetane into the three-neck flask, 130 ml of a 35wtpercent sodium hydroxide solution was dripped into the three-neck flask in 30 minutes. After the dripping, stirring was continued for 1 hour at the same temperature and then for 16 hours at a room temperature. After the reaction, 800 ml of water was poured into the flask followed by violent stirring. The mixture was left to stand to separate a water phase from an organic phase. The organic phase was washed with 400 ml of water and then dried with anhydrous magnesium sulfate over night. Then, the magnesium sulfate was removed by filtration, and the filtrate was concentrated. The thus-obtained crude product was separated and purified by silica gel column chromatography (eluding solution: hexane/ethyl acetate) to obtain a desired substance, i.e. 243.3 g (yield: 90percent) of 2-(3-oxetanyl)butyltosylate as a colorless liquid. |
With pyridine; In ice-water; | First Stage 116 g of 3-ethyl-3-hydroxymethyloxetane (Toa Gosei's trade name, OXT-101) was added to 500 ml of pyridine, and cooled to 0° C. with stirring. 190 g of p-toluenesulfonyl chloride divided into a few portions was added to it intermittently. Kept at 0° C., this was stirred for 5 hours, and then 1 L of ice-water was poured into the reaction mixture. This was extracted with 500 ml of diethyl ether. The diethyl ether layer was washed with 3percent hydrochloric acid until its pH became acidic, and then washed with saturated sodium carbonate solution and water in this order, and thereafter dried with anhydrous magnesium sulfate. The solvent was evaporated away, and 243 g of 3-[(tosyloxy)methyl]-3-ethyloxetane was obtained. | |
With pyridine; sodium carbonate; In water; | Step 1: 3-ethyl-3-hydroxymethyloxetane (trade name of product, OXT-101.(R)., manufactured by Toa Gosei Co.; 116 g) was added to pyridine (500 mL) and cooled to 0° C. while stirring. p-Toluene sulfonyl chloride (190 g) was added divisionally for several times. After stirring for 5 hours while keeping at 0° C., the reaction mixture was poured to iced water (1 L). It was extracted with diethyl ether (500 mL), the pH was rendered acidic with 3percent hydrochloric acid, and extracts were washed with water. Then, the extracts were washed with a saturated solution of sodium carbonate and water successively and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 3-[(tosyloxy) methyl]3-ethyloxetane (243 g). | |
With dmap; In dichloromethane; at 20℃; for 1h; | EXAMPLE 110a Preparation of intermediate toluene-4-sulfonic acid 3-ethyl-oxetan-3-ylmethyl ester To a mixture of (3-ethyl-oxetan-3-yl)-methanol (11.6 g, 0.1 mol) and DMAP (18.3 g, 0.15 mol) in DCM (100 mL) was added 4-methyl-benzenesulfonyl chloride (19 g, 0.1 mol). The mixture was stirred at room temperature for 1 h, then filtered. The filtrate was washed with HCl aq. (1 M) and water, dried over anhydrous Na2SO4 and concentrated to give the title compound (19 g). | |
With triethylamine;dmap; In dichloromethane; at 20℃; | Step 1: Synthesis of (3-ethyloxetan-3-yl)methyl 4 -methylbenzene sulfonate:To a solution of (3-ethyloxetan-3-yl)methanol (15 g, 0.129 mol) in dichloromethane (300 ml), triethyl amine (144 ml, 1.0344 mol) followed by tosyl chloride (123 g, 0.646 mol) was added at 0°C. After addition of catalytic amount of DMAP (16 g, 0131 mol), the reaction mixture was allowed to stir overnight at room temperature. After completion of the reaction as monitored by TLC, the reaction mixture was washed with water, saturated brine solution; the organic layer was dried over anhydrous Na2S04 and concentrated. The obtained product was purified by column chromatographic technique. Yield: 15 gm. 1H NMR (CDC13, 300 MHz): delta 7.83-7.80 (d, 2H, J = 8.4 Hz); 7.39- 7.36 (d, 2H, J = 8.4 Hz); 4.38-4.36 (d, 2H, J=6.3Hz), 4.31-4.29 (d, 2H, J=6.3Hz), 4.17 (s, 2H), 2.47 (s, 3H), 1.78-1.71 (q, 2H), 0.83-0.78 (t, 3H). | |
186 g | With pyridine; In toluene; at 20℃; for 16h;Inert atmosphere; | 100 g of 3-ethyl-3-oxetanylmethanol and 100 g of pyridine were added to 400 ml of toluene, And the mixture was stirred under cooling in a nitrogen atmosphere. Thereto, 197 g of p-toluenesulfonic acid chloride (TsCl) was added. After the addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate The filtrate was separated, and the filtrate was washed with saturated aqueous sodium bicarbonate and water. Water (400 ml) was added to the obtained organic layer, followed by stirring at 40 for 2 hours. The organic layer was separated, The obtained organic layer was washed with saturated aqueous sodium bicarbonate and water, And dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure. The obtained residue was dried under reduced pressure to obtain 186 g of a colorless liquid (ex-1). |
334.6 g | With benzyltrimethylammonium chloride; sodium hydroxide; In water; toluene; at 4 - 7℃; for 5.5h; | A thermometer, a stirrer, a dropping funnel,152 g (1.30 mol) of 3-ethyl-3-hydroxymethyloxetane,1143.8 g of toluene, 275 g of a 35percent sodium hydroxide aqueous solution(2.41 mol as sodium hydroxide),14.9 g (0.08 mol) of benzyltrimethylammonium chloride was charged,While maintaining the internal temperature at 4 to 7 ° C,280 g (1.50 mol) of p-toluenesulfonyl chloride was added at a rate of 22 g / 10 min.After completion of the addition, the reaction was allowed to proceed for 5.5 hours while keeping at 4 to 5 ° C.Next, water was added to the reaction completion liquid obtained,After stirring to separate the aqueous layer,By distilling toluene from the organic layer by distillation under reduced pressure,334.6 g of bottoms liquid was obtained, purity 97.9percent(3-ethyloxetane-3-yl) methyl p-toluenesulfonate having a molecular weight distribution (gel permeation chromatography analysis, areapercent).167.3 g of N-methylpyrrolidone was added to the obtained bottom liquid to prepare a solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In accordance with Scheme 1 below, an acrylic compound having an oxetanyl group (acrylic compound 1) was synthesized using 3-ethyl-3-hydroxymethyloxetane (OXT-101, manufactured by Toagosei Co., Ltd.). The 1H-NMR spectrum of the acrylic compound 1 is shown in Fig. 1. "x" in the figures indicates the peak of the impurities. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Reference Example 2 (Synthesis of 3-ethyl-3-chloromethyloxetane) After adding 3-ethyl-3-hydroxymethyloxetane (58.0 g (0.5 mol)), acetonitrile (300 ml) and triethylamine (61.0 g (0.60 mol)) to a glass flask having an inner volume of 1,000 ml equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, while keeping liquid temperature at about 0°C, methanesulfonyl chloride (63 g (0.55 mol)) was gradually added to react at the same temperature for 3 hours with stirring. After the temperature was raised to room temperature, methanol (200 ml) was added and the reaction was further performed at 50°C for 5 hours. After the completion of the reaction, a reaction solution was concentrated, ethyl acetate (200 ml) and water (100 ml) were added to a concentrate, and a liquid separation was performed. Subsequently after ethyl acetate (100 ml) was added an aqueous layer to perform the extraction, an extract was combined together with a previously extracted organic layer, and the mixture liquid was washed with water (100 ml). A resultant organic layer was concentrated under reduced pressure, and lithium chloride (23.2 g (0.55 mol)) and methanol (200 ml) were added to perform the reaction at room temperature for 5 hours and at 60°C for 6 hours with stirring. After the completion of the reaction, the mixture was cooled to room temperature and a generated salt was filtered. A resultant filtrate was concentrated under reduced pressure, ethyl acetate (200 ml) and water (100 ml) were added to a concentrate, and a liquid separation was performed. Subsequently after ethyl acetate (100 ml) was added to an aqueous layer to perform an extraction, an extract was combined together with a previously extracted organic layer, and the mixture liquid was washed with water (100 ml). A resultant organic layer was distilled under reduced pressure (3.5 kPa, 79-80°C) to give, as a colorless liquid, 3-ethyl-3-chloromethyloxetane having a purity of 99.6percent (an analysis value by a gas chromatography) (44.2g) (an isolated yield based on 3-ethyl-3-hydroxymethyloxetane: 65percent). The physical properties of 3-ethyl-3-chloromethyloxetane were as follows. CI-MS(m/e); 135 (M+1) 1H-NMR (CDCl3, delta (ppm)); 0.90 (3H, t), 1.85 (2H, q), 3.79 (2H, s), 4.42 (4H, s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With tetrabutoxytitanium; for 1.5h;Heating / reflux; | Example 9. To a solution of 3-ethyl-3-hydroxymethyl-oxetane (UBE Industries, 116.2 g, 1 mol) and ethyl-2-cyanoacetate (149 g, 1.3 mol) in a 500 mL one necked flask was added titanium (IV) butylate (Ti(O11Bu)4, 0.7 g, 2 mmol) . The mixture was refluxed for a period of time of 1.5 hours, and then distilled under a 10 mBar vacuum. The resulting orange residue was taken up in dichloromethane (200 mLs) and washed with deionised water (2 x 100 mLs) . The organic layer was dried over sodium sulphate and distilled at a temperature of 150-1550C and pressure of 0.2 mBar to furnish 92 grams of 3- ethyl-3-oxetanylmethyl-2-cyanoacetate, Hl in a yield of 50percent. 60 MHz 1H NMR (ppm, CDCl3 containing 0.1percent TMS internal standard) 4.42 - 4.35 (overlapped, 6H), 3.50 (2H), 1.72 (q) 2H, 0.93 (t) 3H; IR (cm-1) 2965.2, 2877.1, 2261.9, 1744.3, 1460.0, 1397.4, 1336.6, 1259.7, 1178.4, 1004.3, 976.3, 826.9, 787.5, 739.7; GC-MS: 68 m/z, (100percent), 41, 53, 57, 86. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3-Ethyl-3-oxetane methanol (27.03 g, 0.2326 mole), toluene (100 ml), tetrabutyl ammonium hydrogen sulfate (17.38 g, 0.0512 mole) and 50percent sodium hydroxide solution (300 ml) were combined in a 1L 4-neck round bottom flask equipped with a condenser, mechanical mixer and oil bath. The mixture was stirred vigorously and the oil bath was heated to 90 C. at which temperature the solids were totally dissolved. Cinnamyl chloride (35.50 g, 0.2326 mole) was added over approximately 35 minutes. The reaction was heated at 90 C. with mixing for an additional 1.25 hour and then allowed to cool to room temperature. The organic phase was isolated in a separatory funnel and washed four times with 20percent sodium chloride solution (200 ml each). As a result, the washes changed from cloudy yellow to hazy colorless and the pH of the washes dropped from 12 to 6. The last of four more washes (200 ml) using distilled water was an emulsion, which separated over night. After the emulsion separated, a clear orange organic fraction was collected and mixed for one hour with silica gel (60 g). Solids were then filtered out, and the reaction solution was stripped of toluene in vocuo resulting in a clear orange liquid with a viscosity of <100 cPs at 25 C., and a volatility of 93percent at 200 C. as measured by thermogravimetric analysis (TGA). H1 NMR: 7.15-7.51 (m, 5H), 6.12-6.25 (d, 1H), 6.30-6.42 (m, 1H), 4.51-4.71 (d, 2H), 4.41-4.51 (d, 2H), 4.15-4.25 (d, 2H), 3.65 (s, 2H), 1.85-1.90 (m, 2H), 1.85-1.95 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Step 6.2 : 3-(6-f2 2'] bithiophenvl-5-yl-hexvioxymethvl)-3-ethvl-oxetane; 3-Ethyl-3-oxtanemethanol (3.10 g, 26.72 mmol) is added slowly to a suspension of sodium hydride (60 percent dispersion in mineral oil, 1.07 g, 26.72 mmol) in DMF (70 ml) at 0 °C, with stirring, under nitrogen. After complete addition, the ice-bath is removed and the mixture is stirred another 20 min, followed by the addition of 5- (6-chlorohexyl)-2, 2'- bithiophene (7.61 g, 26.72 mmol). The resultant mixture is stirred overnight, then water (100 ml) is added and the mixture extracted with ethyl acetate (3 x 70 ml). The combined extracts are washed with water and brine, then dried (Na2SO4) and evaporated under reduced pressure. The residue is purified by column chromatography, eluting with petroleum ether/ethyl acetate (100: 0 to 9: 1), to give 3- (6- [2, 2'] bithiophenyl-5-yl-hexyloxymethyl)-3-ethyl-oxetane as a brown oil (6.34 g, 65 percent). H NMR (300 MHz, CDCl3) : No. (ppm) 7.15 (dd, J = 5.0 Hz, 1.1 Hz, 1H, Ar-H), 7.05 (dd, J = 3. 6 Hz, 1.1 Hz, 1H, Ar-H), 6.92 (m, 2H, Ar-H), 6.62 (d, J = 3.4 Hz, 1 H, Ar-H), 4.40 (d, J = 5.9 Hz, 2H, OCH2), 4.32 (d, J = 5.9 Hz, 2H, OCH2), 3.45 (s, 2H, OCH2), 3. 38 (t, J = 6.4 Hz, 2H, OCH2), 2.73 (t, J = 7.6 Hz 2H, ArCH2), 1.32-1. 73 (m, 10H, CH2), 0.84 (t, J = 7.5 Hz, 6H, CH3) ; 13C NMR (75 MHz, Ceci3) : 8 (ppm) 144.9 (quat. ), 137.9 (quat. ), 134.8 (quat. ), 127.7 (CH), 124.8 (CH), 123.6 (CH), 123.3 (CH), 122.9 (CH), 78.4 (OCH2), 73.4 (OCH2), 71.4 (OCH2), 43.4 (quat. ), 31.6 (CH2), 30.1 (CH2), 29.5 (CH2), 28.9 (CH2), 26.8 (CH2) 26.0 (CH2), 8.2 (CH3). 364 (M+, 13 percent) 205 (11), 179 (100). | |
65% | 3-Ethyl-3-oxtanemethanol (3.10 g, 26.72 mmol) was added slowly to a suspension of sodium hydride (60 percent dispersion in mineral oil, 1.07 g, 26.72 mmol) in DMF (70 ml) at 0 °C, with stirring, under nitrogen. After complete addition, the ice-bath was removed and the mixture was stirred another 20 min, followed by the addition of 5-(6- chlorohexyl)-2,2'-bithiophene (7.61 g, 26.72 mmol). The resultant mixture was stirred overnight, then water (100 ml) was added and the mixture extracted with ethyl acetate (3 x 70 ml). The combined extracts were washed with water and brine, then dried (Na2S04) and evaporated under reduced pressure. The residue was purified by column chromatography, eluting with petroleum ether/ethyl acetate (100 : 0 to 9: 1), to give 3- (6-[2,2']bithiophenyl-5-yl-hexyloxymethyl) - 3-ethyl-oxetane as a brown oil (6.34 g, 65 percent). 1H NMR (300 MHz, CDC13): No. (ppm) 7.15 (dd, J = 5.0 Hz, 1.1 Hz, 1 H, Ar-H), 7.05 (dd, J = 3.6 Hz, 1.1 Hz, 1 H, Ar-H), 6.92 (m, 2H, Ar-H), 6.62 (d, J = 3.4 Hz, 1 H, Ar-H), 4.40 (d, J = 5.9 Hz, 2H, OCH@), 4.32 (d, J = 5.9 Hz, 2H, OCH2), 3.45 (s, 2H, OCH2), 3.38 (t, J = 6.4 Hz, 2H, OCH@), 2.73 (t, J = 7.6 Hz 2H, ArCH@), 1.32-1.73 (m, 10H, CH2), 0.84 (t, J = 7.5 Hz, 6H, CH3); 13C NMR (75 MHz, CDCl3) : No. (ppm) 144.9 (quat.), 137.9 (quat.), 134.8 (quat.), 127.7 (CH), 124.8 (CH), 123.6 (CH), 123.3 (CH), 122.9 (CH), 78.4 (OCH2), 73.4 (OCH2), 71.4 (OCH2), 43.4 (quat.), 31.6 (CH2), 30.1 (CH2), 29.5 (CH@), 28.9 (CH2), 26.8 (CH2) 26.0 (CH2), 8.2 (CH3). 364 (M+, 13 percent), 205 (11 ), 179 (100) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | 3-Ethyl-3-oxtanemethanol (10.0 g, 86.08 mmol) was added slowly to a suspension of sodium hydride (60 % dispersion in mineral oil, 3.44 g, 86.0 mmol) in DMF (150 ml) at 0 C, with stirring, under nitrogen. After complete addition, the ice-bath was removed and the mixture was stirred another 20 min, followed by the addition of 2-(6- chlorohexyl) thophene (16.22 g, 80.0 mmol). The resultant mixture was stirred overnight, then water (200 ml) was added and the mixture extracted with ethyl acetate (3 x 100 ml). The combined extracts were washed with water and brine, then dried (Na2S04) and evaporated under reduced pressure. The residue was purified by column chromatography, eluting with petroleum ether/ethyl acetate (10: 0 to 9: 1), to afford the product as a brown oil (13.74 g, 61 %). ¹H NMR (300 MHz, CDC13): 8 (ppm) 7.07 (dd, J = 5.1 Hz, 1.1 Hz, 1 H, Ar-H), 6.88 (dd, J = 5.0 Hz, 3.4 Hz, 1 H, Ar-H), 6.76 (m, 1 H, Ar-H), 4.43 (d, J = 5.8 Hz, 2H, OCH2), 4.36 (d, J = 5.8 Hz, 2H, OCH@), 3.50 (s, 2H, OCH2), 3.43 (t, J = 6.4 Hz, 2H, OCH2), 2.81 (t, J = 7.6 Hz 2H, ArCH2), 1.37-1.77 (m, 10H, CH2), 0.87 (t, J = 7.6 Hz, 6H, CH3); ¹³C NMR (75 MHz, CDC13): No. (ppm) 145.6 (quat. ), 126.6 (CH), 123.9 (CH), 122.7 (CH), 78.5 (OCH2), 73.4 (OCH2), 71.5 (OCH2), 43.4 (quat. ), 31.8 (CH2), 29.8 (CH2), 29.5 (CH2), 28.9 (CH2), 26.8 (CH2) 25.9 (CH2), 8.2 (CH3); MS (m/e): 282 (M+, 2 %), 166 (8), 123 (39), 110 (22), 97 (100) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.4% | With Jones reagent; In acetone; at 0 - 20℃; for 6h; | The synthesis was performed with reference to the document [2-4].46 mL (1.5 eq) of Jones reagent and 300 mL of acetone were added to a 500 mL eggplant flask and stirred at 0 ° C. to this,3-ethyl-3-hydroxymethyloxetane (EHO)A mixture of 5.56 g (24 mmol) and 100 mL of acetone was added dropwise over 5 h, followed by stirring at room temperature for 1 h.After completion of the reaction, 5 mL of isopropyl alcohol was added at 0 ° C. to stop the reaction. The resulting mixture is filtered under reduced pressure,After that, natural filtration was performed with Celite. next,The filtrate obtained was subjected to removal of acetone and isopropyl alcohol under reduced pressure using a rotary evaporator.After adding aqueous NaOH solution to the remaining liquid to adjust to pH 11,Washing was carried out three times with dichloromethane.The aqueous layer was adjusted to pH 1 by adding H 2 SO 4, extraction was performed with dichloromethane, and the organic layer was subjected to dehydration treatment with anhydrous magnesium sulfate.Then, after removing the solvent under reduced pressure,A colorless and transparent liquid was obtained. The yield is 3.137 g,The yield was 50.4percent. |
Tags: 3047-32-3 synthesis path| 3047-32-3 SDS| 3047-32-3 COA| 3047-32-3 purity| 3047-32-3 application| 3047-32-3 NMR| 3047-32-3 COA| 3047-32-3 structure
[ 15833-61-1 ]
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H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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