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USD 15-60
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USD 80+
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Structure of 1805-32-9 * Storage: {[proInfo.prStorage]}
* 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.
General procedure: The alcohol (1 mmol) was added to a mixture of TBHP(1 mmol) and VO(ephedrine)2MNPs (50 mg) in PEG(1 mL), and then the mixture was refluxed at 80 C for thetime specified. The progress was monitored by TLC (EtOAc/n-hexane, 1/2). After completion of the reaction, the catalystwas separated from the product by an external magnet(within 5 s), and the mixture was washed with EtOAc(25 mL) and decanted. The decanted mixturewas washedwith 30percent NaOH (5 mL) and the organic layer was dried overanhydrous Na2SO4. The evaporation of EtOAc underreduced pressure gave the pure products in 85e98percent yields.
86%
With dihydrogen peroxide In water; ethyl acetate at 45℃;
General procedure: All the reactions were carefully carried out at 40°C in a 25ml flask. In a typical procedure an amount of catalyst along with H2O2 was used for the oxidation process under mild conditions. The oxidation process was monitored by thin layer chromatography technique.
72.3%
With dihydrogen peroxide In neat (no solvent) at 80℃; for 2 h;
General procedure: All reactions were carried out in a glass reactor (∼50 mL) withbenzyl alcohol (1 mmol) as model substrate. The optimized amountof nano catalyst (0.04 g), H2O2(30 wtpercent in water) was added tothe reaction mixture and vigorously stirred at optimized reactionconditions. The aliquots of the reaction mixture were analysedby GC.
62%
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; C20H36N5(3+)*3Br(1-); oxygen; copper In water at 35℃; for 6 h; Schlenk technique
General procedure: A 30-mL Schlenk tube was evacuated and filled with O2, the benzyl alcohol (1 mmol), Cu powder (5percent mol), imidazolium (5percent mol), TEMPO (5percent mol), and H2O (3 mL) was added and stirred at 35 °C under an O2 atmosphere by connecting an O2 balloon. When the reaction was complete, the mixture was extracted with CH2Cl2 (3 × 10 mL). The combined extracts were dried (MgSO4). Then the solvent was removed and the mixture was purified by column chromatography (silica gel) to give the product.
92 %Chromat.
With Graphite oxide In toluene at 80℃; for 2 h; Sonication
General procedure: To a solution of alcohol (0.1 g) in2 mL of solvent was added the appropriate amount of GO (as indicated in Table2). The resulting mixture was irradiated in an ultrasonic bath or with an ultrasonic probe (methods A to G) for the time indicated in Table 2 prior to GC/MS analysis. The mixture was filtered through a sintered funnel and evaporated under reduced pressure. Purification was achieved by column chromatography using hexane as the eluent. The spectroscopic data of the obtained aldehydes were compared with authentic samples.16 Other products were also known compounds10–12 and were characterized by 1H NMR, mass spectrometry, and FT-IR spectroscopy.
Reference：
[1] Comptes Rendus Chimie, 2017, vol. 20, # 4, p. 435 - 439
[2] RSC Advances, 2014, vol. 4, # 90, p. 48777 - 48782
[3] Applied Organometallic Chemistry, 2017, vol. 31, # 5,
[4] Tetrahedron Letters, 2003, vol. 44, # 12, p. 2553 - 2555
[5] RSC Advances, 2016, vol. 6, # 80, p. 77020 - 77029
[6] Materials Research Bulletin, 2015, vol. 70, p. 753 - 761
[7] Journal of Molecular Catalysis A: Chemical, 2015, vol. 409, p. 42 - 49
[8] Synthesis (Germany), 2013, vol. 45, # 24, p. 3387 - 3391
[9] Applied Organometallic Chemistry, 2010, vol. 24, # 9, p. 663 - 666
[10] Acta Chemica Scandinavica, Series B: Organic Chemistry and Biochemistry, 1983, vol. 37, # 6, p. 499 - 508
[11] Journal of the Chemical Society - Perkin Transactions 1, 1998, # 15, p. 2239 - 2241
[12] Advanced Synthesis and Catalysis, 2007, vol. 349, # 7, p. 1173 - 1179
[13] Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2010, vol. 40, # 8, p. 516 - 520
[14] Inorganic Chemistry Communications, 2010, vol. 13, # 1, p. 195 - 198
[15] Catalysis Communications, 2010, vol. 11, # 5, p. 498 - 501
[16] Tetrahedron Letters, 2010, vol. 51, # 49, p. 6403 - 6405
[17] Inorganic Chemistry Communications, 2010, vol. 13, # 11, p. 1289 - 1292
[18] Inorganic Chemistry Communications, 2011, vol. 14, # 1, p. 155 - 158
[19] Green Chemistry, 2011, vol. 13, # 4, p. 991 - 997
[20] Inorganic Chemistry Communications, 2011, vol. 14, # 5, p. 690 - 693
[21] Phosphorus, Sulfur and Silicon and the Related Elements, 2012, vol. 187, # 3, p. 376 - 381
[22] Journal of Coordination Chemistry, 2012, vol. 65, # 15, p. 2671 - 2682
[23] Tetrahedron Letters, 2012, vol. 53, # 37, p. 4962 - 4965
[24] European Journal of Organic Chemistry, 2012, # 24, p. 4548 - 4554
[25] ACS Combinatorial Science, 2014, vol. 16, # 8, p. 397 - 402
[26] New Journal of Chemistry, 2015, vol. 39, # 6, p. 4933 - 4938
[27] Journal of Molecular Structure, 2017, vol. 1146, p. 644 - 659
2
[ 1805-32-9 ]
[ 3218-49-3 ]
Reference：
[1] Scientia Pharmaceutica, 2001, vol. 69, # 4, p. 329 - 350
3
[ 1805-32-9 ]
[ 18880-04-1 ]
Reference：
[1] Scientia Pharmaceutica, 2001, vol. 69, # 4, p. 329 - 350
4
[ 1805-32-9 ]
[ 5807-30-7 ]
Reference：
[1] Scientia Pharmaceutica, 2001, vol. 69, # 4, p. 329 - 350
5
[ 3112-85-4 ]
[ 1805-32-9 ]
[ 2039-83-0 ]
Reference：
[1] Chemical Communications, 2015, vol. 51, # 36, p. 7729 - 7732
6
[ 6287-38-3 ]
[ 1805-32-9 ]
Yield
Reaction Conditions
Operation in experiment
100%
With sodium tetrahydroborate In methanol at 0℃; Inert atmosphere
General procedure: Aldehyde (1 mmol) was dissolved in 10 ml ofmethanol(ethanol for ketones) and cooled to 0oC. NaBH4 (3 mmol) was then added inone portion and the reaction was allowed to stir until completion as indicatedby TLC (9:1 heptanes/ethyl acetate). The reaction was quenched with 0.1 N NaOH(10 ml) and extracted three times with ethyl actetate. The organic layer waswashed with brine and dried over Na2SO4. The solvent wasremoved under reduced pressure and the resulting yellow oil was subjected toflash chromatography.
90%
With sodium tetrahydroborate In methanol at 0 - 20℃; for 4 h;
General procedure: To a solution of 3,4-dimethoxybenzaldehyde (1 g, 6 mmol) in methanol was added NaBH4 (0.27, 7.2 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 4 h, quenched with 3percent aqueous HCl solution, and evaporated to dryness. The residue was extracted with CH2Cl2 and the organic layer was dried with MgSO4. Evaporation of the dried organic layer yielded 0.96g (3,4-dimethoxyphenyl)methanol (6D0) as a white solid.
Reference：
[1] European Journal of Medicinal Chemistry, 2016, vol. 108, p. 564 - 576
[2] Synthetic Communications, 2002, vol. 32, # 2, p. 219 - 223
[3] Bulletin of the Korean Chemical Society, 2015, vol. 36, # 6, p. 1676 - 1680
[4] Phytochemistry, 1999, vol. 51, # 5, p. 621 - 627
[5] Journal of Medicinal Chemistry, 1999, vol. 42, # 6, p. 1007 - 1017
[6] Patent: WO2011/46920, 2011, A1, . Location in patent: Page/Page column 89-90
[7] Tetrahedron Letters, 2014, vol. 55, # 32, p. 4458 - 4462
[8] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 12, p. 3145 - 3157
[9] Patent: DE1109700, 1959, ,
7
[ 1162648-58-9 ]
[ 1805-32-9 ]
Yield
Reaction Conditions
Operation in experiment
98%
at 20℃; for 0.0666667 h; Green chemistry
General procedure: A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4 (6.5 mg, ∼0.02 mmol) in methanol (2 mL) was stirred at room temperature. After completion of the reaction (monitored by TLC), solvent was evaporated, water (1 mL) was added to the mixture, and stirred vigorously. Decantation of the mixture gave almost pure product(s). The products were characterized by comparison of their IR and NMR data. The ionic liquid was dried at 65 ◦C under vacuum to remove moisture, and then reused.
96%
With poly (ethylene glycol)-sulfonated sodium montmorillonite nanocomposite In methanol at 20℃; for 0.0583333 h;
General procedure: A mixture of the substrate (1 mmol) and the PEG-SANMnanocomposite (8 mg) in methanol (2 mL) was stirred at roomtemperature. After completion of the reaction (monitored byTLC), the catalyst was filtered off and the solvent was evaporatedunder reduced pressure. The crude product was purifiedby column chromatography on silica gel to yield pure alcoholsand phenols.
Reference：
[1] Journal of Molecular Catalysis A: Chemical, 2012, vol. 365, p. 15 - 23
[2] Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 6, p. 944 - 951
[3] Journal of the Chinese Chemical Society, 2008, vol. 55, # 5, p. 943 - 946
8
[ 51-44-5 ]
[ 1805-32-9 ]
Reference：
[1] Journal of the American Chemical Society, 1973, vol. 95, p. 3757 - 3763
9
[ 6287-38-3 ]
[ 51-44-5 ]
[ 1805-32-9 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1930, vol. 49, p. 1082,1087
10
[ 75-91-2 ]
[ 1805-32-9 ]
[ 2905-68-2 ]
Yield
Reaction Conditions
Operation in experiment
85%
With copper (II)-fluoride In water; dimethyl sulfoxide at 120℃; for 12 h; Schlenk technique; Inert atmosphere; Green chemistry
General procedure: To a 50 mL Schlenk tube equipped with a stir bar was added 0.5 mmol of benzylic alcohol followed by 0.05 mmol of CuF2 (0.1 equiv). The mixture of DMSO (1.5 mL) and H2O (1.5 mL) was added, followed by 6 mmol of TBHP(12 equiv). The glass tube was vacuumed and purged with argon three times before it was tightly screw-capped. The reaction mixture was stirred at 120 Cfor 12 h, cooled to room temperature, poured into brine and extracted with EtOAc. The combined extracts were dried over MgSO4, filtered, and evaporated. The residue was purified by column chromatography (petroleumether/EtOAc) to afford the methyl ester
Stage #1: at 80℃; for 1 h; Sonication Stage #2: With Oxone In toluene for 2 h; Sonication
General procedure: To a solution of alcohol (1mmol) in 2mL of toluene was added GO (0.3g). The resulting mixture was sonicated in an Elmasonic P ultrasonic cleaning unit (ultrasonic bath) with a frequency of 37kHz and 100percent output power at 80°C for the time indicated in Table 4. Then Oxone (1mmol) and 2mL of an alcoholic solvent was added in the reaction medium and the resulting mixture was irradiated for the time indicated in Table 4. The mixture was filtered through a sintered funnel and evaporated under reduced pressure, and extracted with ethyl acetate. The organic layer was dried over Na2SO4, filtered and evaporated under reduced pressure. Purification was achieved by column chromatography using n-hexane/EtOAc: 100/3 as eluent. The spectroscopic data of the obtained esters were compared with authentic samples [5,40,42,43]. Spectroscopic data for methyl 3,4-dichlorobenzoate (entry 9, Table 4): Pale yellow, M.P. 44.7°C; IR (KBr) ν=3089, 3022, 2958, 1729, 1589, 1435, 1378, 1301, 1110, 757cm−1; 1H NMR (300MHz, CDCl3) δ=3.94 (s, 3H, CH3), 7.53 (d, J=8.3Hz, 1H, CH Arom), 7.87 (dd, J=8.3, 1.9Hz, 1H, CH Arom), 8.13 (d, J=1.9Hz, 1H, CH Arom); 13C NMR (75MHz, CDCl3) δ=52.54, 128.63, 129.94, 130.52, 131.53, 132.92, 137.56, 165.21; MS (EI) (70eV), m/z (percent): 208 (5) [M+4]+, 206 (31) [M+2]+, 204 (50) [M]+, 177 (10), 175 (62), 173 (100), 145 (30), 109 (20), 74 (18).
With 1,4-diaza-bicyclo[2.2.2]octane; TEMPOL; ammonia; copper(l) chloride In water; acetonitrile at 20℃; for 24 h;
General procedure: To a 25-mL Schlenk tube equipped with a magnetic stirrer, CuCl (0.05 mol, 5 molpercent), DABCO (0.10 mol, 10 molpercent), 4-HO-TEMPO (0.05 mmol, 5 molpercent) were added. Substrates 1 (1 mmol) and NH3 (aq, 25-28percent, 3 mmol, 3.0 equiv) in CH3CN (2 mL) were added subsequently. Then the reaction mixture was stirred at room temperature for 24 h in the presence of an air balloon. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4. Subsequently, the combined organic layer was concentrated under reduced pressure and the crude product was purified by column chromatography to afford the corresponding products.
Reference：
[1] Chinese Chemical Letters, 2018, vol. 29, # 3, p. 464 - 466
With borane-THF; In tetrahydrofuran; at 0 - 20℃; for 2h;
3,4-Dichlorobenzoic acid 3a (5.0 g, 26.32 mmol) was dissolved in 50 mL of tetrahydrofuran, and a borane tetrahydrofuran solution (52.6 mL, 52.64 mmol, 1 M/THF) was added dropwise at 0 C, and the mixture was reacted at room temperature for 2 hours. At 0 C, 50 mL of a 10% aqueous sodium hydroxide solution was added to quench the reaction. The organic layer was washed with saturated sodium chloride (50 mL). EtOAcjjjjjjjjj Methanol 7a (4.4 g, white solid), yield: 94.4%.
With tert.-butylhydroperoxide; at 80℃; for 7h;Green chemistry;
General procedure: The alcohol (1 mmol) was added to a mixture of TBHP(1 mmol) and VO(ephedrine)2MNPs (50 mg) in PEG(1 mL), and then the mixture was refluxed at 80 C for thetime specified. The progress was monitored by TLC (EtOAc/n-hexane, 1/2). After completion of the reaction, the catalystwas separated from the product by an external magnet(within 5 s), and the mixture was washed with EtOAc(25 mL) and decanted. The decanted mixturewas washedwith 30% NaOH (5 mL) and the organic layer was dried overanhydrous Na2SO4. The evaporation of EtOAc underreduced pressure gave the pure products in 85e98% yields.
86%
With dihydrogen peroxide; In water; ethyl acetate; at 45℃;
General procedure: All the reactions were carefully carried out at 40C in a 25ml flask. In a typical procedure an amount of catalyst along with H2O2 was used for the oxidation process under mild conditions. The oxidation process was monitored by thin layer chromatography technique.
72.3%
With dihydrogen peroxide; In neat (no solvent); at 80℃; for 2h;
General procedure: All reactions were carried out in a glass reactor (?50 mL) withbenzyl alcohol (1 mmol) as model substrate. The optimized amountof nano catalyst (0.04 g), H2O2(30 wt% in water) was added tothe reaction mixture and vigorously stirred at optimized reactionconditions. The aliquots of the reaction mixture were analysedby GC.
62%
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; C20H36N5(3+)*3Br(1-); oxygen; copper; In water; at 35℃; for 6h;Schlenk technique;
General procedure: A 30-mL Schlenk tube was evacuated and filled with O2, the benzyl alcohol (1 mmol), Cu powder (5% mol), imidazolium (5% mol), TEMPO (5% mol), and H2O (3 mL) was added and stirred at 35 C under an O2 atmosphere by connecting an O2 balloon. When the reaction was complete, the mixture was extracted with CH2Cl2 (3 × 10 mL). The combined extracts were dried (MgSO4). Then the solvent was removed and the mixture was purified by column chromatography (silica gel) to give the product.
92%Chromat.
With Graphite oxide; In toluene; at 80℃; for 2h;Sonication;
General procedure: To a solution of alcohol (0.1 g) in2 mL of solvent was added the appropriate amount of GO (as indicated in Table2). The resulting mixture was irradiated in an ultrasonic bath or with an ultrasonic probe (methods A to G) for the time indicated in Table 2 prior to GC/MS analysis. The mixture was filtered through a sintered funnel and evaporated under reduced pressure. Purification was achieved by column chromatography using hexane as the eluent. The spectroscopic data of the obtained aldehydes were compared with authentic samples.16 Other products were also known compounds10-12 and were characterized by 1H NMR, mass spectrometry, and FT-IR spectroscopy.
With potassium hydroxide; In dimethyl sulfoxide; at 20 - 130℃;
Examples 204-206 were prepared according to the method described below: 6'-[(3R)-3-[tert-Butyl(dimethyl)silyl]oxy}pyrrolidin-1-yl]-2-oxo-2H-1,3'-bipyridin-4-yl 4-bromobenzenesulfonate from Preparation 47 (197 mg, 0.324 mmol), the appropriate benzyl alcohol (0.982 mmol) and potassium hydroxide (55 mg) in DMSO (3 ml) were heated at 130 C. under nitrogen for 1 hour then allowed to stand at r.t. overnight. The reactions were diluted with methanol (3 ml) and passed down a SCX column, washed with methanol and the product eluted with 2M NH3 in methanol, evapourated to dryness. The residue was chromatographed on Biotage 12×150 mm silica column eluting with DCM/MeOH/NH3 98/2/0 to 93/7/1. Solvent removed in vacuo to give the title compound as solids. 204 LC-MS RT = 1.20 min m/z (APCI & ESI) 432 [MH+](2 min run)
With potassium carbonate; In ethyl acetate; N,N-dimethyl-formamide;
Step B Preparation 2-[(3,4-dichlorobenzyl)oxy]nitrobenzene A solution of <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> (25.0 g, 141 mmol), 2-fluorobenzaldehyde (14.9 mL, 141 mmol) and potassium carbonate (39.0 g, 282 mmol) in 100 mL of dry DMF was stirred a 60 C. overnight. The DMF was removed in vacuo, and the resulting product was taken up in EtOAc/water. The organic phase was washed with brine, dried (Na2SO4), filtered, and concentrated in vacuo to provide the titled compound.
With potassium carbonate; In ethyl acetate; N,N-dimethyl-formamide;
Step B Preparation 2-[(3,4-dichlorobenzyl)oxy]nitrobenzene A solution of <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> (25.0 g, 141 mmol), 2-fluorobenzaldehyde (14.9 mL, 141 mmol) and potassium carbonate (39.0 g, 282 mmol) in 100 mL of dry DMF was stirred a 60 C. overnight. The DMF was removed in vacuo, and the resulting product was taken up in EtOAc/water. The organic phase was washed with brine, dried (Na2SO4), filtered, and concentrated in vacuo to provide the titled compound.
With potassium carbonate; In ethyl acetate; N,N-dimethyl-formamide;
Step A Preparation 2-[(3,4-dichlorobenzyl)oxy]nitrobenzene A solution of <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> (25.0 g, 141 mmol), 2-fluorobenzaldehyde (14.9 mL, 141 mmol) and potassium carbonate (39.0 g, 282 mmol) in 100 mL of dry DMF was stirred a 60 C. overnight. The DMF was removed in vacuo, and the resulting product was taken up in EtOAc/water. The organic phase was washed with brine, dried (Na2 SO4), filtered, and concentrated in vacuo to provide the titled compound which was used in the next reaction without further purification.
b) 14.08 g (40 mmol) of bis(3,4-dichlorobenzyl) sulfide and 10.47 g (58.8 mmol) of <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> in 50 ml of methylene chloride are initially introduced under an N2 atmosphere into a reaction vessel equipped with stirrer and thermometer. 20.15 g (123.9 mmol) of hydrogen tetrafluoroborate (54% in diethyl ether) are added dropwise to the solution over a period of 10 minutes at an inside temperature of 20-30 C. with stirring, and the reaction mixture is stirred at RT for 4 hours. Another 1.13 g of hydrogen tetrafluoroborate (54% in diethyl ether) are added to the reaction mixture and stirring at RT is continued for 3 hours. The reaction mixture is then filtered, and the residue is dried at RT in a high vacuum. The crude product is again stirred in 100 ml of water at RT, filtered, and the residue is dried at RT overnight in a high vacuum. This gives 18.3 g (76.41% of theory) of tris(3,4-dichlorobenzyl) sulfonium tetrafluoroborate in the form of white crystals of melting point 201-203 C. 1 H-NMR (100 MHz, DMSO) in ppm: 4.8 (singlet, 6H); 7.32-7.64 (multiplet, 9H).
1-(3,4-dichlorobenzyloxy)-2,3-epoxypropane[ No CAS ]
2-[(3,4-dichlorobenzyloxy)methyl]morpholine hydrogen maleate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
EXAMPLE 13 2-[(3,4-Dichlorobenzyloxy)methyl]morpholine hydrogen maleate Application of the procedure of Example (1a) to <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> enables 1-(3,4-dichlorobenzyloxy)-2,3-epoxypropane to be prepared. The latter, when condensed with 2-aminoethyl hydrogen sulfate (ester) according to Example (1b), yields the compound of formula: STR22 Empirical formula: C16 H19 Cl2 N2 O6 Molecular mass: 392.23 Melting point: 144 C. Thin layer chromatography: support: silica gel Merck 60 F 254 solvent: chloroform/methanol/ammonia solution (80:18:2) visualization: UV and iodine Rf: 0.60 Solubility: soluble to 1% in water.
With potassium tert-butylate; trichlorophosphate; In N-methyl-acetamide; ethyl acetate;
EXAMPLE 8 1-(3,4-Dichlorobenzyloxy)-3-methyl-4-isoquinoline Acetic Acid 1,2-Dihydro-3-methyl-1-oxo-4-isoquinoline acetic acid (770 mg., 3.30 mmol) and phosphorous oxychloride (1.0 ml. 10.7 mmol) were refluxed in 8 ml. ethyl acetate for 16 hr then vacuum evaporated to dryness. The residue was partitioned between water and ethyl acetate. The aqueous phase was washed with ether. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered, and vacuum evaporated to yield a viscous, homogeneous oil, 1-chloro-3-methyl-4-isoquinoline acetic acid; 772 mg. (99%). This oil (623 mg., 2.65 mmol) in 6 ml. dimethylformamide was added to a solution of <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> (2.75 g., 15.5 mmol) and potassium tert-butoxide (600 mg., 534 mmol) in 2 ml. dimethylformamide and the mixture was heated at 115 for 3 hr. After cooling the mixture was poured onto crushed ice and washed with 3*60 ml. ether. The basic aqueous layer was acidified to pH 3 with 1 N hydrochloric acid and extracted 3*100 ml. ether. The organic extract was dried over magnesium sulfate, filtered, and vacuum evaporated to an oily solid; 568 mg. (57%). Trituration of this residue with methanol then hexane and fractional crystallization from chloroform afforded pure title compound: 44 mg. (4%), mp 180-183.
With triphenylphosphine on polystyrene; di-isopropyl azodicarboxylate; In tetrahydrofuran; at 0 - 20℃;
Step 2:[180] A mixture of polymer-supported triphenylphosphine (1.46 g, ~ 4.4 mmol) and <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> (0.65 g, 3.6 mmol) was stirred in THF (10 mL) at 0 C. Keeping the reaction mixture at 0 0C, a solution of diisopropylazodicarboxylate (0.87 mL, 4.4 mmol) in THF (2.1 mL) was added dropwise. 2-(2,6-Dioxo-piperidin-3-yl)-4-hydroxy- isoindole-l,3-dione (1.00 g, 3.60 mmol) was then added as a solid, the reaction mixture was stirred at 0 0C for 1 h and then at room temperature overnight. The solvent was evaporated under vacuum and the residue was chromatographed using a methanol-CH2Cl2 gradient, eluting the product at 95:5 CH2Cl2-methanol. This material was dissolved in ethyl acetate (150 mL) and water (100 mL) was added. The organic phase was then washed with 10% dilute aqueous sodium carbonate (2 x 50 mL) and water (3 x 50 mL). The solvent was removed under vacuum and the resulting solid was triturated with ether, filtered and dried to provide the title compound as a white solid (0.41 g, 26% yield); mp 245-247 0C; HPLC, Waters Symmetry C-18, 3.9 x 150 mm, 5 mum, 1 mL/min, 240 nm, 60/40 CH3CN/0.1 % H3PO4, 3.50 (99.78%); 1H NMR (DMSO-J6) delta 2.02-2.07 (m, IH), 2.45-2.62 (m, 2H), 2.82- 2.96 (m, IH), 5.12 (dd, J = 12.6 Hz, J = 5.4 Hz, IH), 5.38 (s, 2H), 7.49-7.51 (m, 2H)5 7.57 (d, J = 8.5 Hz, IH), 7.71 (d, J = 8.2 Hz, IH), 7.81-7.88 (m, 2H), 1 1.12 (s, IH); 13C NMR (DMSO-J6) delta 22.0, 30.9, 48.8, 68.5, 115.9, 116.8, 120.1, 127.3, 129.0, 130.5, 130.8, 131.2, 133.3, 137.1, 137.5, 155.1, 165.3, 166.8, 169.9, 172.8; Anal. Calcd for C20H14N2O5Cl2 + 0.3 H2O: C, 54.76; H, 3.35; N, 6.39. Found: C, 54.48; H, 3.07; N, 6.29.
With methanol; 1,3-disulfonic acid imidazolium hydrogen sulfate; at 20℃; for 0.0666667h;Green chemistry;
General procedure: A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4 (6.5 mg, ?0.02 mmol) in methanol (2 mL) was stirred at room temperature. After completion of the reaction (monitored by TLC), solvent was evaporated, water (1 mL) was added to the mixture, and stirred vigorously. Decantation of the mixture gave almost pure product(s). The products were characterized by comparison of their IR and NMR data. The ionic liquid was dried at 65 ?C under vacuum to remove moisture, and then reused.
96%
With poly (ethylene glycol)-sulfonated sodium montmorillonite nanocomposite; In methanol; at 20℃; for 0.0583333h;
General procedure: A mixture of the substrate (1 mmol) and the PEG-SANMnanocomposite (8 mg) in methanol (2 mL) was stirred at roomtemperature. After completion of the reaction (monitored byTLC), the catalyst was filtered off and the solvent was evaporatedunder reduced pressure. The crude product was purifiedby column chromatography on silica gel to yield pure alcoholsand phenols.
95%
With Nanoporous Na+-Montmorillonite Perchloric Acid; In ethanol; at 20℃; for 0.0333333h;
General procedure: A mixture of the substrate (1 mmol) and MMT-HClO4(10 mg) in ethanol (2 mL) was stirred at room temperature.The progress of the reaction was monitored by TLC, ethylacetate: n-hexane (3:7). After completion of the reactionthe catalyst was filtered off and the solvent was evaporatedunder reduced pressure. The crude product was purifiedby column chromatography on silica gel (EtOAc:hexane=1:4) to gave the pure alcohol and/or phenol derivative ingood to high yields.
With 1,3-disulfonic acid imidazolium hydrogen sulfate; In neat (no solvent); at 20℃; for 0.0166667h;Green chemistry;
General procedure: Ionic liquid [Dsim]HSO4 (6.5 mg, ?0.02 mmol) was added to a stirred mixture of alcohol, phenol or naphthol (1.0 mmol) and HMDS (80 mg, 0.5 mmol) at room temperature under solvent free conditions. After completion of the reaction (monitored by TLC, It should be noted that when addition of HMDS is finished stirring of the mixture is stopped after 1 min. TLC showed that in most of the cases the reaction is completed immediately after the addition of HMDS), the product was extracted with Et2O and the ionic liquid was recovered and was dried at 65 ?C under vacuum to remove moisture, and then reused. Evaporation of the solvent under reduced pressure gave the highly pure product without further purification. The desired pure products were characterized by comparison of their IR, NMR and MS data as well as boiling poin twith those of known compounds
95%
With C10H10N2O6S2(2+)*2HO4S(1-); at 20℃;
General procedure: A mixture of the substrate (1 mmol), hexamethyldisilazane (0.70 mmol), and/or 3,4-dihydro-2H-pyran (1.4 mmol) and BiPy(SO3H)2(HSO4)2 (10 mg, 1.95 mol%) in CH3CN(3 mL) and/or CH2Cl2 (3 mL) was stirred at room temperature. The progress of thereaction was monitored by TLC (n-hexane: EtOAc; 10:1) and/or GC. After completion ofthe reaction, the mixture was filtered to separate the solid catalyst. Then the solution wasfiltered through a silica gel pad and washed with CH3CN (2 × 3 mL) and/or CH2Cl2 (2 ×3 mL). Evaporation of the solvent gave the desired products in high purity.
95%
With poly(4-vinylpyridine) supported copper(II) oxide nanoparticles; In acetonitrile; at 75℃; for 0.0333333h;
General procedure: A mixture of the substrate (1 mmol), HMDS (1 mmol) and PC-NPs (20 mg), in acetonitrile (3 mL), was refluxed at 75 C. After completion of the reaction (monitored byTLC using a 1:1 mixture of EtOAc/n-hexane), the mixture was filtered and the residue was washed with acetonitrile (5 mL). Evaporation of the solvent gave almost the pure product(s). Further purification was proceeded by bulb-to-bulb distillation under reduced pressure or recrystallization to afford the pure silyl ether.
93%
With poly (ethylene glycol)-sulfonated sodium montmorillonite nanocomposite; In acetonitrile; at 20℃; for 0.0666667h;
General procedure: HMDS (0.5 mmol) was added to a stirring mixture of the substrate(1 mmol), and the PEG-SANM nanocomposite (8 mg)in CH3CN (2 mL) at room temperature. The progress of thereaction was monitored by TLC. After completion of the reaction,the mixture was filtered and the recovered catalyst waswashed with acetonitrile and acetone, dried at 80C and reusedfor the same reaction. Evaporation of the solvent gave almostpure product. Further purification proceeded by recrystallizationto yield pure silyl ether.
92%
With Nanoporous Na+-Montmorillonite Perchloric Acid; In acetonitrile; at 20℃; for 0.0333333h;
General procedure: To a stirring mixture of the substrate (1 mmol) and MMTHClO4(7 mg) in CH3CN (3 mL), HMDS (0.75 mmol)was added at room temperature. After completion of thereaction, indicated by TLC, ethyl acetate: n-hexane (3:7),the mixture was filtered to separate the catalyst. The filtratewas washed with acetonitrile (5 mL). Removal of the solvent under reduced pressure gave almost pure productin good to high yields. Further purification was carriedout by column chromatography on silica gel (eluting withEtOAc:hexane = 1:4), if necessary.
82%
With rice husk ash; In acetonitrile; at 20℃; for 0.133333h;Green chemistry;
General procedure: To a stirring mixture of the substrate (1 mmol) and RiHA (0.08 g) in CH3CN (3 mL),HMDS (0.75 mmol, 0.120 g) was added at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was filtered and the residue was washed with acetonitrile (5 mL). Evaporation of the solvent gave almost pure product(s). Further purification was carried out by bulb-to-bulb distillation under reduced pressure or recrystallization to afford pure silyl ether(s).
Preparation of Examples 6-18 - 6-22 Preparation of 3,4-dichlorobenzyl 2-(5,6,7,8-tetrahydro-1,8-naphthyridin-2- yl)ethylcarbamate (6-22)A solution of carbonyl diimidazole (53 mg, 0.30 mmol) in anhydrous methylene chloride (1 mL) was added slowly to a solution of <strong>[1805-32-9]3,4-dichlorobenzyl alcohol</strong> (49 mg, 0.30 mmol) in anhydrous methylene chloride (1 mL) at 0 C under nitrogen. The mixture was warmed to room temperature after which a suspension of 2- (5,6,7,8-tetrahydro-1 ,8-naphthyridin-2-yl)ethanamine hydrochloride (64 mg, 0.30 mmol) and resin-bound diisopropylethylamine (225 mg, 0.90 mmol) in anhydrous methylene chloride (2 mL) was added. The mixture was stirred for 2 h after which the solids were removed by filtration and the solvents were removed from the filtrate under reduced pressure. The residue was purified by flash column chromatography on silica gel, eluting with methanol/methylene chloride (1 :19), to provide 3,4-dichlorobenzyl 2-(5,6,7,8-tetrahydro-1 ,8- naphthyridin-2-yl)ethylcarbamate (39 mg, 34%) as a white solid: 1H NMR (300 MHz, CDCI3) delta 7.48-7.38 (m, 2H), 7.17 (d, 1H), 7.07 (d, 1H), 6.34 (d, 1H), 5.65 (br s, 1 H), 5.06 (S1 2H), 4.78 (br s, 1 H), 3.57-3.45 (m, 2H), 3.45-3.36 (m, 2H), 2.78-2.65 (m, 4H), 1.97-1.86 (m, 2H) ppm; ESI MS m/z 380 .
With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; toluene; at 20℃; for 2h;Inert atmosphere;
(39A) 2-Chloro-4-(3,4-dichlorobenzyloxy)benzaldehyde 2-Chloro-4-hydroxybenzaldehyde (324 mg, 2.07 mmol), 3,4-dichlorobenzyl alcohol (513 mg, 2.90 mmol), and triphenylphosphine (760 mg, 2.90 mmol) were dissolved in tetrahydrofuran (8 mL), and a diethyl azodicarboxylate toluene solution (2.2 M, 1.32 mL, 2.90 mmol) was slowly added dropwise thereto at room temperature, and then, the resulting mixture was stirred under a nitrogen atmosphere at room temperature for 2 hours. The solvent in the reaction solution was distilled off under reduced pressure, and the resulting residue was washed with hexane/dichloromethane (6/1 (v/v)), whereby the objective title compound was obtained as a white solid (244 mg, yield: 37percent). 1H NMR (CDCl3, 400 MHz): delta5.06 (2H, s), 6.93 (1H, dd, J=2.3, 8.6 Hz), 6.99 (1H, d, J=2.3 Hz), 7.24 (1H, m), 7.47 (1H, d, J=8.6 Hz), 7.52 (1H, d, J=2.3 Hz), 7.90 (1H, d, J=8.6 Hz), 10.3 (1H, s)
37%
With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; toluene; at 60℃; for 4h;Inert atmosphere;
General procedure: To a solution of 18 (100 mg,0.420 mmol) and [4-(trifluoromethyl)phenyl]methanol (111 mg,0.630 mmol) in THF (10.0 mL), PPh3 (178 mg, 0.68 mmol), a 40percentdiethyl azodicarbonate toluene solution (309 lL, 0.680 mmol)were added at room temperature, and stirred under N2 atmosphereat 60 C for 4 h. After cooling to room temperature, the solvent wasdistilled off under reduced pressure. The residue was purified bysilica gel column chromatography (hexane/AcOEt = 100:0 to 95:5(v/v)) to obtain 19k as colorless oil (125 mg, 75percent).
With triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; toluene; at 60℃; for 4h;Inert atmosphere;
General procedure: To a solution of 18 (100 mg,0.420 mmol) and [4-(trifluoromethyl)phenyl]methanol (111 mg,0.630 mmol) in THF (10.0 mL), PPh3 (178 mg, 0.68 mmol), a 40%diethyl azodicarbonate toluene solution (309 lL, 0.680 mmol)were added at room temperature, and stirred under N2 atmosphereat 60 C for 4 h. After cooling to room temperature, the solvent wasdistilled off under reduced pressure. The residue was purified bysilica gel column chromatography (hexane/AcOEt = 100:0 to 95:5(v/v)) to obtain 19k as colorless oil (125 mg, 75%).
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