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CAS No. : | 2211-94-1 | MDL No. : | MFCD00005135 |
Formula : | C10H12O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AVWGFHZLPMLKBL-UHFFFAOYSA-N |
M.W : | 180.20 | Pubchem ID : | 16646 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P201-P202-P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P308+P313-P312-P332+P313-P337+P313-P362-P403+P233-P405-P501 | UN#: | N/A |
Hazard Statements: | H315-H319-H335-H341 | 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 |
---|---|---|
97.3% | Stage #1: 4-methoxy-phenol With potassium carbonate In acetone at 20℃; for 0.5h; Stage #2: 3-chloro-1,2-epoxypropane In acetone at 60 - 65℃; for 72h; | 1.A [Example 1] Synthesis of Diacylglycerol Lactone Compound (EC-A129) A. As shown in Reaction 1a below, 50 g (402.77 mmole) of 4-methoxyphenol was dissolved in 1500 ml of acetone. Then, 278 g (2013.8 mmole) of K2CO3 was added and stirred at room temperature for 30 minutes. 126 ml (1611.1 mmole) of epichlorohydrin was added to the 4-methoxyphenol solution, the temperature was raised to 60 to 65° C., and refluxed for 72 hours. The reaction was confirmed by TLC (ethylacetate(EA):hexane(Hex)=1:9). When the reaction was completed, the reaction solution was filtered by a celite filter, the filtrate was concentrated. The concentrate was purified with a flash column (eluent:ethyl acetate(EA):hexane(Hex)=1:10 (volume ratio) mixture) to obtain 68 g of the target compound (yield: 97.3%) |
93.7% | Stage #1: 4-methoxy-phenol With potassium carbonate In acetone at 20℃; for 0.5h; Stage #2: 3-chloro-1,2-epoxypropane at 60 - 65℃; for 72h; | 1.1a Reaction 1a As shown in the above Reaction 1a, after dissolving 50 g (402.77 mmole) of 4- methyoxyphenol in 1500 ml of acetone, 278 g (2013.8 mmole) of K2CO3 was added to the mixture and stirred at room temperature for 30 minutes. 126 ml (1611.1 mmole) of epichlorohydrin was added to that 4-methyoxyphenol mixture solution and refluxed at a temperature of 60 to 65 C for 72 hours. The reaction was monitored by TLC(EA:Hex=1:9). When the reaction was completed, the reaction mixture was filtered by Celite filter and concentrated. The concentrate was purified by flash column chromatography using mixed solution of (EA:Hex) = 1:10 (volume ratio) to afford 69 g of the target compound at yield of 93.7%. |
78% | With sodium hydroxide In water monomer at 82 - 85℃; for 3h; |
77% | Stage #1: 4-methoxy-phenol With tetrabutylammonium bromide; sodium hydroxide In water monomer at 20℃; for 0.333333h; Stage #2: 3-chloro-1,2-epoxypropane In water monomer at 20℃; for 9.5h; | 2-(Phenoxymethyl)oxirane (6). General procedure: To a stirred solution of phenol (1 g, 10.62 mmol) in 15 ml ethanol was added NaOH (510 mg, 12.74 mmol). After stirring for 20 min at RT, epichlorohydrin (3.33 mL, 42.5 mmol) was added dropwise for 30 min. The resulting mixture was stirred at RT for 9h. After completion of reaction, solvent was removed under reduced pressure, added water (20 mL) and extracted twice with EtOAc. The organic phases were combined and washed with water, brine, dried over Na2SO4, concentrated to give crude product. Crude product was purified by column chromatography using EtOAc/pet ether (1 : 9) on silica gel to afford 6 as a colorless oil (1.12 g, 70% yield) |
76.5% | With tetrabutylammonium hydrogensulfate; sodium hydroxide at 0 - 20℃; for 18h; | To 1.3 ml of NaOH (50%) was added 4- methoxyphenol (500 mg, 4.03 mmol), (R-C4Hg)4N+HSO4" (54 mg, 0.16 mmol) and 2- (chloromethyl) oxirane (1.26 ml, 16.13 mmol) in portions at 0 0C. The reaction mixture was stirred overnight (about 18 hours) at room temperature. Then, IN NaOH was added and the solution was extracted with dichloromethane, combined the organic layers, dried with anhydrous Na2SO4, concentrated under vacuum. The residue was purified via column chromatography to obtain 555 mg of the desired product as yellow oil (yield: 76.5%) . |
73% | With potassium carbonate at 120℃; for 4.5h; | |
48% | With sodium hydroxide In water monomer at 100℃; for 3h; | 1A IA) 2- [ (4-methoxyphenoxy) methyl] oxiraneA solution of NaOH (0.35 g) in 10 mL of water was added to a mixture of 4-methoxyphenol (1.10 g, 8.5 mmol) and epichlorohydrin (0.80 mL, 10.2 mmol) . The mixture was heated at 100 °C for 3 h. After cooling, the mixture is taken up with AcOEt (50 mL) . The organic phase was separated, washed with brine, dried over a2S04 and evaporated under reduced pressure. The crude residue was chromatographed (Petroleum ether/AcOEt, 4:1, as eluent) to afford pure compound in 48% yield. 1 NMR (CDC13) : δ 2.73-2.75 (m, 1H) , 2.89 (app t, 1H) , 3.31-3.36 (m, 1H) , 3.76 (s, 3H) , 3.88-3.93 (m, 1H) , 4.14-4.20 (m, 1H) , 6.81- 6.88 (m, 4H) . |
48% | With sodium hydroxide In water monomer at 100℃; for 3h; | 1.A 1A) 2-[(4-methoxyphenoxy)methyl]oxirane 1A) 2-[(4-methoxyphenoxy)methyl]oxirane A solution of NaOH (0.35 g) in 10 mL of water was added to a mixture of 4-methoxyphenol (1.10 g, 8.5 mmol) and epichlorohydrin (0.80 mL, 10.2 mmol). The mixture was heated at 100° C. for 3 h. After cooling, the mixture is taken up with AcOEt (50 mL). The organic phase was separated, washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude residue was chromatographed (Petroleum ether/AcOEt, 4:1, as eluent) to afford pure compound in 48% yield. 1H NMR (CDCl3): δ 2.73-2.75 (m, 1H), 2.89 (app t, 1H), 3.31-3.36 (m, 1H), 3.76 (s, 3H), 3.88-3.93 (m, 1H), 4.14-4.20 (m, 1H), 6.81-6.88 (m, 4H). |
46% | With potassium carbonate In acetonitrile at 70℃; for 24h; Inert atmosphere; | |
With sodium hydroxide | ||
With sodium hydroxide 1.) 80 deg C, 2.) 4 h; Yield given. Multistep reaction; | ||
With sodium hydroxide In water monomer | ||
With sodium hydroxide; anhydrous tetramethylammonium chloride 1.) RT, 7 d, 2.) H2O, Et2O, RT, 7 h; Yield given. Multistep reaction; | ||
With potassium carbonate In acetonitrile Heating; | ||
Stage #1: 4-methoxy-phenol With sodium hydride In N,N-dimethyl-formamide Stage #2: 3-chloro-1,2-epoxypropane In N,N-dimethyl-formamide | ||
With sodium hydroxide at 20℃; for 12h; | ||
With potassium carbonate In butanone Heating; | ||
With sodium hydroxide In water monomer at 100℃; for 3h; | ||
With tetrabutylammonium hydrogensulfate; sodium hydroxide In water monomer | ||
With sodium hydroxide Reflux; | ||
With potassium carbonate In acetone for 24h; Inert atmosphere; Reflux; | General method for synthesis of glycidyl ethers: General procedure: An oven dried 250 mL round bottom flask containing dry acetone (88 mL) was charged with target phenol (8.83 mmol, 1 equiv) and ground potassium carbonate (17.6 mmol, 2 equiv) under N2 and stirring. Epichlorohydrin (26.5 mmol, 3 equiv) was then ran in and the solution was heated under reflux for 24 h or until consumption of the phenol was visualized by TLC. Upon completion, the resulting solution was filtered and volatiles removed by rotary evaporation. The residue was loaded directly onto a silica gel column for purification. | |
Stage #1: 4-methoxy-phenol With sodium hydroxide In ethanol at 20℃; for 0.333333h; Stage #2: 3-chloro-1,2-epoxypropane In ethanol at 20℃; for 24h; | ||
With sodium hydroxide In water monomer at 50℃; for 6h; | ||
With potassium carbonate In acetone at 80℃; Sealed tube; | Typical procedure for the preparation of 1-13 General procedure: K2CO3 (4 mmol), epichlorohydrin (2 mmol), and the corresponding phenol (1 mmol) were mixed in a flask and then acetone (10 mL) was added as solvent. The suspension was reflux overnight at 80 °C. Then the mixture was filtrated with celite and the filtrate was concentrated under reduced pressure. The residue was purified by chromatograph on silica gel (petroleum ether/acetone = 100/1, v/v) to give compound 1-13. These products were consistent with the standard spectra reported in the literature [1]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With thiourea In methanol for 0.25h; Molecular sieve; Reflux; | |
98% | With CuFe2O4/Mg(OH)2; thiourea In water at 20℃; for 3.7h; Green chemistry; | 4.4. Conversion of epoxides to thiiranes using thiourea catalyzed by CuFe2O4/Mg(OH)2 nanocomposite: a general procedure General procedure: In a round-bottomed flask equipped with amagnetic stirrer, a mixture of epoxide (1mmol), thiourea (0.47 g, 3mmol) and CuFe2O4/Mg(OH)2 nanoparticles (0.05 g, 0.17mmol) in H2O (2mL) was prepared and stirred at room temperature for 1-3.5 h. The progress of the reaction was monitored by TLC using n-hexane: EtOAc (10:4) as an eluent. After completion of the reaction, CuFe2O4/Mg(OH)2 nanoparticles were recovered with an external magnet, washed with ethyl acetate, and used for subsequent cycles after drying under vacuum. The reaction mixture was extracted by CH2Cl2 (3×5mL) and then dried over anhydrous Na2SO4. The organic solvent was evaporated to give crude thiirane for further purification by a short-column chromatography over silicagel (70-99% yield) (Table 2). All products are known compounds and were characterized by comparison of their spectra ((FT-IR, 1H NMR and 13C NMR)) with those of valid samples; [34,51] these data are presented in the supplementary information (http://dx.doi.org/10.1080/17415993.2019.1567728). |
96% | With thiourea on CaCO3 at 60 - 70℃; for 0.2h; neat (no solvent); |
95% | With alumina immobilized thiourea In neat (no solvent) at 20℃; for 0.0666667h; Green chemistry; | Solvent-free conversion of epoxides to thiiranes withalumina immobilized thiourea, general procedure General procedure: A mixture of epoxide (1 mmol) and alumina immobilized thiourea (0.752 g, 25% w/w) was ground in amortar for 2-9 min at room temperature without a solvent. The progress of the reaction was monitored by TLC using n-hexane:EtOAc (5:2) as an eluent. After completion of the reaction, the mixture was washed with EtOAc (3 × 5 mL). The combined washing solvents were evaporated under reduced pressure to give the crude thiirane for further purification by a short-column chromatography over silica gel (83-98% yield) |
95% | With copper(II) ferrite; thiourea In ethanol for 0.583333h; Reflux; Green chemistry; | 4.3. Conversion of epoxides to thiiranes using thiourea in the presence of nanoCuFe2O4: a general procedure General procedure: 4.3. Conversion of epoxides to thiiranes using thiourea in the presence of nanoCuFe2O4: a general procedure In a round-bottomed ask (25 mL) equipped with a magnetic stirrer and condenser, a solu-tion of the epoxide (1 mmol) and thiourea (0.076 g, 1 mmol) in EtOH (3 mL) was prepared.Nano CuFe2O4 (0.05 mmol) was then added to the resulting solution and the reaction mix-ture was stirred magnetically under reux condition for 34-45 min. The progress of thereaction was monitored by TLC. After completion of the reaction, EtOH was evaporatedand EtOAc (2 5 mL) was added to the reaction mixture followed by stirring for 5 min.In order to separate the catalyst, a magnet was externally appended to the ask, and themagnetic nano CuFe2O4 was accumulated at the walls of the ask. Then, the mixture was filtered and the organic layer was washed with water (20 mL) and dried over anhydrousNa2SO4. The organic solvent was evaporated to give crude thiirane for further puricationby a short-column chromatography over silica gel (80-95% yield) (Table 2). The collectednano CuFe2O4 was washed with ethanol, then with water and nally dried and preserved for the next run. All products are known compounds and were identied by comparison of their properties (FT-IR, 1HNMRand13C NMR) with those of authentic samples[10,12,13,22]; these data were given in the Supporting information. |
94% | With potassium thioacyanate In various solvent(s) at 20℃; for 0.75h; | |
94% | With potassium thioacyanate; β‐cyclodextrin In water; acetone at 20℃; for 3.5h; | |
94% | With ammonium thiocyanate at 20℃; for 0.5h; neat (no solvent); | |
93% | With iodine; ammonium thiocyanate In acetonitrile at 20℃; for 2.5h; | |
92% | With potassium thioacyanate; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate In water at 20℃; for 3h; | |
91% | With thiourea; β‐cyclodextrin In water; acetone at 20℃; for 4h; | |
90% | With ammonium thiocyanate In water for 0.166667h; Microwave irradiation; | |
90% | With (x)H2O*Fe2NiO4; ammonium thiocyanate In neat (no solvent) at 60℃; for 0.316667h; Green chemistry; | 4.3. Conversion of epoxides to thiiranes using ammonium thiocyanate in the presence of nano-MFe2O4 (M = Mg, Ni) under solvent-free conditions 4.3.1. A general procedure General procedure: An experimental tube containing a mixture of an epoxide (1 mmol), ammonium thiocyanate (0.076 g, 1mmol), and nano-MFe2O4 (M = Mg, Ni) (0.05 mmol) was placed in an oil bath at 60°C for an appropriate time as mentioned in Table 3. The progress ofthe reaction was monitored by TLC. After completion of the reaction, the reaction mixture was cooled at room temperature and poured into water while stirring, and then ethyl acetate was added for extraction (3×5mL). MFe2O4 nanoparticles were recovered with an external magnet, washed with ethyl acetate, and used for subsequent cycles after drying under vacuum. Pure thiiranes were obtained by the evaporation of the solvent, followed by column chromatography over silica gel. All products are known compounds and were identified by comparison of their properties (FT-IR, 1H NMR, and 13C NMR) with those of authentic samples [5,6,8,37]. The spectral data are given in the Supplementary information. |
78% | With potassium thioacyanate In acetonitrile at 20℃; for 0.75h; | |
68% | With water; potassium thioacyanate; silica gel In toluene at 90℃; for 19h; | |
60% | With potassium thioacyanate In water at 40℃; for 24h; | |
60% | With potassium thioacyanate In water at 40℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With acetic acid; lithium chloride In tetrahydrofuran for 18h; Ambient temperature; | |
98% | With hydrogenchloride; β‐cyclodextrin In methanol; water; acetone at 20℃; for 12h; | |
98% | With pivaloyl chloride In water at 20℃; for 6h; regioselective reaction; |
92% | With oxygen; trichloroacetonitrile; copper dichloride In water; N,N-dimethyl-formamide at 25℃; for 1h; Irradiation; | General Procedure for the Halohydrin Synthesis General procedure: To an oven-dried test tube equipped with a stir bar was added epoxide 1 (0.20 mmol, 1.0 equiv), CuCl2(2.7 mg, 0.02 mmol, 10 mol %), a 99:1 mixture of DMF/H2O (v/v, 2.0 mL, 0.1 M), and trichloroacetonitrile(60 L, 0.60 mmol, 3.0 equiv). The atmosphere was replaced with oxygen (x 3) using a diaphragm pump. Themixture was then placed 0.2 cm from a Kessil A160WE TUNA BLUE at maximum blue/brightness, andirradiated with continuous fan cooling. After stirring at 25 °C for 1 h, the mixture was treated with H2O (3mL). The aqueous layer was extracted with Et2O (5 mL x 3). The organic layers were combined, washed withH2O (15 mL x 2), dried over Na2SO4, filtered, and concentrated. Flash column chromatography (SiO2: 8 g)yielded halohydrin 2. |
90% | Stage #1: 2,3-epoxypropyl p-methoxyphenyl ether With β‐cyclodextrin In water; acetone at 60℃; Stage #2: With thionyl chloride In water; acetone at 20℃; for 10h; | |
89% | With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; lithium chloride at 65℃; for 3h; | |
81% | With C25H21OP; trichloroacetonitrile In water; N,N-dimethyl-formamide at 25℃; for 6h; Inert atmosphere; Irradiation; | |
78% | With 1-(carboxymethyl)-3-methylimidazolium chloride at 60 - 65℃; for 1.8h; | |
77% | With sodium chlorodifluoroacetate In N,N-dimethyl-formamide for 1h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With morpholine-borane; boron trifluoride diethyl etherate In diethyl ether for 2h; Ambient temperature; | |
97% | With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); potassium <i>tert</i>-butylate; hydrogen In toluene at 75℃; for 24h; regioselective reaction; | |
87% | With lithium aluminium tetrahydride In tetrahydrofuran for 5h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With perchloric acid In water at 80℃; | |
43% | With TEA; potassium carbonate at 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With acetic acid; lithium bromide In tetrahydrofuran for 36h; Ambient temperature; | |
98% | With pivaloyl bromide In water at 20℃; for 6h; regioselective reaction; | |
92% | With hydrogen bromide; β‐cyclodextrin In methanol; water; acetone at 20℃; for 12h; |
90% | With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; lithium bromide at 20℃; for 2.5h; | |
75% | With allyltin tribromide; <i>L</i>-proline In tetrahydrofuran at 20℃; for 10h; Reflux; regioselective reaction; | |
75% | With (2S)-1-benzyl-2-(hydroxydiphenylmethyl)pyrrolidine 1-oxide; allyltin tribromide In dichloromethane at 20℃; for 4h; Reflux; regioselective reaction; | |
87 % Chromat. | With C21H21N3O4S; bromine In dichloromethane at 20℃; for 0.75h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With acetic acid; lithium iodide In tetrahydrofuran for 0.25h; Ambient temperature; | |
98% | With 2,2-Dimethylpropanoyl iodide In water at 20℃; for 6h; regioselective reaction; | |
92% | With 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; lithium iodide at 20℃; for 2h; |
90% | With hydrogen iodide; β‐cyclodextrin In methanol; water; acetone at 20℃; for 12h; | |
80% | With 1-(carboxymethyl)-3-methyl-1H-imidazol-3-ium iodide at 60 - 65℃; for 1.6h; | |
80 % Chromat. | With C21H21N3O4S; iodine In dichloromethane at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 20h; Ambient temperature; | |
69% | With dihydrogen peroxide In methanol; water; acetonitrile at 40℃; for 90h; chemoselective reaction; | |
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 45℃; for 48h; |
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium hydride; In N,N-dimethyl-formamide; at 0 - 20℃; | General procedure: To a suspension of NaH (1.1 mmol) in anhydrous DMF, cooled at 0 C, a solution of 4-methoxyphenol (0.19 g, 1.5 mmol) and (R)-or (S) glycidol nosylate (0.41 g, 1.5 mmol) in the same solvent was added dropwise. The reaction mixture was stirred at room temperature overnight, quenched with H2O and extracted with AcOEt (3 × 20 mL). The organic layers were collected, dried over Na2SO4 and concentrated under reduced pressure. The crude was purified on a silica gel column (n-hexane/AcOEt, 7:3 as eluent) to give pure compound as a white semisolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: benzylic alcohol With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 2,3-epoxypropyl p-methoxyphenyl ether In N,N-dimethyl-formamide at 80℃; for 4h; | |
78.3% | Stage #1: benzylic alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Stage #2: 2,3-epoxypropyl p-methoxyphenyl ether In N,N-dimethyl-formamide; mineral oil at 80℃; for 3h; | 1.B B. As shown in Reaction 1b below, 0.73 ml (7.0755 mmole) of benzylalcohol was dissolved in 4 ml of dimethylformamide (DMF). 283 mg (7.0755 mmole) of 60%-NaH was slowly added and stirred at room temperature for 30 minutes. 850 mg (4.717 mmol) of the product of Reaction 1a (SM) was dissolved in 3 ml of dimethylformamide (DMF). The dissolved solution was slowly added dropwise to the reaction solution, followed by stirring at 80° C. for 3 hours. The reaction was confirmed by TLC (EA:Hex=1:2). When the reaction was completed, H2O was added to the reaction solution to quench the reaction, extracted with ethyl acetate (EA)/H2O. Thereafter the organic layer was washed with purified water 3 times, water was removed with MgSO4, and then concentrated. The concentrate was purified with a flash column (eluent:ethyl acetate (EA):hexane (Hex)=1:4 (volume ratio) mixture) to obtain 1.07 g of the target compound (yield: 78.3%). |
78.3% | Stage #1: benzylic alcohol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Stage #2: 2,3-epoxypropyl p-methoxyphenyl ether In N,N-dimethyl-formamide; mineral oil at 80℃; for 3h; | 1.1b Reaction 1b As shown in the above Reaction 1b, after dissolving benzylacohol 0.73ml (7.0755 mmole) in 4 ml of dimethylformamide, DMF, 60%-NaH 283mg (7.0755 mmole) was slowly added and stirred at inner room temperature for 30 minutes. A solution prepared by dissolving 850 mg(4.717mmole) of the product(SM) of the Reaction 1a in 3 ml of dime was slowly dropped in the reaction solution and stirred at a temperature of 80 C for 3 hours. The reaction was monitored as TLC(EA:Hex=1:2). When the reaction was completed, H2O was added to the reaction solution to quench the reaction, and extracted with (EA)/ H2O. The organic layer was washed with distilled water three times, and water in the organic layer was revoved by using MgSO4, and then the organc layer was concentrated. The concentrate was purified by flash column chromatography using mixed solution of (EA:Hex) = 1:4 (volume ratio) to afford 1.07 g of the target compound at yield of 78.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With (R,R)-(-)-N,N′-bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediaminocobalt(II); water; acetic acid In diethyl ether at 20℃; for 120h; | |
33% | With (1R,2R)-(-)-N,N'-bis(3,5-di-tert-butylsalicydene)-1,2-cyclohexanediaminocobalt(II); water; acetic acid In 1,4-dioxane; toluene at 20℃; for 18h; | |
Multi-step reaction with 3 steps 1: 100 percent / LiCl, AcOH / tetrahydrofuran / 18 h / Ambient temperature 3: 91 percent / NaOH / tetrahydrofuran / 22 h / Ambient temperature |
99 % ee | With 6C26H22N2O6(2-)*3C10H8N2*8Zn(2+)*2O(2-) In acetone at 20℃; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.4% | With water at 20℃; | The mixture of 16 (100 mg, 0.56 mmol1, 2, 3, 4-tetrahydroisoquinoline (148 mg, 1.1 mmol^ and H2O (0.2 mL) was stirred overnight at room temperature. The reaction mixture was extracted with dichloromethane and washed with water and brine, dried with anhydrous sodium sulfate, concentrated under vacuum to afford 180 mg of crude product as yellow oil. The crude product was purified by preparative thin-layer chromatography to obtain 141 mg of the target product (yield: 80.4%) . The structure was confirmed by 1H NMR & MS, purity 99.2 % by HPLC. |
58% | Stage #1: 1,2,3,4-tetrahydroisoquinoline; 2,3-epoxypropyl p-methoxyphenyl ether In dichloromethane at 60℃; Stage #2: With isatoic anhydride-N-(CH2)3-C8F17 In dichloromethane at 60℃; for 2.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With gold(III) chloride; silver trifluoromethanesulfonate In 1,2-dichloro-ethane at 83℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium azide; montmorillonite K10 Clay In water; acetonitrile at 80℃; for 7h; regioselective reaction; | General method for epoxide ring opening General procedure: To a mixture of epoxide (1 equiv) and NaN3 (1.5 equiv) in CH3CN-H2O (8:2, 10 mL) Montmorillonite K 10 (5% w/w) was added. The reaction mixture was stirred at 80°C for a specified time as required to complete the reaction. After completion as indicated by TLC, the reaction mixture was then filtered, the filter pad was washed with CH3CN and the combined filtrates were evaporated. The reaction mixture was extracted with EtOAc, the combined organic layers were washed with H2O and brine, dried over anhydrous Na2SO4, and evaporated under reduced pressure. The crude product was then purified by column chromatography over silica gel using EtOAc/petroleum ether as eluent to provide the pure azido alcohol. Characterization data of all the products are shown below. |
94% | With sodium azide In water at 65℃; for 4h; | |
With sodium azide In [(2)H6]acetone; water for 3h; Reflux; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In dichloromethane at 20℃; for 2h; | |
75% | With tetrabutylammomium bromide; potassium carbonate; palladium dichloride In water at 60℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In ethanol at 140℃; for 0.0666667h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sulfated zirconia In neat (no solvent) at 20℃; for 0.5h; regioselective reaction; | 2.3. Catalytic procedure for aminolysis of epoxide (AoE) using SZcatalyst General procedure: A solid SZ catalyst (20 mg), an epoxide (1 mmol) and an amine(1 mmol) were taken in a 5 mL screw capped vial and stirred mag-netically for a given time period (monitored by GC or TLC) undersolvent free condition at RT. On completion of the reaction, vis-cous liquid or solid product obtained was treated with methanol(2 × 3 mL) and centrifuged for the complete removal of organiccompounds from the solid catalyst. The evaporation of solvent fromthe combined organic layers furnished the crude product. A smallfraction of the crude product was directly injected to HPLC to findout the regioselectivity. The remaining portion of the crude mix-ture was purified by flash column chromatography (hexane/ethylacetate, 80:20) to get the major regioisomer in pure form. The puri-fied product was characterized by1H and13C NMR analysis. Theresidue thus obtained from centrifugation was dried in air (2 h) andthen at 200C for 3 h to get back the active catalyst (>97% recovery)for the next catalytic run. |
80% | With antimony(III) chloride In acetonitrile at 20℃; for 4.5h; regioselective reaction; | |
76% | With sulfated zirconia at 60℃; for 1h; |
85 % Chromat. | With zirconium(IV) sulfate at 60℃; for 0.166667h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | In isopropyl alcohol at 80℃; for 12h; | B25 Example 25; Preparation of compound 133; A solution of compound 131 (0.00248 mol) and [(4-memoxyphenoxy)methyl]- oxirane15 (0.00289 mol) in 2-propanol (15ml) was stirred at 80°C for 12 hours. A solid wasfiltered off and dried. The residue was purified by column chromatography over silicagel (35-70 jtm) (eluent: DCMMeOBMftjOH 95/5/0.1). The desired fractions werecollected and the solvent was evaporated. The residue was crystallized from methylethyl keton and diethyl ether. The precipitate was filtered off and dried, yielding 0.72g20 (50%) of compound 133, melting point 219°C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | Stage #1: 2,3-epoxypropyl p-methoxyphenyl ether; phenylhydrazine In ethanol for 1h; Heating / reflux; Stage #2: With hydrogenchloride In methanol; diethyl ether; ethanol | 4 To a stirred solution of phenyl hydrazine (1.08 g, 10 mmol) in EtOH (20 mi) 3- (p-methoxy-phenoxy)-1, 2-epoxypropane (1.80 g, 10 mmol) was added dropwise and the mixture was heated under reflux for 1 h. The solvent was evaporated off and the oily residue was dissolved in methanol (5 ml) and converted to the crystalline hydrochloride salt by using 22% ethanolic hydro- gen chloride (2 ml) and diethyl ether. Crystals were filtered off and recrystal- lized. 'H-NMR (400 MHz, D20) d (ppm): 3.35-3. 60 (2H, m, NCH2), 3.80 (3H, s OCH3), 4.02-4. 13 (2H, m, OCH2), 4.40-4. 48 (1H, m, OCH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With water at 20℃; for 18h; | The mixture of 16 (200 mg, 1.1 mmol), 2,6- dimethylmorpholine (0.27 ml, 2.2 mmol) and H2O (0.3 mL) was stirred overnight (about 18 hours) at room temperature. After the reaction was complete, the reaction mixture was extracted with dichloromethane and washed with water and brine, dried with anhydrous sodium sulfate, concentrated under vacuum to afford 324 mg of crude product as colorless oil (yield: 98.9%) . The crude product (120 mg) was purified by preparative thin-layer chromatography to obtain 48 mg of the title product (yield: 40%) . The structure was confirmed by 1H NMR & MS, purity 96.6 % by HPLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With water at 20℃; for 18h; | The mixture 16 (144 mg, 0.8 mmol), indoline (143 mg, 1.2 mmol) and H2O (0.2 mL) was stirred overnight (about 18 hours) at room temperature. The reaction mixture was extracted with ethyl acetate and the organic layer was washed with water and brine, dried with anhydrous sodium sulfate, concentrated under vacuum to afford the crude product. The crude product was purified by silica gel to obtain the title product (172 mg, yield: 72%) . The structure was confirmed by 1H NMR and the purity was 99.1% by HPLC.1H NMR (400 MHz, CDCl3) : 7.11 (d, J = 7.2Hz, IH) , 7.08 (t, J = 7.6 Hz, IH) , 6.92-6.83 (m, 4H) ; 6.70 (t, J = 7.6 Hz, IH) ; 6.57 (d, J = 7.2 Hz, IH) ; 4.25 (m, IH) ; 4.08-4.00 (m, 2H) ; 3.79 (s, 3H) ; 3.52 (dd, J = 16.8, 8.8 Hz, IH) ; 3.41 (dd, J = 18.0, 8.8 Hz, IH) ; 3.35 (dd, J = 18.0, 7.2 Hz, IH) ; 3.23 (dd, J = 13.2, 4.8 Hz, IH) ; 3.01 (t, J = 8.4 Hz, 2H) ; 2.67 (s, IH) ; LCMS (ESI) calcd for Ci8H2iNO3 (m/z) : 299.36. found: 300.3 [M+l] +. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With potassium carbonate In acetonitrile for 7h; Reflux; | 4.1.2 General procedure for the synthesis of oxiranes 4,7 General procedure: Epibromohydrin (2mmol), p-methoxyphenol or p-chlorophenol (2mmol) and potassium carbonate (3mmol) were dissolved in acetonitrile (10ml) and stirred at reflux for 7h. The mixtures were cooled and diluted with ethyl acetate and washed with water. Crude products were then purified by chromatography on silica gel, eluent chloroform. |
With potassium carbonate In butanone at 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With ferrocenium(III) tetrafluoroborate at 25℃; for 20h; | General procedure: The catalyst Fe(Cp)2BF4 (5 mol %) was added to a cooledepoxide (2 mmol), then methanol (1-8 equiv or 5 mL or 10 mL) was added. The resulting mixture was stirred at room temperature for specified time. Thereaction progress was checked by GC. After completion of the reaction thecrude product was purified by column chromatography or passed through apad of celite. |
73% | With cellulose sulfate at 0 - 25℃; for 24h; Cooling with ice; regioselective reaction; | General procedures for the ring-opening of epoxides with alcohols General procedure: Epoxide (1-5 mmol) was cooled in the ice bath for 2 min, then cellulose sulfate (2) (0.4-6.8 mg/mmol) was added to it, which followed by the addition of alcohol (1-10 equiv.) and the resulting reaction mixture was stirred at room temperature for the specified time. Reaction progress was monitored by gas chromatography. Excess amount of alcohol was removed on rotary evaporator and the resulting crude products 6, 8, 10a, 10b, 12a, 12b, and 14 were passed through a pad of the silica gel by eluting with hexane/diethyl ether (9/1). The solvent was removed on rotary evaporator to afford products as liquid. The crude products 4a, 4b, 4c, 4d, 16, 18, 20, 22, and 24 were purified by column chromatography by using hexane/ethyl acetate as an eluent on silica gel. |
47% | With allyltin tribromide at 20℃; for 15h; Reflux; |
With activated metal-organic framework on base of Cu(2+) and urea-containing V-shaped dicarboxylate ligand at 60℃; for 24h; | 2.2. Catalytic procedure General procedure: As shown in the structure of MOF 1 (Scheme 1 and Fig. S1), theguest DMF molecules remained in the framework through hydrogenbonding to urea moieties. Therefore, the active urea NeH sites in thechannels of 1 were blocked. To remove the guest DMF molecules withinthe cavities, 1 was treated with anhydrous MeOH and CH2Cl2, followedby placing in vacuum for two hours at 100 °C. The activated MOF 1 wasnamed as 1a. General procedure for cyanosilylation reaction: 1.5 mol%1a (catalyst loading based on aldehydes) was added to a solution ofindicated aldehyde (0.10 mmol), TMSCN (0.12 mmol), and dry MeOH(0.5 mL). The resulting mixture was stirred at 60 °C. For Henry reaction:a reaction mixture consisting of 1.5 mol% 1a (based on aldehydes),indicated aldehyde (0.10 mmol), and MeNO2 (1.0 mmol) was stirred at60 °C. For methanolysis reaction of epoxides: a reaction mixture consistingof 1.5 mol% 1a (based on epoxides), indicated epoxide(0.10 mmol), and dry MeOH (0.5 mL) was stirred at 60 °C. The threereactions were carried out for 24 h, and the yields were determined by1H NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With iron(III) chloride In neat (no solvent) at 20℃; for 0.0833333h; regiospecific reaction; | General procedure General procedure: Epoxide (0.01 mmol) is treated with pivaloyl halides (0.01 mmol) in presence of catalytic amount of Lewis acid (a-i). The reaction was stirred for 5 to 10 min and monitored the progress of the reaction by TLC. |
98% | at 20℃; for 12h; Neat (no solvent); regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | at 20℃; for 12h; Neat (no solvent); regioselective reaction; | |
99% | With iron(III) chloride In neat (no solvent) at 20℃; for 0.0833333h; regiospecific reaction; | General procedure General procedure: Epoxide (0.01 mmol) is treated with pivaloyl halides (0.01 mmol) in presence of catalytic amount of Lewis acid (a-i). The reaction was stirred for 5 to 10 min and monitored the progress of the reaction by TLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | at 20℃; for 12h; Neat (no solvent); regioselective reaction; | |
99% | With iron(III) chloride In neat (no solvent) at 20℃; for 0.0833333h; regiospecific reaction; | General procedure General procedure: Epoxide (0.01 mmol) is treated with pivaloyl halides (0.01 mmol) in presence of catalytic amount of Lewis acid (a-i). The reaction was stirred for 5 to 10 min and monitored the progress of the reaction by TLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With ammonium bromide; acetic acid In tetrahydrofuran; water at 20℃; for 3h; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With tert-butylamine hydrobromide In neat (no solvent) at 20℃; for 4h; | |
93% | With dicyclohexylamine hydroiodide In 1-methyl-pyrrolidin-2-one at 45℃; for 24h; | |
93% | With C25H22OP(1+)*Br(1-) In chlorobenzene at 120℃; for 12h; |
92% | With C80H48N8Ni2O4; 8Ni(2+)*6C40H24N4O2(2-)*4HO(1-)*2H2O; tetra-(n-butyl)ammonium iodide In neat (no solvent) at 70℃; for 12h; | |
89% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc dibromide In N,N-dimethyl-formamide at 80℃; for 10h; Schlenk technique; | |
95.7 %Spectr. | With C30H16O8(4-)*2Ni(2+)*4H2O*C3H7NO; tetrabutylammomium bromide In neat (no solvent) at 99.84℃; for 12h; Autoclave; Green chemistry; | |
92 %Chromat. | With tetrabutylammomium bromide at 80℃; for 2h; Schlenk technique; Green chemistry; | |
>99 %Spectr. | With [Ga(η4-(tris(2-oxy-3,5-dimethylbenzyl)amine)]; tetra-(n-butyl)ammonium iodide In butanone at 90℃; for 18h; Sealed tube; | |
With triethylamine In acetonitrile at 25℃; for 1h; Irradiation; Schlenk technique; | ||
90 %Spectr. | With tetrabutylammomium bromide; [Zn3(tca)2(dpta)]*(DMA)2(H2O)}n In neat (no solvent) at 99.84℃; for 1.5h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With dihydrogen peroxide In diethyl ether at 20℃; for 0.25h; Green chemistry; regioselective reaction; | |
88% | With dihydrogen peroxide In diethyl ether at 20℃; for 0.25h; regioselective reaction; | General procedure for synthesis of β-hydroxyhydroperoxides General procedure: A mixture of epoxide (1 mmol), 20 mg Fe3O4/GO-Mo(0.02 mmol of Mo) in 5 cm3 ethereal H2O2 solution (ca.1.0 mol dm3), was stirred at room temperature for anappropriate time. The progress of the reaction was followedby TLC. After completion of the reaction, the catalyst wasseparated from the solution by a permanent magnet(0.5-0.7 T), then washed with Et2O, air-dried, and savedfor the next round of reactions. After that, 20 cm3 Et2O wasadded to the reaction mixture and then washed with 5 cm3H2O. The aqueous layer was back-extracted with EtOAc(3 9 20 cm3). The combined organic layers were washedin turn with water (2 9 10 cm3) and brine (2 9 10 cm3),dried over anhydrous MgSO4, and concentrated underreduced pressure. The crude product was purified by flashcolumn chromatography on silica gel (n-hexane/EtOAc) toobtain the pure β-hydroxyhydroperoxides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In ethanol for 5h; Reflux; | 2 4.7. General procedure for the preparation of compounds 7-16 General procedure: A mixture of the appropriate 1-arylpiperazine (1.2 mmol) and the appropriate epoxide (1.0 mmol) in 20 mL of ethanol was refluxed for 5 h. After cooling, the solvent was removed in vacuo. The crude residue was chromatographed as detailed below to give desired pure compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium hydride; In N,N-dimethyl-formamide; at 0 - 20℃; | General procedure: To a suspension of NaH (1.1 mmol) in anhydrous DMF, cooled at 0 C, a solution of 4-methoxyphenol (0.19 g, 1.5 mmol) and (R)-or (S) glycidol nosylate (0.41 g, 1.5 mmol) in the same solvent was added dropwise. The reaction mixture was stirred at room temperature overnight, quenched with H2O and extracted with AcOEt (3 × 20 mL). The organic layers were collected, dried over Na2SO4 and concentrated under reduced pressure. The crude was purified on a silica gel column (n-hexane/AcOEt, 7:3 as eluent) to give pure compound as a white semisolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With water In isopropyl alcohol for 20h; Reflux; | Propanol derivatives (3a-3g). General procedure General procedure: A mixture of 1.2 g (4 mmol) of tetrahydroiso-quinoline(1), 4 mmol of substituted 2-phenoxy-methyloxirane2-2g, and 1 drop of water in 20 mL of 2-propanolwas boiled for 20 h. The solvent was distilled off, theresidue was crystallized from ethyl ether andrecrystallized from a mixture benzene-hexane, 2 : 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Stage #1: 2,3-epoxypropyl p-methoxyphenyl ether; 2-methyl-2-(4-methylphenyl)propan-1-amine With water In isopropyl alcohol for 20h; Heating; Stage #2: oxalic acid In diethyl ether | Salts of aminopropanoles (3a-3o). General method. General procedure: Mixture of 0.01 mol of amine 2a-2c, 0.011 mol of substituted aryloxymethyloxirane, and 2-3 drops of water in 30 mL of isopropyl alcohol were stirred for 20 h at boiling. The solvent was distilled off till dryness, the residue was dissolved in 30 mL of anhydrous ether and by treatment with ether solution of oxalic acid or hydrogen chloride oxalates or hydrochlorides were obtained and recrystallized from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: 2,3-epoxypropyl p-methoxyphenyl ether; 1-[1-(4-methylphenyl)cyclopentyl]methylamine With water In isopropyl alcohol for 20h; Heating; Stage #2: oxalic acid In diethyl ether | Salts of aminopropanoles (3a-3o). General method. General procedure: Mixture of 0.01 mol of amine 2a-2c, 0.011 mol of substituted aryloxymethyloxirane, and 2-3 drops of water in 30 mL of isopropyl alcohol were stirred for 20 h at boiling. The solvent was distilled off till dryness, the residue was dissolved in 30 mL of anhydrous ether and by treatment with ether solution of oxalic acid or hydrogen chloride oxalates or hydrochlorides were obtained and recrystallized from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: 2,3-epoxypropyl p-methoxyphenyl ether; [4-(4-methylphenyl)tetrahydro-2H-pyran-4-yl]methylamine With water In isopropyl alcohol for 20h; Heating; Stage #2: With hydrogenchloride In diethyl ether | Salts of aminopropanoles (3a-3o). General method. General procedure: Mixture of 0.01 mol of amine 2a-2c, 0.011 mol of substituted aryloxymethyloxirane, and 2-3 drops of water in 30 mL of isopropyl alcohol were stirred for 20 h at boiling. The solvent was distilled off till dryness, the residue was dissolved in 30 mL of anhydrous ether and by treatment with ether solution of oxalic acid or hydrogen chloride oxalates or hydrochlorides were obtained and recrystallized from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In dimethyl sulfoxide at 100℃; for 13h; regioselective reaction; | Synthesis of 3a-o; general procedure General procedure: In a round bottom flask (50 mL), a mixture of potassium carbazol-9-ide (0.01 mol) and the appropriate epoxide (0.015 mol) in DMSO (20 mL) was heated at 100 °C until TLC monitoring indicated no further improvement in the reaction (7-15 h). After completion of the reaction, the solvent was evaporated in vacuo. The foam obtained was dissolved in CHCl3 (100 mL) and subsequently washed with water (2 × 100 mL). The organic layer was dried over anhydrous sodium sulphate and evaporated. The crude product was purified by short column chromatography on silica gel eluting with n-hexane:EtOAc. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tetrabutyl ammonium fluoride In neat (no solvent) at 60℃; for 3h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.73 g | With caesium carbonate; In dimethyl sulfoxide; at 130℃; for 4h; | dimethyl sulfoxide (300 mL) suspension of (2S)-2-[4-(methoxy)phenoxy]methyl}oxirane (10.9 g), <strong>[2034-22-2]2,4,5-tribromo-1H-imidazole</strong> (14.3 g) and cesium carbonate (18.4 g) was stirred for 4 hours at 130C . The reaction mixture was allowed to cool to room temperature, after the addition of water and ethyl acetate, the organic layer was separated and the water layer. The aqueous layer was extracted twice with ethyl acetate, combined organic layer, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (Reveleris, mobile phase: hexane / ethyl acetate = 90/10 ~ 50/50; v / v) to give the title compound (Intermediate 1: 4.73 g, pale yellow oil) was obtained . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: 2,3-epoxypropyl p-methoxyphenyl ether; 1-amino-2-propene In N,N-dimethyl-formamide at 60℃; for 12h; Sealed tube; Stage #2: With water In N,N-dimethyl-formamide at 60℃; for 12h; Sealed tube; regioselective reaction; | General method for synthesis of amino alcohols: General procedure: In a 20 mL pressure tube (for volatile amines) was combined epoxide (1.0 mmol, 1.0 equiv) and amine (1.5 mmol, 1.5 equiv) 6.7 mL of reagent grade DMF. The reaction vessel fitted with a stirbar, sealed, and heated at 60°C for 12 h after which the vessel was allowed to cool to ambient temperature (not necessary for reactions not ran in pressure vessels) before receiving deionized water (50 equiv) in one portion. The vessel was resealed and stirred at 60°C for an additional 12 h. Solvent was removed on a rotary evaporator (22.5 mbar at 35°C) and the crude residue loaded directly onto a silica gel column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With water In isopropyl alcohol for 18h; Reflux; | Amino alcohols 4a-4h (general procedure) General procedure: A mixture of 1.0 g (5.1 mmol) of compound 3, 5.2 mmol of substituted (phenoxymethyl)oxirane, and 2-3 drops of water in 30 mL of propan-2-ol was refluxed for 18 h. The solvent was distilled off to dryness, and the residue was purified by column chromatography on aluminum oxide (Brockmann activity grade II; eluent benzene-ethyl acetate, 5 : 1). The solvent was distilled off from the eluate to isolate oily base 4a-4h. The product was converted into the corresponding hydrochloride by treatment of its solution in diethyl ether with a solution of HCl in diethyl ether. The precipitate was filtered off and recrystallized from propan-2-ol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium hydrogencarbonate; 1-n-butyl-3-methylimidazolim bromide; lithium chloride In neat (no solvent) at 40℃; for 24h; chemoselective reaction; | 4.3. General procedure for the synthesis of dithiocarbonates General procedure: To a 4 mL of vial was charged with [Bmim]Br (43.8 mg, 0.2 mmol), NaHCO3 (8.4 mg, 0.1 mmol), LiCl (4.2 mg, 0.1 mmol), epoxide (2 mmol) and CS2 (364 mL, 6 mmol). The reaction mixture was stirred at 40 °C for 24 h, after which time, water (5 mL) was added into the reaction mixture. The organic layer was extracted with CH2Cl2 (3 x 5 mL). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 4:1 as eluent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With 1-n-butyl-3-methylimidazolim bromide; potassium hydroxide; lithium bromide In neat (no solvent) at 70℃; for 24h; chemoselective reaction; | 4.4. General procedure for the synthesis of trithiocarbonates General procedure: To a 4 mL of vial was charged with [Bmim]Br (109.5 mg, 0.5 mmol), KOH (39.3 mg, 0.7 mmol), LiBr (60.8 mg, 0.7 mmol), epoxide (1 mmol) and CS2 (364 mL, 6 mmol) under air. The reaction mixture was stirred at 70 °C for 24 h, after which time, water (5 mL) was added into the reaction mixture. The organic layer was extracted with CH2Cl2 (3 x 5 mL). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate 4:1 as eluent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With N,N'-dimethylbenzylamine In isopropyl alcohol; butan-1-ol for 1.5h; Reflux; | Synthesis of 8-Bromo-7-(2-hydroxy-3-p-methoxyphenoxypropyl-1)theophylline (2) A mixture of8-bromotheophylline (1, 52 g, 0.2 mol) [9], p-methoxyphenoxymethyloxirane (39.6 g, 0.22 mol), BuOH-1 (200 mL), propanol-2(100 mL), and N,N-dimethylbenzylamine (2 mL) was refluxed for 1.5 h and filtered hot. The filtrate was cooled, left for 1 d,filtered. The solid was rinsed with cold propanol-2, NH4OH solution (5%), and H2O and crystallized from propanol-1.C17H19BrN4O5, mp 154-156, yield 83.0%. 1 NMR spectrum (400 MHz, DMSO-d6, , ppm, J/Hz): 6.78 (4, s, -15-18),5.19 (1, d, J = 4.7, 13-), 4.52-4.21 (3, m, -12, 13), 3.95 (2, d, J = 3.8, -14), 3.71 (3, s, -19), 3.46 (3, s, -11),3.21 (3, s, -10). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With (2-hydroxy-5-methylphenyl)triphenylphosphonium iodide In chlorobenzene at 100℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine In acetonitrile at 70℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In isopropyl alcohol Reflux; | 16 Example 16. Preparation of Compound 17 (BC1604) 2,2-Diplienylethylarnine (5 mmol) and 2-{(4-methoxyphenoxy)methylj-oxirane (5 mmol) were dissolved in isopropanol (20 rnL) and heated to reflux overnight. Solvent was then removed under vacuum to obtain the final product as yellow crystals (1 .7 g, 90% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With iodine; triphenylphosphine In toluene at 80℃; Sealed tube; | Typical procedure for the preparation of 1a-13a General procedure: To a solution of triphenylphosphine (1.05 mmol) in anhydrous toluene (2 mL) were added iodine (1.05 mmol) at room temperature, the mixture was stirred for 10 minutes until it became yellow turbid solution. Then epoxide (1 mmol) was added, followed by the addition of formic acid (1.05 mmol). Then the reaction was refluxed for 15 - 40 minutes. After completion of the reaction, the liquid was poured into DCM (20 mL), washed with 5% Na2S2O3 solution (215 mL), water (215 mL) and brine (20 mL).The combined organic layers were dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by chromatograph on silica gel (petroleum ether/acetone = 50/1, v/v) to give 1a-13a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium salts of magnetic graphitic carbon nitride at 70℃; | General procedure General procedure: A mixture of TMSCN (1.2 mmol), epoxide (1.0 mmol),and 30 mg Fe3O4g-C3N4-K was stirred at 70 °C undersolvent-free conditions for the appropriate time (Table 2).After completion of the reaction (monitored by TLC andGC), 10 cm3ethyl acetate added, and the catalyst removedby the external magnet. The reaction mixture was washedwith 10 cm3water and organic solvent evaporated underreduced pressure. In a few cases, the resulting crude productwas purified by flash chromatography on silica gel toafford an analytically pure corresponding product in yieldsgiven in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 12h; Inert atmosphere; regioselective reaction; | First step: General procedure: A mixture of 5 (106 mg, 0.5 mmol), epoxide 3 (0.5 mmol) and K2CO3 (103 mg, 0.75 mmol) in DMF (5 mL) was heated at 80 °C under N2 atmosphere for 12 h. The reaction was terminated by the addition of water (10 mL), and then diethyl ether (20 mL) was added. The organic layer was separated, washed by brine (20 mL) and dried over anh. Na2SO4. After filtration, the solution was evaporated to dryness under reduced pressure. The resulting crude product was further dried by a high vacuum pump, and then used it for the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With butyl methyl imidazolium silica sulfate In acetonitrile for 12h; Reflux; | 4.3. General procedure for synthesis of new 1,2-diol monoester of IBPderivatives (1a-1o) General procedure: In a round-bottomed flask, it was added IBP (10 mmol), epoxide (12mmol) and 0.2 g [BMIm]SS in 30 mL anhydrous acetonitrile. The reactionmixture was placed on magnetic stirrer under reflux conditionsfor 12-36 h (Fig. 10). After completion of the reaction (TLC check), thecatalyst was separated by a sintered glass, and the solvent was evaporatedin vacuo (rotary evaporator). Then, the residue was diluted inCHCl3 (150 mL) and washed with H2O (3 × 150 mL). Afterward, theproduct was purified by a short column chromatography eluted by solventsdescribed below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | In tetrahydrofuran at 60℃; for 24h; | 4.1.1 General procedure for the synthesis of alcohols 1,10 General procedure: Mixtures of triazole (1mmol) and 1,2-epoxy-3-phenoxypropane (for 1) or styrene oxide (for 10) (1mmol) in THF (4ml) were heated at 60°C and stirred for 24h. After this time, the solvent was evaporated at reduced pressure, and obtained crude mixtures were purified by column on silica gel (chloroform/methanol) or crystallization to obtain desired products. (0035) The same reaction scheme was applied to obtain triazole alcohols 5,8 and imidazole alcohols 12,14. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With pyridine In isopropanol for 6h; Reflux; | 4.4. Synthesis and Structure Confirmation of Target Compounds (CHJ) General procedure: Compounds CHJ were synthesized by nucleophilic reaction between 1-phenoxy-2,3-epoxypropanes (6) (1.0 eq) and intermediate compounds (5) (1.2 eq). In their isopropanolsolution, the catalytic amount of pyridine was added. The whole was heated to reflux for6 h and detected by TLC (dichloromethane:methanol = 10:1). The resulting mixture wasextracted with ethyl acetate. The extract was washed with H2O and brine, then dried overNa2SO4. The filtrate was concentrated under reduced pressure to afford crude product thatwas purified by silica gel column chromatography (dichloromethane:methanol = 20:1) togive the title compounds (CHJ) with yields of 80-90%. |
Tags: 2211-94-1 synthesis path| 2211-94-1 SDS| 2211-94-1 COA| 2211-94-1 purity| 2211-94-1 application| 2211-94-1 NMR| 2211-94-1 COA| 2211-94-1 structure
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Code | Phrase |
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Code | Phrase |
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Code | Phrase |
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P378 | |
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Code | Phrase |
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Code | Phrase |
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Health hazards | |
Code | Phrase |
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H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
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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 |
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