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CAS No. : | 6117-80-2 | MDL No. : | MFCD00002924 |
Formula : | C4H8O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ORTVZLZNOYNASJ-UPHRSURJSA-N |
M.W : | 88.11 | Pubchem ID : | 643790 |
Synonyms : |
|
Num. heavy atoms : | 6 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.5 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 23.19 |
TPSA : | 40.46 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) : | -7.41 cm/s |
Log Po/w (iLOGP) : | 1.23 |
Log Po/w (XLOGP3) : | -0.81 |
Log Po/w (WLOGP) : | -0.47 |
Log Po/w (MLOGP) : | -0.33 |
Log Po/w (SILICOS-IT) : | -0.2 |
Consensus Log Po/w : | -0.12 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | 0.26 |
Solubility : | 159.0 mg/ml ; 1.8 mol/l |
Class : | Highly soluble |
Log S (Ali) : | 0.44 |
Solubility : | 242.0 mg/ml ; 2.75 mol/l |
Class : | Highly soluble |
Log S (SILICOS-IT) : | 0.47 |
Solubility : | 261.0 mg/ml ; 2.96 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.99 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P260-P264-P270-P273-P301+P312+P330-P314-P501 | UN#: | N/A |
Hazard Statements: | H302-H373-H402 | 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 |
---|---|---|
72% | With toluene-4-sulfonic acid In dichloromethane at 20℃; for 3 h; Inert atmosphere | To a solution of cis-but-2-ene-1,4-diol (1, 9.3 mL, 113 mmol) in DCM, p-TSA·H2O (1.08 g, 6.2 mmol) was added under argon at room temperature followed by 2,2-dimethoxypropane (27.9 mL, 227 mmol). The reaction mixture was allowed to stir for 3 h. After the completion ofthe reaction, the reaction mixture was quenched with sat. NaHCO3 solution (50 mL) and extracted with DCM (2 × 50 mL). The combined organic layers were washed with brine (25 mL), dried over MgSO4 and the solvent was very slowly removed in vacuo to yield 6 as colourless oil(10.5 g, 72percent). The crude product was directly taken to the next step without purification. Rf = 0.51 (EtOAc/hexane 20percent); 1H NMR (400 MHz, CDCl3) δ 5.66 (2H, t, J = 1.6 Hz, H-1), 4.25 (4H, 2, J = 1.6 Hz, H-2), 1.43 (6H, s, H-4) ppm; 13C NMR (101 MHz, CDCl3 ): δ 129.5 (2C, C-1),102.0 (1C, C-3), 61.4 (2C, C-2), 24.0 (2C, C-4) ppm. Data matches literature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With triethylamine In tetrahydrofuran at 20℃; for 16 h; | To a stirred solution of 20.5 mL (0.25 mol) but-2-ene-1 ,4-diol and 105 mL (0.75 mol) triethylamine in 400 mL tetrahydrofuran was added 60 mL (0.63 mol) acetic anhydride at ambient temperature. After 16 h stirring, 300 mL saturated aq. sodium bicarbonate solution and 300 mL diethylether were added. The aq. layer was extracted with 200 mL diethylether and the combined organic phase was washed with 300 mL brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by vacuum distillation (3 mbar, 80-820C) to give 39.3 g of the diacetate, corresponding to a yield of 91percent based on but-2-ene-1 ,4-diol. To a stirred solution of 17.2 g diacetate (100 mmol) in a mixture of 150 mL acetone and 50 mL water were added 26 g N-methylmorpholine-N-oxide (NMO, 200 mmol) and 270 mg K2OsO4-H2O <n="19"/>(0.75 mmol) at ambient temperature. After 3 h stirring, TLC showed complete conversion of the diacetate and 300 ml. saturated aq. sodium hydrogen sulfite solution and 300 mL ethylacetate were added. The aq. layer was extracted with 600 mL ethylacetate and the combined organic phase was washed with 400 mL brine, dried (Na2SO4) and concentrated in vacuo to give 18.5 g of the diol as white crystals, corresponding to a yield of 90percent yield based on the diacetate. To a stirred solution of 8.2 g diol (40 mmol) in 150 mL dichloromethane was added 80 g sodium periodate on silica (55 mmol) at ambient temperature. After 1 .4 h stirring, TLC showed complete conversion. The silica was removed by filtration and rinsed with 100 mL dichloromethane. The combined filtrates were concentrated in vacuo and the residue purified by careful distillation to give 4.1 g of the aldehyde, corresponding to 50percent yield based on the diol. The identity of the compound was confirmed by 1H and 13C NMR spectroscopy. |
89% | With pyridine In dichloromethane at 0 - 20℃; for 18.5 h; Inert atmosphere | The entire synthesis was performed in an inert atmosphere. First, 79.63 g (0.78 mol) fresh distilled acetic acid anhydride was added dropwise to a solution of 20.26 g(0.23 mol) cis-2-butene-1,4-diol in 20 mL abs. dichloromethane at 0 °C. Afterwards, 55.37 g (0.7 mol) pyridine was added dropwise and the solution was stirred for 30 min at 0 °C. After being stirred for 18 h at room temperature, the reaction solution was washed three times with 30 mL 2 M HCl and with 25 mL brine. The organic product phase was dried with MgSO4. After that, the solvent of the reaction was removed. A 35.10-g amount of cis-1,4-diacetoxy-2-butene 5 (0.20 mol, 89 percent) were isolated as a colorless liquid with a purity of about 98.5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | at 60℃; for 2 h; | General procedure: In a typical procedure, in a capped vessel alcohol 3a (0.5 mmol) and ester 2a (1.5 mmol) were added sequentially to the TEAHC (35.0 mg, 0.15 mmol); the reaction mixture was stirred for 2 h at 60 °C and then transferred in a round-bottomed flask and concentrated under reduced pressure. The residue mixture was then extracted with diethyl ether (3 times with 10 cm3). After removal of the solvent from the combined ethereal layers under reduced pressure, the crude reaction mixture was analyzed by 1H and 13C NMR and thin-layer chromatography (TLC). All products were purified by using flash chromatography (n-hexane / ethyl acetate, 95/5) and identified on the basis of NMR spectroscopic analysis by comparison with reported data. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With Oxone; sodium hydrogencarbonate; In water; acetone; at 20℃; for 4h; | General procedure: Oxone (169 mmol)was slowly added by portions to a stirred solutionof 1,3-dioxacyclohept-5-en 1 (130.2 mmol) and NaHCO3(619 mmol) in 100 ml of acetone-water mixture (1 : 1 v/v)for 3 hours at 20C. (en, the reaction mixture was additionallystirred for 1 hour. (e product was extracted withCH2Cl2 (2 × 50 ml). Organic layers were combined and driedover MgSO4. (e solvent was evaporated under reducedpressure, and the product was purified by column chromatographyon silica gel (eluent petroleum ether-ethylacetate, 7 : 1). |
With 3-chloro-benzenecarboperoxoic acid; In water; ethyl acetate; at 20℃; for 96h; | To a mixture of 4 g of cis-2-buten-1,4-diol and 100 ml and ethyl acetate was added 10 g of m-chloroperbenzoic acid (70% content) under ice-cooling, followed by stirring as it was at room temperature for 4 days. The reaction mixture was concentrated and the resulting m-chlorobenzoic acid was separatedby filtration, and then 2.3 g of crystals of the entitled compound was obtained from the mother liquor.1H-NMR(CDCl3) deltappm=2.07(2H, m) , 3.24-3.32(2H, m) , 3.78-3.94(4H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With triethylamine; In tetrahydrofuran; at 20℃; for 16h; | To a stirred solution of 20.5 mL (0.25 mol) but-2-ene-1 ,4-diol and 105 mL (0.75 mol) triethylamine in 400 mL tetrahydrofuran was added 60 mL (0.63 mol) acetic anhydride at ambient temperature. After 16 h stirring, 300 mL saturated aq. sodium bicarbonate solution and 300 mL diethylether were added. The aq. layer was extracted with 200 mL diethylether and the combined organic phase was washed with 300 mL brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by vacuum distillation (3 mbar, 80-820C) to give 39.3 g of the diacetate, corresponding to a yield of 91% based on but-2-ene-1 ,4-diol. To a stirred solution of 17.2 g diacetate (100 mmol) in a mixture of 150 mL acetone and 50 mL water were added 26 g N-methylmorpholine-N-oxide (NMO, 200 mmol) and 270 mg K2OsO4-H2O <n="19"/>(0.75 mmol) at ambient temperature. After 3 h stirring, TLC showed complete conversion of the diacetate and 300 ml. saturated aq. sodium hydrogen sulfite solution and 300 mL ethylacetate were added. The aq. layer was extracted with 600 mL ethylacetate and the combined organic phase was washed with 400 mL brine, dried (Na2SO4) and concentrated in vacuo to give 18.5 g of the diol as white crystals, corresponding to a yield of 90% yield based on the diacetate. To a stirred solution of 8.2 g diol (40 mmol) in 150 mL dichloromethane was added 80 g sodium periodate on silica (55 mmol) at ambient temperature. After 1 .4 h stirring, TLC showed complete conversion. The silica was removed by filtration and rinsed with 100 mL dichloromethane. The combined filtrates were concentrated in vacuo and the residue purified by careful distillation to give 4.1 g of the aldehyde, corresponding to 50% yield based on the diol. The identity of the compound was confirmed by 1H and 13C NMR spectroscopy. |
89% | With pyridine; In dichloromethane; at 0 - 20℃; for 18.5h;Inert atmosphere; | The entire synthesis was performed in an inert atmosphere. First, 79.63 g (0.78 mol) fresh distilled acetic acid anhydride was added dropwise to a solution of 20.26 g(0.23 mol) cis-2-butene-1,4-diol in 20 mL abs. dichloromethane at 0 C. Afterwards, 55.37 g (0.7 mol) pyridine was added dropwise and the solution was stirred for 30 min at 0 C. After being stirred for 18 h at room temperature, the reaction solution was washed three times with 30 mL 2 M HCl and with 25 mL brine. The organic product phase was dried with MgSO4. After that, the solvent of the reaction was removed. A 35.10-g amount of cis-1,4-diacetoxy-2-butene 5 (0.20 mol, 89 %) were isolated as a colorless liquid with a purity of about 98.5 %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 1,2,3-Benzotriazole; thionyl chloride In dichloromethane at 20℃; | |
87% | With thionyl chloride; triethylamine In ethyl acetate at -10℃; for 0.166667h; | |
With dimethylsulfite |
With dimethylsulfite at 110 - 120℃; | ||
With 1H-imidazole; thionyl chloride In dichloromethane for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | To a suspension of 55% NaH (13.0 g, 298 mmol) in DMF (250 mL), a solution of 6 (10.0 g, 114 mmol) in DMF (50 mL) was added at 0 C. After the mixture was stirred at room temperature for 1 h, benzyl bromide (35.3 mL, 398 mmol) was added dropwise to the mixture. The resulting mixture was stirred for 4 h at room temperature. The reaction was then quenched by addition of saturated aqueous NH4Cl solution, diluted with ether, and washed with water and brine. The organic layer was dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/AcOEt=8:1) to give 7 (30.2 g, 99%) as a colorless oil.1H NMR (500 MHz, CDCl3) delta: 7.36-7.25 (m, 10H), 5.82-5.76 (m, 2H), 4.49 (s, 4H), 4.06 (d, 4H, J=4.3 Hz). 13C NMR (125 MHz, CDCl3) delta: 138.3, 129.6, 128.3, 127.9, 127.8, 72.4, 65.9. FAB-LRMS m/z: 269 (MH+). FAB-HRMS m/z: 269.1550 (calcd for C18H21O2: 269.1542). | |
99% | To a mixture of 55% NaH (13.0 g, 298 mmol) and DMF (250 mL) was slowly added a solution of 1 (10.0 g, 114 mmol) in DMF (50 mL) at 0 C. After stirring the mixture for 1 h at r.t., benzyl bromide (35.3 mL, 398 mmol) was added dropwise. The resulting mixture was stirred for 4 h at r.t. The reaction was quenched by the addition of sat. aq NH4Cl solution, followed by extraction with EtOAc. The organic layer was washed with H2O, dried over MgSO4 and concentrated to afford crude compound 2. The crude was purified by silica gel column chromatography (hexane-EtOAc, 8:1) to give 2 (28.4 g, 99%) as a colorless oil. 1H NMR (500 MHz, CDCl3): delta = 4.15-4.16 (d, J = 2.5 Hz, 4 H), 4.58 (s, 4H), 5.89 (br s, 2 H), 7.36-7.42 (m, 10 H). 13C NMR (125 MHz, CDCl3): delta = 66.0, 72.3, 127.8, 127.9, 128.6, 129.7, 138.6. HRMS: m/z [M + H]+ calcd for C18H21O2: 269.1542; found: 269.1536. | |
98% | To a solution of 60 sodium hydride (2.4g, 60% disp. in 61 mineral oil, 59.0mmol, 2.6equiv) in dry 66 DMF (50mL), a solution of 67 (Z)-but-2-ene-1,4-diol (1.87mL, 22.7mmol) in dry DMF (10mL) was added under argon at 0C. The resulting solution was warmed gradually to room temperature and stirred for 1h. Then 68 benzyl bromide (9.4mL, 79.5mmol, 3.5equiv) was added dropwise. After stirring overnight, the reaction was quenched with satd aq NH4Cl (30ml). The aqueous layer was washed with Et2O (3×20mL). The combined organic layers were washed with H2O (30mL), brine (30ml), dried over Na2SO4, and filtered. The filtrate was concentrated under reduced pressure to give the crude 69 product, which was purified by silica gel column chromatography (1:15 AcOEt/hexanes); to afford 5.97g (98%) of 10 as a yellow oil. Rf=0.52 (1:6 AcOEt/hexanes); 1H NMR (300MHz, CDCl3) delta 7.44-7.31 (m, 10H), 5.88-5.83 (m, 2H), 4.55 (s, 4H), 4.14-4.11 (m, 4H); 13C NMR (75MHz, CDCl3) delta 138.9, 130.2, 129.1, 128.5, 128.3, 72.9, 66.5 |
83% | To a stirring solution of (Z)-but-2-ene-l,4-diol (SM) (100 g, 1.136 mol) in DMF (2.5 L) was added NaH (60% dispersion in mineral oil, 136 g, 3.409 mol) at 0 C under nitrogen atmosphere. After being stirred for 1 h, benzyl bromide (407 mL, 3.409 mol) in DMF (500 mL) was added drop wise. The reaction mixture was brought to room temperature and stirred for 16 h. After consumption of the starting material (by TLC), the reaction mixture was poured into ice water (5 L) and extracted with Et20 (3 x 1.5 L). The combined organic layer was dried over anhydrous Na2S04 and concentrated under reduced pressure. The crude was purified by combi- flash column chromatography eluting with 10% EtOAc /hexane to afford compound Int-A (225 g, 83%) as colorless liquid. (0567) MHz, DMSO-ifc) d 7.42 - 7.22 (m, 10H), 5.78 - 5.65 (m, 2H), 4.44 (s, 4H), 4.04 (d, J = 4.6 Hz, 4H); LCMS (ESI): m/z 269.3 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With triethylamine; In dichloromethane; at 20℃; for 0.5h;Cooling with ice; | [00149] Compound 2: A solution of (Z)-but-2-ene-l,4-diol (0.93 ml, 11.3 mmol) and triethylamine (3.3 ml, 24 mmol) in DCM (50 mL) was added in a dropwise fashion to a stirring ice cold solution of methanesulfonyl chloride (1.9 ml, 24 mmol) in DCM (50 mL). After stirring for 0.5h at r.t. the mixture was poured onto ice and extracted. The organic layer was collected, dried (MgS04), filtered and reduced to 2.66 g, 96% of compound 2, which was judged by NMR to be sufficiently pure for direct use in the next step of the reaction. [00150] 1H NMR (399 MHz, CDC13) delta 5.94 (ddd, J = 5.4, 4.1, 1.3 Hz, 2H), 4.83 (dd, J = 4.1, 1.3 Hz, 4H), 3.04 (s, 6H); 13C NMR 128.34, 64.38, 38.27; MS (ESI +ve): calc (M+NH4): 262.04, found: 262.05. Rf = 0.3 (1 : 1 EtOAc/hexane). |
96% | With triethylamine; In dichloromethane; at 20℃; for 0.5h;Cooling with ice; | A solution of (Z)-but-2-ene-l,4-diol (0.93 ml, 11.3 mmol) and triethylamine (3.3 ml, 24 mmol) in dichloromethane (DCM, 50 mL) was added in a dropwise fashion to a stirring ice cold solution of methanesulfonyl chloride (1.9 ml, 24 mmol) in DCM (50 mL). After stirring for 0.5h at r.t. the mixture was poured onto ice and extracted. The organic layer was collected, dried (MgS04) and filtered. After removal of solvent, 2.66 g compound 2 was obtained (96%), which was judged by NMR to be sufficiently pure for direct use in the next step of the reaction. 1H NMR (399 MHz, CDC13) delta 5.94 (ddd, J = 5.4, 4.1, 1.3 Hz, 2H), 4.83 (dd, J = 4.1, 1.3 Hz, 4H), 3.04 (s, 6H); 13C NMR 128.34, 64.38, 38.27; MS (ESI +ve): calc (M+NH4)+: 262.04, found: 262.05; Rf = 0.3 (1 :1 EtOAc/hexane). |
With triethylamine; In dichloromethane; at 0℃; | EXAMPLES Example 1Preparation of 1-[(1 alpha,5alpha,6alpha)-3-(2,4-difluorophenyl)-3-azabicyclo[3.1.0]hex-6-yl]-3-(5-terf- butyl) thiadiazol-2-yl)urea:Step 1 : Preparation of(2Z)-but-2-ene-l,4-diyl dimethanesulfonate:To a solution of methanesulfonyl chloride (40 ml, 0.527moles) in anhydrous dichloromethane (300 mL) is added slowly a mixture of cis-2-butene-l,4-diol (10.5 ml, 0.127 mol) and triethylamine (84 ml, 0.604 mol) at O0C under nitrogen atmosphere and stirred for about 30-60 minutes. After the mixture is stirred for about 30 min more, it is then transferred to a separatory funnel and washed successively with chilled water, hydrochloric acid (10%), saturated sodium bicarbonate solution and saturated sodium chloride solution. The dichloromethane layer is separated and dried over anhydrous sodium sulfate. The removal of solvent in vacuum resulted in a yellow powder (10 g) obtained. IR (KBr) 2929, 1624, 1319, 1 173, 1 144, 1056, 1018, 934,795 cm"1 . 1H NMR (300 MHz, CDCl3) delta 5.90 (m, 2H), 4.80 (d, 4H), 3.03 (s, 6H). |
With triethylamine; In ethyl acetate; at 0℃; | In an ice bath, 26 ml of methanesulfonyl chloride was added dropwise in to a mixture of 10 g of cis-2-buten-1,4-diol, 63 ml of triethylamine and 1000 ml of ethyl acetate, followed by stirring at the same temperature for 3 hours. Then, the insoluble matters were removed by filtration. The filtrate was further filtered through silica gel and washed with ethyl acetate. Then, the filtrate was evaporated, to give 21.4 g of cis-1,4-bis(methanesulfonyloxy)-2-butene. | |
With N-ethyl-N,N-diisopropylamine; In dichloromethane; at -40 - 10℃; for 1h;Inert atmosphere; | 10 g of cis-but-2-ene-1,4-diol (113 mmol) and 3.0 equivalents of diisopropylethylamine (44 g, 340 mmol, 60 ml) were dissolved in 250 ml of dichloromethane and cooled in an argon atmosphere to -40 C., after which 2.4 equivalents of methanesulfonyl chloride (30.9 g, 270 mmol, 20.9 ml) were added portionwise and the reaction mixture was allowed to warm up to +10 C. for 1 h. The clear, yellow solution was poured into 500 ml ice-cold water and the organic phase was washed with further 500 ml of cold water, then with 200 ml of 2 N HCl, then twice with 200 ml each of saturated NaHCO solution, and finally again twice with 200 ml each of water. The dichloromethane solution of the product was dried over Na2SO4 and the solvent was withdrawn in vacuo until a white precipitate appeared, whereafter the minimum amount of dichloromethane was added in order to again obtain a clear solution. After the addition of 25 ml of diethylether, the product was left to crystallize from the solution at -20 C., whereafter 10 g of cis-1,4-bis(methylsulfonyloxy)-but-2-ene were isolated as a crystalline, white solid. 1H NMR (400 MHz, CDCl3) delta (ppm): 3.04 (s, 3H), 4.84 (m, 2H), 5.95 (m, 1H). 9.2 Preparation of polyaminoguanidine (9) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In propan-1-ol at 89.9℃; | ||
With hydrogen; copper(II) sulfate In ammonium hydroxide; water at 40℃; Title compound not separated from byproducts; | ||
With hydrogen In isopropyl alcohol at 30℃; for 1h; Autoclave; optical yield given as %de; stereoselective reaction; |
With 5% Pd-CaCO3; hydrogen In hexane at 25℃; | ||
89.362 % de | With hydrogen In ethanol at 22℃; for 1.5h; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrabutyl-ammonium chloride; potassium carbonate In N,N-dimethyl-formamide at 60℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With hydrogen for 30h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sulfuric acid; mercury(II) sulfate In water at 50℃; for 0.05h; microwave oven; | |
66% | With sulfuric acid; mercury(II) sulfate In water at 50℃; for 0.0833333h; Irradiation; | |
65% | With sulfuric acid; mercury(II) sulfate In water at 100℃; for 3h; |
64% | With mercury(II) sulfate In sulfuric acid | |
62% | With sulfuric acid In water Heating; | |
61% | With sulfuric acid; mercury(II) sulfate for 3h; Heating; | |
61% | With sulfuric acid; mercury(II) sulfate In water for 1.5h; Reflux; | i) (±)-3-Butene-1, 2-diol (8) i) (±)-3-Butene-1, 2-diol (8)Procedure: A mixture of 2-butene-1, 4-diol 7 (80 g, 90.9 mmol), water (35 mL),catalytic amount of concentrated sulphuric acid (0.5 mL) and mercuric sulphate (0.36g) was heated under reflux. After 1.5 h the reaction mixture was cooled to 0 oC andneutralized with 10 % sodium hydroxide to pH 7. The contents of the flask weredistilled by using a 12’ vigreaux fractionating column. The first fraction boiledbetween 38-43 oC/15 mm contained water, second fraction collected between 78-90oC/15 mm contained 3-butene-1, 2-diol 8 (49 g, 61 %) as a colourless syrup andsubsequently, third fraction obtained had traces of unreacted starting material at 110-115 oC/15mm.Yield: 61 %; B.P: 85 oC /15 mm; IR (CHCl3, cm-1): 3456, 1621; 1H NMR (CDCl3 +CCl4, 200MHz): δ 3.45 (dd, J = 10.56, 7.71 Hz, 1H), 3.63 (dd, J = 11.49, 3.28 Hz,1H), 3.94 (s, 2H, OH), 4.22 (m, 1H), 5.18 (dt, J = 10.56, 1.52 Hz, 1H), 5.32 (dt, J =17.31, 1.52 Hz, 1H), 5.81 (ddd, J = 17.31, 10.56, 5.56 Hz, 1H); 13C NMR(CDCl3+CCl4, 50MHz): δ 66.0, 73.2, 116.3, 136.6; Elemental analysis: Analysiscalcd. for C4H8O2: C, 54.52; H, 9.15. Found: C, 54.14; H, 9.46. |
60% | With sulfuric acid; mercury(II) sulfate at 80℃; for 1.5h; | |
60% | With sulfuric acid; mercury(II) sulfate In water for 1.5h; Heating; | |
With sulfuric acid; mercury(II) sulfate In water at 100℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In various solvent(s) at 150℃; for 4h; | |
With hydrogen Ambient temperature; | ||
95 % Chromat. | In diethylene glycol dimethyl ether at 130℃; for 5h; other catalysts, solvents, temperatures and reaction times; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; phosphorus tribromide 1.) diethylether, 85 deg C, 15 mm Hg, 2.) petroleum ether, 10-15 Torr; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 5 wt% Pd nanoparticles loaded on phosphate anion exchanged [Mg6Al2(OH)16]CO3*xH2O; air at 50℃; for 6h; Irradiation; | |
78% | With Celite; silver carbonate In benzene for 2h; Heating; | |
77% | With allyl methyl carbonate In toluene for 6h; Heating; |
50% | at 30℃; for 24h; Nocardia corallina B-276; | |
With sodium hydrogencarbonate; sodium carbonate at 20℃; for 3h; anodic oxidation on PbO2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Step 3: (Z)-4-(benzyloxy)but-2-en-1-olTo a suspension of NaH (5.44 g, 1 13.6 mmol) in DMF (100 ml) was added (Z)-but-2- ene-1 ,4-diol (10 g, 136.1 mmol) in DMF (50 ml). Bromomethyl-benzene (29 g, 170.4 mmol) was added in DMF (50 ml) at 0C, the mixture was stirred at room temperature for 2 hours, quenched with water (500 ml), and extracted with Et20 (500 ml *3). The organic layers were combined, dried (Na2S04), concentrated, and purified by flash chromatography to afford (Z)- 4-(benzyloxy)but-2-en-1 -ol (1.1 g, 95% yield) | |
32% | NaH (60 % in mineral oil, 135.6 g, 5.65 mmol, 1 equiv)was added very slowly to a solution of cis-2-butene-1,4- diol (1 g, 11.3 mmol, 2 equiv) inTHF (30 mL) at 0 C. The resulting mixture was stirred at room temperature for 30 minand then benzyl bromide (0,69 mL, 5.65 mmol, 1equiv) was added. The reaction mixturestirred for 12 h at room temperature. The reaction was quenched with NH4Cl. Theaqueous phase was extracted three times with EtOAc and the combined organic phaseswere dried over Na2SO4. After removal of solvent under reduced pressure the residue waspurified by silica gel column chromatography (hexane/AcOEt = 95:5 to 90:10) to give a yellow oil (313.6 mg, 32 %) NMR data was in accordance with what was previouslyreported | |
In N,N-dimethyl-formamide; | (a) 14.6 g of sodium hydride (60% in oil) was washed with n-pentane under argon, and dried. 150 ml of dry DMF was added thereto for suspension, and 75 g of (Z)-2-buten-1,4-diol was dropwise added thereto over a period of 30 minutes under stirring at 0 C. The mixture was stirred at room temperature for 1.5 hours, and then 44 g of benzyl bromide was added thereto under stirring at 0 C. The mixture was stirred at the same time for 30 minutes and then the temperature was returned to room temperature and stirred at 50 C. overnight. The reaction solution was poured into ice water, extracted with ether, and the ether solution was washed sequentially with water and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to distillation under reduced pressure (2.5 mmHg, 134-138 C.) to obtain 29 g of (Z)-4-benzyloxy-2-buten-1-ol as colorless oily substance. Rf: 0.49 (n-hexane/ethyl acetate=1/1). |
The monobenzyl ether 52b of <strong>[6117-80-2]cis-2-Butene-1,4-diol</strong> 52a was prepared as reported3 by treating this diol byNaH in THF, the formed alkoxide then being reacted with benzyl bromide to afford, after separation bycolumn chromatography (hexane/EtOAc), 52b as a colourless oil |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With pyridine at 20℃; for 27h; Inert atmosphere; | |
84% | With pyridine for 24h; | |
81% | With dmap; triethylamine In dichloromethane at 20℃; for 24h; |
81% | With dmap; triethylamine In dichloromethane at 20℃; for 24h; | 1 4-Trityloxy-but-2-en-1-ol (1) Trityl chloride (557 mg; 2 mmol) Et3N (0.306 ml ; 2.2 mmol) and DMAP (10 mg; 0.08 mmol) were added to an emulsion of cis-2-buten-1, 4-diol (1.76 g; 20 mmol) in DCM (10 ml). The mixture was stirred at room temperature under atmosphere of nitrogen for 24 hours. After such period of time the complete disappearance of trityl chloride was observed by TLC (EtOAC/Hexane 50: 50). DCM (20 ml) and water (10 ml) were added to the mixture. The phases were separated and the organic layer was washed with water (10 mi) and brine (10 ml). The solvent was dried over MgSO4 and evaporated under reduced pressure affording a residue (white oil) which was purified by flash chromatography using Hexane/EtOAc 70: 30 + 40: 60 as gradient which gave the title product as a colourless oil (563 mg, 81%). |
80% | With dmap; triethylamine In dichloromethane at 20℃; for 24h; | |
73% | With dmap; triethylamine In dichloromethane at 20℃; | |
61.4% | With dmap; triethylamine In dichloromethane at 0 - 20℃; for 3h; | |
61.4% | With dmap; triethylamine In dichloromethane at 20℃; for 3h; | 1.d The compound cis-butene-1,4-diol (5g, 56. 82mmol) miscible in 100mL of methylene chloride, the ΤΕΑ (8. 7mL, 62. 50mmol), DMAP (0. 28g, 2. 27mmol) , was added portionwise under stirring triphenylchloromethane (15. 84g, 56. 82mmol), stirred for 3 hours at room temperature, TLC (PE/EA=5/1) monitoring the reaction, to be after the reaction is complete, add dichloromethane dilution, water, saturated ammonium chloride aqueous solution, the saturated salt water washing, dry anhydrous sodium sulfate, column chromatography (PE/EA=10/1, 5/1), to obtain rosiness jelly 11.52g, yield: 61.4%. |
56% | Stage #1: 1,4-butenediol With sodium hydride In N,N-dimethyl-formamide at 25℃; for 2h; Stage #2: trityl chloride In N,N-dimethyl-formamide at 25℃; for 16h; | |
With bisacodyl; triethylamine | ||
With pyridine at 20℃; for 16h; | ||
With TEA In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium hydroxide;tetrabutylammomium bromide; In water; at 60 - 95℃; for 2h; | 1,4-Dibenzyloxy-2-butene (18); EMI32.0[0153] To 48% aqueous sodium hydroxide (127.8 g) was added tetra-n-butylammonium bromide (3.3 g, 10 mmol). The mixture was heated to 60[deg.] C. To the mixture was added 2-butene-1,4-diol (17) (30.0 g, 340 mmol), to which was added dropwise benzyl chloride (94.8 g, 743 mmol) at 80+-15[deg.] C. The mixture was stirred at the same temperature for 2 hours. The reaction mixture was cooled down, and separated after the addition of water (90 ml). To the organic layer was added sulfuric acidic brine. The solution was neutralized by aqueous sodium hydrogen carbonate, separated, mixed with ethyl acetate and concentrated under reduced pressure to yield the objective (18) (104.5 g, quantitative) as an oil residue. [0154] <1>H-NMR (CDCl3-TMS) [delta] ppm: 4.05 (d, J=3.8 Hz, 2H), 4.48 (s, 2H), 5.78 (m, 2H), 7.31 (m, 10H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Step 1: To a stirred solution of sodium hydride (60% wt in oil, 750 mg,18.90 mmol, 1 equiv.) in dry THF (28 mL), was added cis-but-2-ene, 1,4 diol (1.68 g, 18.90 mmol, 1 equiv.) dropwise over 50 minutes at 0C under azote atmosphere. The reaction mixture was warmed to room temperature and stirred for 1 hour. Then, tert-butyldimethylsilyl chloride (2.84 g, 18.90 mmol, 1 equiv.) in dry THF (28 mL) was added dropwise over 50 minutes and stirred for 1 hour. The reaction mixture was quenched by addition of a saturated solutionof ammonium chloride (35 mL). After evaporation of THF, the aqueous layer was extracted twice with DCM and the combined organic layers were dried over Na2SO4, filtered and concentrated under vacuum. A purification of the residue by flash column chromatography (10-30% EtOAc in cyclohexane) provided (2)-4-[tert-butyl(dimethyl)silyl]oxybut-2-en-1-ol (3.14 g, 88%) as ayellow oil. 1H NMR (300 MHz, ODd3) 5.70-5.68 (m, 2H), 4.26-4.25 (m, 2H),4.20-4.18 (m, 2H), 0.90 (5, 6H), 0.09 (5, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With p-toluenesulfonic acid monohydrate; | REFERENCE EXAMPLE 1 Production of Compound [2] (Step 1) To a mixture of (z)-2-butene-1,4-diol (compound [1], 211.4 g, 2.4 mol) and 2,2-dimethoxypropane (590.2 ml, 4.8 mol) was added p-toluenesulfonic acid monohydrate (30 mg). The solution thus obtained was evaporated under atmospheric pressure to give a colorless transparent liquid of 2,2-dimethyl-4,7-dihydro-1,3-dioxepine (compound [2], 245 g, yield 80%), melting point 140-145 C./760 mmHg. 1 H-NMR (CDCl3, 300 MHz) delta: 5.67 (diffused s, 2H), 4.26 (diffused s, 4H), 1.44 (s, 6H) |
80% | With p-toluenesulfonic acid monohydrate; | EXAMPLE 1 Production of compound [2] (Step 1) To a mixture of (z)-2-butene-1,4-diol (compound [1], 211.4 g, 2.4 mol) and 2,2-dimethoxypropane (590.2 ml, 4.8 mol) was added p-toluenesulfonic acid monohydrate (30 mg). The solution thus obtained was evaporated under atmospheric pressure to give a colorless transparent liquid of 2,2-dimethyl-4,7-dihydro-1,3-dioxepine (compound [2], 245 g, yield 80%), boiling point 140-145 C./760 mmHg. 1 H-NMR (CDCl3, 300 MHz) delta: 5.67 (diffused s,2H), 4.26 (diffused s, 4H), 1.44 (s,6H) |
72% | With toluene-4-sulfonic acid; In dichloromethane; at 20℃; for 3h;Inert atmosphere; | To a solution of cis-but-2-ene-1,4-diol (1, 9.3 mL, 113 mmol) in DCM, p-TSA·H2O (1.08 g, 6.2 mmol) was added under argon at room temperature followed by 2,2-dimethoxypropane (27.9 mL, 227 mmol). The reaction mixture was allowed to stir for 3 h. After the completion ofthe reaction, the reaction mixture was quenched with sat. NaHCO3 solution (50 mL) and extracted with DCM (2 × 50 mL). The combined organic layers were washed with brine (25 mL), dried over MgSO4 and the solvent was very slowly removed in vacuo to yield 6 as colourless oil(10.5 g, 72%). The crude product was directly taken to the next step without purification. Rf = 0.51 (EtOAc/hexane 20%); 1H NMR (400 MHz, CDCl3) delta 5.66 (2H, t, J = 1.6 Hz, H-1), 4.25 (4H, 2, J = 1.6 Hz, H-2), 1.43 (6H, s, H-4) ppm; 13C NMR (101 MHz, CDCl3 ): delta 129.5 (2C, C-1),102.0 (1C, C-3), 61.4 (2C, C-2), 24.0 (2C, C-4) ppm. Data matches literature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With 4,4'-diaminostilbene-2,2'-disulfonic acid In dichloromethane for 0.5h; Further byproducts given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 4,4'-diaminostilbene-2,2'-disulfonic acid In dichloromethane for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | Stage #1: Hexa-2,4-diyne-1,6-diol With hexacarbonyldicobalt In dichloromethane at 20℃; for 1h; Stage #2: 1,4-butenediol With boron trifluoride diethyl etherate In dichloromethane at 20℃; Stage #3: With ammonium cerium(IV) nitrate In acetone at 0℃; for 0.166667h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: 1,4-butenediol With tetrabutylammomium bromide; sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: (Z)-1,2-bis(phenylsulfonyl)ethene In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With dmap; triethylamine In dichloromethane at 20℃; | |
75% | With triethylamine In dichloromethane at 0 - 20℃; for 12.75h; Inert atmosphere; | 3.2 Step 2: Preparation of (S,Z)-4-hydroxybut-2-enyl 2-(6-methoxynaphthalen-2-yl)-propanoate (CD1-L2-OH) A solution of naproxen chloride (5.0 g, 20.0 mmol) in 10 mL of DCM was added to a stirred solution of cis-2-butene-1,4-diol (HO-L2-OH, 5.3 mL, 60.0 mmol) in 100 mL of DCM at 0° C. under a nitrogen atmosphere. To this stirred mixture was added triethylamine (4.2 mL, 30.0 mmol) drop-wise over 15 minutes and the resulting mixture was stirred at 0° C. for 30 minutes and at RT for overnight (~12 h), when TLC analysis of the mixture indicated formation of two product spots (i.e., mono and bis-acylated products). The mixture was washed with saturated sodium bicarbonate (3*100 mL), brine (3*100 mL), dried over anhydrous Na2SO4 and concentrated to afford 7.0 g of crude oily residue which was purified by column chromatography (150.0 g of silica gel, 200-400 mesh, eluted with 10% EtOAc in petroleum ether to isolate the bis-acylated compound and with 20% EtOAc in petroleum ether to isolate the desired mono-acylated product). The title compound was obtained as a white solid. Mp: 69-71° C.; Yield: 4.5 g (75%); 1H NMR (CDCl3, 300 MHz): δ 1.57 (d, J=6.9 Hz, 3H), 1.99 (br s, 1H), 3.85 (q, J=6.9, 7.2 Hz, 1H), 3.91 (s, 3H), 4.18 (t, J=4.8 Hz, 2H), 4.60-4.73 (m, 2H), 5.50-5.62 (m, 1H), 5.75-5.85 (m, 1H), 7.09-7.17 (m, 2H), 7.38 (dd, J=8.4, 1.5 Hz, 1H), 7.65 (br s, 1H), 7.70 (d, J=8.7 Hz, 2H); MS m/z: 323.1 [M+Na]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Ru metathesis catalyst In water at 45℃; for 12h; | ||
In water-d2 at 30℃; for 2h; | ||
With C19H14NO3Ru*F6P(1-) In water-d2 |
With C43H66Cl2N5ORu(2+)*2Cl(1-) In water at 25℃; for 0.166667h; | 6 Example 6 - isomerization of c/s-l,4-butenediol in water. 75 Appropriate amount of catalyst (0,5 mol%) was added on air, at 25 °C to a solution of 75 (12 mg, 0.14 mmol) in D20 (0,7 ml). Reaction mixture was transferred to an NMR tube and conversion and was determined using NMR method. Entry Catalyst Time [min] Conversion 1 47 8 93 | |
94 %Spectr. | With C106H182Cl2N2O34Ru In water-d2 at 20℃; for 24h; | |
With C106H182Cl2N2O34Ru In water-d2 at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Ru metathesis catalyst In water at 45℃; for 12h; Title compound not separated from byproducts; | ||
With Hoveyda-Grubbs catalyst second generation; 5,11,17,23-tetrakis(trimethylammoniomethyl)-25,26,27,28-tetrapropoxycalix<4>arene tetrachloride In water at 45℃; for 24h; optical yield given as %de; | ||
83.607 % de | With C39H58Cl2N4ORu(1+)*Cl(1-) In water-d2 at 25℃; for 24h; | 7 Example 7 - self metathesis of allyl alcohol in water. Appropriate amount of catalyst (2.5 or 5 mol%) was added on air to a solution of allyl alcohol (12 mg, 0.2 mmol) in D20 (1 ml). Reaction mixture was stirred at 25 °C. 0,7 ml of reaction mixture was transferred to an NMR tube and conversion was determined using NMR method. Entry Catalyst (loading mol %) Time [h] Conversion [%] E/Z |
78.947 % de | With C106H182Cl2N2O34Ru In water at 20℃; for 24h; Overall yield = 93 %Spectr.; | |
78.947 % de | With C106H182Cl2N2O34Ru In water-d2 at 20℃; for 24h; Overall yield = 94 percent; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | In 1,4-dioxane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine In tetrahydrofuran at 0 - 20℃; for 20h; | 150 Example 150; Carbonic acid 4-methoxycarbonyloxy-but-2-enyl ester methyl ester; Combine methyl chloroformate (7.04 g, 80.0 mmol) in THF (70 mL) and add dropwise to a ice-water cold solution of 2-buten-1, 4-diol (majority Z form) (19.7 g, 208 mmol) and pyridine (16.5 g, 208 mmol) in THF (150 mL). Warm the mixture to room temperature and stir for 20 hours. Remove the pyridine salt by filtration and concentrate the filtrate to a residue. Dissolve the residue with CH2C12 and wash sequentially with 1 N HCl and brine. Dry the organic layer over Na2S04 and concentrate the solvent in vacuo to give a residue. Purification by chromatography using hexanes : EtOAc = 12: 1 as the eluents give the title compound: 1H NMR (CDC13) : 85. 82-5.79 (m, 2H), 4.75 (d, J = 4.8 Hz, 4H), 3.79 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 97 - 210℃; Inert atmosphere; | 1 A Teflon (registered trademark) pouch containing E30N4 (γ-alumina, ring-form pellets (inner diameter: 2 mm, outer diameter: 5 mm, height: 3.8 mm), product of Nikki Chemical Co., Ltd.) (2.5 g) was securely placed in a pressure reactor (capacity: 100 mL). Under nitrogen, cis-2-butene-1,4-diol (35 mL (37.8 g, 0.43 mol)) and dibutylene glycol, an ether compound, (35 mL, (35.4 g, 0.21 mol) equivalent to 2.9 mol/L) were added to the aforementioned reactor, and γ-alumina was completely immersed in the liquid, followed by heating at 180°C for 10 hours. Subsequently, the mixture was cooled to room temperature, and the Telfon (registered trademark) pouch including γ-alumina was removed from the reactor. The thus-separated pouch was securely placed in a three-neck flask (capacity: 500 mL) equipped with an electromagnetic stirrer. To a first neck of the flask, a distillation column (inner diameter: 25 mm × length: 400 mm, no filler, NTP: 2) was connected, and a water-cooling reflux condenser was connected to the top of the distillation column. A thermometer was set in a second neck, and the third neck was employed as an inlet.Dehydration-cyclization reaction: cis-2-Butene-1,4-diol- (200 mL) was added to the aforementioned flask, and, under nitrogen, heated to 210°C at ambient pressure. 2,5-Dihydrofuran, water, and low-boiling-point by-products (e.g., crotonaldehyde and 4-hydroxybutanal) were distilled out through the top of the distillation column (97 to 101°C/ambient pressure), whereby the rate of distillation of 2,5-dihydrofuran was analyzed. The results are shown in table 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With C37H40Cl2N2ORuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; diastereoselective reaction; | |
58% | With 3,6-dichlorobenzene-1,2-dithiol; Hoveyda-Grubbs catalyst second generation; diethylzinc In tetrahydrofuran; hexane at 22℃; for 4h; Inert atmosphere; Sealed tube; stereoselective reaction; | |
40% | With C37H43N2ORuS2 In tetrahydrofuran at 22℃; for 6h; Inert atmosphere; diastereoselective reaction; | (Z)-4-phenylbut-2-en-l-ol (25b) [00592] (Z)-4-phenylbut-2-en-l-ol (25b) (Z-isomer is confirmed by comparison with the data reported in literature for Z and E-isomers: (a) Stille, J. K. Tetrahedron 1989, 45, 979. (b) Ely, R. J.; Morken, J. P. J. Am. Chem. Soc. 2010, 132, 2534): A solution of 6a (2.4 mg, 3.4 μιηο, 3.0 mol %) in tetrahydrofuran (230 μ) was transferred by syringe to a vial containing 23 (10.0 mg, 0.114 mmol, 1.00 equiv) and 24b (40.2 mg, 0.341 mmol, 3.00 equiv). The resulting mixture was allowed to stir for 6 hours at 22 °C. Analysis of the 1H NMR (400 MHz) spectrum revealed -50%) conv of the substrate, and the corresponding ROCM product 25b was obtained in >98:2 ZIE ratio. The resulting oil was purified by silica gel chromatography (20% EtOAc in hexanes to 40%) EtOAc in hexanes) to afford product 25b (6.1 mg, 0.046 mmol, 40%> yield) as colorless oil. 1H NMR (400 MHz, CDC13): Z-isomer (major): δ 7.20-7.30 (5H, m), 5.75 (2H, m), 4.32 (2H, d, J= 4.4 Hz), δ 3.45 (2H, d, J= 5.6 Hz). |
40% | With C42H49Cl2N3O3RuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; Glovebox; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C37H41Cl2N2ORuS2; In tetrahydrofuran; at 22℃; for 8h;Inert atmosphere; | General procedure: [00613] General Procedure for Cross-Metathesis (CM) Reactions [00614] In N2-filled glove box, an oven-dried 8 mL vial equipped with a magnetic stir bar was charged with alkene substrate (1.0 equiv) and cz's-2-butene-l,4-diol (2.0 equiv). To this vial, a solution of Ru complex Alb (5.0-7.5 mol %) in tetrahydrofuran or dichloromethane was added. The resulting solution was allowed to stir for 4-12 hours at 22C, after which the reaction was quenched by addition of wet diethyl ether and concentrated in vacuo (percent conversion was determined by 400 MHz or 500 MHz 1H NMR analysis). Purification was performed through silica gel chromatography or Kugelrohr distillation [00639] (Z)-3-(4-(trifluoromethyl henyl)-2-propene-l-ol (A71) [00640] Following the general procedure, a solution of Alb (7.3 mg, 9.5 muetaiotaomicron, 7.5 mol %) in tetrahydrofuran (255 mu) was transferred by syringe to a vial charged with 4- (trifluoromethyl)styrene (21.9 mg, 0.127 mmol, 1.00 equiv) and cz's-2-butene-l,4-diol (24.2 mg, 0.254 mmol, 2.00 equiv). The resulting solution was allowed to stir for eight hours at 22 C. Analysis of the unpurified mixture revealed 65% consumption of 4-(trifluoromethyl)styrene. The resulting brown oil was purified by silica gel chromatography (10% Et20 in hexanes to 40% Et20 in hexanes) to afford A71 (14.9 mg, 0.0737 mmol, 58% yield) as pale yellow oil in 92:08 ZIE ratio; 1H NMR (400 MHz, CDC13): Z-isomer (major): delta 7.60 (2H, d, J= 8.0 Hz), 7.32 (2H, d, J = 8.0 Hz), 6.60 (1H, d, J = 11.8 Hz), 6.00 (1H, dt, J = 12.4, 6.4 Hz), 4.42 (2H, s), 1.50 (1H, s). Coupling constant (J= 11.8 Hz) of the signal at delta 6.60 ppm is indicative of Z-A71. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With C42H49Cl2N3O3RuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; Glovebox; stereoselective reaction; | |
72% | With C37H41Cl2N2ORuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; diastereoselective reaction; | (Z)-2-tridecene-l-ol (A9) [00644] (Z)-2-tridecene-l-ol (A9) [00645] Following the general procedure in Section 2, a solution of lb (4.9 mg, 6.3 μηιο, 5.0 mol %) in tetrahydrofuran (255 μ) was transferred by syringe to a vial charged with 1- dodecene (21.4 mg, 0.127 mmol, 1.00 equiv) and cz's-2-butene-l,4-diol (24.2 mg, 0.254 mmol, 2.00 equiv). The resulting solution was allowed to stir for four hours at 22 °C. Analysis of the unpurified mixture revealed 81% consumption of 1-dodecene. The resulting brown oil was purified by silica gel chromatography (10% Et20 in hexanes to 40% Et20 in hexanes) to afford A9 (18.1 mg, 0.091 mmol, 72% yield) as pale yellow oil in 96:04 ZIE ratio. The spectral data for this compound were identical to those reported in the literature. Insect pheromone precursor 9 has been previously elaborated to (+)-disparlure over three steps in 49%> overall yield. |
72% | With C37H40Cl2N2ORuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; diastereoselective reaction; |
64% | With 3,6-dichlorobenzene-1,2-dithiol; Hoveyda-Grubbs catalyst second generation; diethylzinc In tetrahydrofuran; hexane at 22℃; for 4h; Inert atmosphere; Sealed tube; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With C42H49Cl2N3O3RuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; Glovebox; stereoselective reaction; | |
70% | With C37H40Cl2N2ORuS2 In tetrahydrofuran at 22℃; for 4h; Inert atmosphere; diastereoselective reaction; | |
62% | With 3,6-dichlorobenzene-1,2-dithiol; Hoveyda-Grubbs catalyst second generation; diethylzinc In tetrahydrofuran; hexane at 22℃; for 4h; Inert atmosphere; Sealed tube; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Hoveyda-Grubbs catalyst second generation In chlorobenzene at 0 - 110℃; for 3.5h; Inert atmosphere; | 7 [0076] Example 7- Cross Metathesis of Methyl Oleate and cis-1,4-Butenediol [0077] Methyl oleate (250 mg, 0.84 mmol) and cis-2-butene-1,4-diol (374.2 mg, 4.2474 mmol) were taken to a 25-mL three neck flask. The mixture was stirred at 0 °C in an ice bath under argon atmosphere. After 20 mins, solution of dichloro [1,3 -bis(2-methylphenyl)-2-imidazolidinylidene](2- isopropoxyphenylmethylene)ruthenium(II) (1.2 mg, 0.002 mmol; Stewart-Grubbs catalyst (5)) in 1.0 mL ethyl acetate) was added drop-wise over 1 h using a syringe pump. After 6 h at 0 °C, the reaction mixture was warmed to room temperature with continuous stirring. The reaction mixture was passed through a small plug of silica gel. An additional 2.0 mL of ethyl acetate was used to flush the silica gel plug. The filtrate was concentrated and purified by silica gel flash column chromatography (ethyl acetate:hexane, 1:9-*1:4). The desired product was obtained as a clear colorless liquid (114 mg, 76 % BORSM). 41 mg of unreacted starting material was recovered. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Stewart-Grubbs catalyst In ethyl acetate at 0℃; for 22h; Inert atmosphere; | 7 [0076] Example 7- Cross Metathesis of Methyl Oleate and cis-1,4-Butenediol [0077] Methyl oleate (250 mg, 0.84 mmol) and cis-2-butene-1,4-diol (374.2 mg, 4.2474 mmol) were taken to a 25-mL three neck flask. The mixture was stirred at 0 °C in an ice bath under argon atmosphere. After 20 mins, solution of dichloro [1,3 -bis(2-methylphenyl)-2-imidazolidinylidene](2- isopropoxyphenylmethylene)ruthenium(II) (1.2 mg, 0.002 mmol; Stewart-Grubbs catalyst (5)) in 1.0 mL ethyl acetate) was added drop-wise over 1 h using a syringe pump. After 6 h at 0 °C, the reaction mixture was warmed to room temperature with continuous stirring. The reaction mixture was passed through a small plug of silica gel. An additional 2.0 mL of ethyl acetate was used to flush the silica gel plug. The filtrate was concentrated and purified by silica gel flash column chromatography (ethyl acetate:hexane, 1:9-*1:4). The desired product was obtained as a clear colorless liquid (114 mg, 76 % BORSM). 41 mg of unreacted starting material was recovered. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15% | With trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron In toluene at 130℃; for 18h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron In toluene at 130℃; for 18h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In water at 120℃; for 6h; | 2.3. Catalytic reaction tests The catalyst was reduced at 200 °C for 1.5 h under an atmosphere consisting of Ar:H2 = 2:1. The freshly reduced catalyst(0.05 g) was mixed with BYD (0.568 g) and 1,2-propylene glycol (an internal standard required for gas chromatography analysis) in 10 mL of H2O. The mixture was transferred into a 50 mL batch reactor. The reactor was flushed with H2 three times, and catalytic hydrogenation was then carried out at a given H2 pressure and temperature. A blank test was performed following a conventional catalytic test procedure at 120°C and p(H2) = 2 MPa, using pure ZIF-8 as the catalyst. Less than2% conversion was obtained, indicating that ZIF-8 was inactive for the hydrogenation of BYD. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With C35H38N2O3RuS2 In tetrahydrofuran at 55℃; for 4h; Inert atmosphere; diastereoselective reaction; | |
26% | With C41H45N2ORuS2 In tetrahydrofuran at 55℃; for 8h; Inert atmosphere; | 4.1.2.1. General procedure for cross-metathesis General procedure: 4.1.2. General procedure for experimental procedure for ZStereoselectivecross- metathesis (CM) reactions4.1.2.1. General procedure for cross-metathesis (Table 1). In an ovendried10 mL vial equipped with a magnetic stir bar were placed thealkene substrate (0.15 mmol, 1.0 equiv) and Z-2-butene-1,4-diol(0.30 mmol, 2.0 equiv) under N2 atmosphere. The mixture wasadded a solution of 9 (5.0 mol %) in tetrahydrofuran (0.3 mL) andthen was vigorously stirred for 8 h at 55 °C to the end of the reaction.Organic solvent was removed in vacuo, and then the residuewas purified by silica gel column chromatography (30% Et2O inhexanes to 50% Et2O in hexanes) to give the desired product.4.1.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With [2,2]bipyridinyl; sodium carbonate; nickel dichloride In toluene at 130℃; for 36h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate In acetonitrile at 70℃; for 8h; Inert atmosphere; | 159 Synthesis of (Z)-4-(3-amino-4-nitrophenoxy)but-2-en-1 -ol: To a solution of (Z)-but-2- ene-1 ,4-diol (2.25 g, 25.6 mmol) in CH3CN (20.0 mL), at r.t under Ar (g) atmosphere, was added Cs2C03(6.26 g, 19.2 mmol) followed with 5-fluoro-2-nitroaniline (2.00 g, 12.8 mmol) and the reaction mixture was stirred at 70 °C for 8 h. The reaction mixture was filtered through a celite-pad, and the pad was washed with EtOAc (50 mL). The filtrate was concentrated under vacuum to obtain the crude product. The product was purified by silicagel chromatography. Fractions containing only the pure product were combined for concentration to obtain (Z)-4-(3- amino-4-nitrophenoxy)but-2-en-1 -ol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3.7 g | With pyridine; dmap In dichloromethane at -10℃; for 4h; | 1.2 2) Preparation of menthyl dicarbonate add the liquid phase containing L-menthyl chloroformate in the first step to the reactor, continue to place it in a cold well and keep the temperature at -10°C, add 10ml of dichloromethane, and then Add 0.8g (0.009mol) of 1,4-maleic diol, add 1.5ml of pyridine and 0.048g of DMAP into the dropping funnel and use 20ml of dichloromethane to fully dissolve and mix uniformly. The solution is slowly added dropwise to the reactor. The dropping rate was controlled at 1 drop per second, stirred and reacted for 4 hours, organic chromatography crystals, the organic phase was washed with dilute hydrochloric acid, saturated sodium bicarbonate, saturated brine in turn, the organic layer was dried with anhydrous magnesium sulfate, and finally performed with absolute ethanol Recrystallized to obtain 3.70 g of white solid menthyl dicarbonate. The yield was calculated to be 91.04% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium methylate In para-xylene at 150℃; for 36h; Sealed tube; Inert atmosphere; | 2.3. Synthesis of pyrrole from nitroarenes General procedure: To an oven dried 9 mL screw cap tube, a magnetic stir-bar,nitroarene (0.5 mmol), alkene-diol/alkyne-diol (2.0 mmol), NaOMe(0.375 mmol), Co(OAc)2-CC-800 (15 mol%) and p-xylene (2.5 mL)were added under argon atmosphere. Then, the tube was sealedand placed in a preheated oil bath at 150 C for 36 h. After completionof the reaction, the tube was allowed to cool at room temperature.The solvent was evaporated under reduced pressure, and thefinal product was purified by silica gel column chromatographyusing ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With sodium methylate In para-xylene at 150℃; for 36h; Sealed tube; Inert atmosphere; | 2.3. Synthesis of pyrrole from nitroarenes General procedure: To an oven dried 9 mL screw cap tube, a magnetic stir-bar,nitroarene (0.5 mmol), alkene-diol/alkyne-diol (2.0 mmol), NaOMe(0.375 mmol), Co(OAc)2-CC-800 (15 mol%) and p-xylene (2.5 mL)were added under argon atmosphere. Then, the tube was sealedand placed in a preheated oil bath at 150 C for 36 h. After completionof the reaction, the tube was allowed to cool at room temperature.The solvent was evaporated under reduced pressure, and thefinal product was purified by silica gel column chromatographyusing ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sodium methylate In para-xylene at 150℃; for 36h; Sealed tube; Inert atmosphere; | 2.3. Synthesis of pyrrole from nitroarenes General procedure: To an oven dried 9 mL screw cap tube, a magnetic stir-bar,nitroarene (0.5 mmol), alkene-diol/alkyne-diol (2.0 mmol), NaOMe(0.375 mmol), Co(OAc)2-CC-800 (15 mol%) and p-xylene (2.5 mL)were added under argon atmosphere. Then, the tube was sealedand placed in a preheated oil bath at 150 C for 36 h. After completionof the reaction, the tube was allowed to cool at room temperature.The solvent was evaporated under reduced pressure, and thefinal product was purified by silica gel column chromatographyusing ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In 1,4-dioxane at 139.84℃; for 24h; |
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H412 | Harmful to aquatic life with long-lasting effects |
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H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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