* 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.
With potassium carbonate In acetonitrile for 12 h; Reflux
2-hydroxybenzaldehyde 9 (0.5 ml, 4.69 mmol, Sigma-Aldrich catalogue id: S356) was dissolved in CH3CN (10 ml) and K2CO3 (0.97 ml, 7.03 mmol) and 3-bromoprop- 1 -ene (0.45 ml, 5.16 mmol, Sigma-Aldrich catalogue id: 337528) were added. Mixture was stirred at reflux for 12 hours. Solvent was then evaporated in vacuum and the residue dissolved in EtOAc (5 ml_). Water (10 ml) was added and the mixture stirred for 10 min at room temperature. Organic phase was then separated and the aqueous layer was extracted with EtOAc (2x10 ml). The combined organic phases were dried over Na2SO4, filtered and concentrated under reduced pressure to give title compound 10. Yield 99percent. 1H NMR (400 MHz, CDCI3) δ = 10.25 (1 H, s), 7.54-7.52 (1 H, m), 7.23- 7.19 (1 H, m), 6.72-6.66 (2H, m), 5.82-5.75 (1 H, m), 5.20-5.15 (1 H, d, J=17.6 Hz), 5.05-5.03(1 H, d, J=10.8 Hz), 4.33-4.31 (2H, m) ppm. 13C NMR (CDCI3) δ 188.9, 160.6, 135.6, 132.2, 127.8, 124.7, 120.5, 1 17.5, 1 12.7, 68.7 ppm, Liquid chromatography Mass Spectroscopy (LCMS) m/z (ES+) m/z: 347.0 [2M + Na]+, 185.0 [M + Na]+, 163.0 [M + H]+. Elemental analysis for Ci0H10O2: Calcd. C 74.06, H 6.21 ; Found C 74.36, H 6.52.
96%
With potassium carbonate In acetonitrile for 2 h; Reflux
To a solution of 2-hydroxybenzaldehyde (15 g, 123 mmol, 1 equiv) and allylbromide (11.7 mL, 135 mmol, 1.1 equiv) in MeCN (250 mL) was added K2C03 (23.8 g, 172 mmol, 1.4 equiv). The yellow slurry was then heated to reflux. After 2 h, TLC indicated complete conversion. The now pale cream colored mixture was removed from heat and filtered. The filtrate was concentrated invacuo to provide 2-(allyloxy)benzaldehyde (19.15 g, 96percent) as a yellow oil. 1H NMR (400 MHz, CDCl3) 8 10.64- 10.49 (m, 1H), 7.86 (dd, J = 7.7, 1.9 Hz, 1H), 7.61 -7.49(m, 1H), 7.11-6.90(m,2H),6.10(ddt,J= 17.3, 10.5,5.2Hz, 1H),5.47(dq,J=17.3, 1.5 Hz, 1H), 5.36 (dq, J = 10.5, 1.4 Hz, 1H), 4.68 (dt, J = 5.1, 1.6 Hz, 2H).
87%
Stage #1: With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.25 h; Stage #2: at 60℃; for 12 h;
General procedure: To the stirred solution of salicylic aldehyde (0.1 mol) (or 2-hydroxy-3-methoxybenzaldehyde (o-vanilin)) in DMF (40 mL), dry K2CO3 (0.12 mol) was added and the mixture was stirred for 15 min at 20 °C. Then corresponding alkyl halide (0.1 mol) was added, and the reaction mixture was stirred for 12 h at 60 °C. The cooled reaction mixture was poured into water (250 mL) and extracted by CH2Cl2 (40 mL). An organic layer was separated, washed with NH4OH 5percent (5×25 mL) and water (50 mL), and dried over Na2SO4. A solvent was removed in vacuo and the residue was crystallized by adding of cyclohexane (in case of the solid compounds, see p.p. 4.2.1–4.2.4), or distilled in vacuo 1 mm. Hg (in case of liquids, see p.p. 4.2.5–4.2.7).
85%
With potassium carbonate In acetone for 6 h; Reflux
K2CO3 (2.25g, 0.016 moles) was added to the stirred solution of 2-hydroxybenzaldehyde (1g, 0.008 moles) in acetone (8 ml) and followed by allyl bromide (0.99 g, 0.008moles). These contents were stirred under reflux conditions for 6 h. After completion of the reaction (TLC), the reaction mixture was filtered, the solvent was removed under reduced pressure, the crude reaction mixture was quenched with water and extracted with diethyl ether (3 x 20 ml), the layers were separated and the organic layer was dried over Na2SO4. Solvent was removed under reduced pressure; the crude product was purified by column chromatography (hexane) to afford the desired product 1aa as colourless solid in 85percent yield.The compound was well characterised by spectral data.
84%
With 18-crown-6 ether; potassium carbonate; potassium iodide In acetonitrile at 75℃; for 18 h; Inert atmosphere
To a stirred solution of salicylaldehyde (20.0 g, 164 mmol) in acetonitrile (200 mL) was added allylbromide (27) (29.0 mL, 333 mmol), KI (544 mg, 3.28mmol), 18-crown-6 (432 mg, 1.64 mmol) and K2CO3 (66.0 g, 478 mmol) at rt after which the solution was refluxed at 75 °C for 18 h. The K2CO3 was filtered off and the solvent removed under reduced pressure. H2O (100 mL) was added and the aqueous layer extracted with EtOAc (2×100 mL). The organic layers were combined, washed with brine (50 mL), dried (Na2SO4) and the solvent removed under reduced pressure to yield the title compound as an orange oil (24.2 g, 84percent). TLC Rf=0.28 (Hexane/EtOAc 19:1). IR νmax (neat)/cm−1: 2861 w (C–H str), 1681 s (C=O str), 1598 s (C=C str), 1483 m (C=C str), 1457 m (C=C str). 1H NMR (400 MHz, CDCl3): δ 10.51 (1H, s, –CHO), 7.80 (2H, dd, J 7.5, 1.7 Hz, ArH), 7.50 (1H, ddd, J 8.5, 7.5, 2.0 Hz, ArH), 6.99 (1H, t, J 7.5 Hz, ArH), 6.95 (1H, d, J 8.5 Hz, ArH), 6.10–6.00 (1H, m, –CHCH2), 5.43 (1H, dq, J 17.4, 1.7 Hz, –CH2), 5.31 (1H, dq, J 10.6, 1.4 Hz, –CH2), 4.63 (1H, dt, J=5.1, 1.4 Hz, –CH2–). 13C NMR (125 MHz, CDCl3): δ 189.7, 160.9, 135.9, 132.4, 128.4, 125.1, 120.9, 118.1, 112.9, 69.2. HRMS (ESI+) m/z=163.0751 [M+H]+ found, C10H11O2+ required 163.0754.
82.3%
With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 15 h;
The o-hydroxybenzaldehyde is first reacted with 3-bromopropene,To give intermediate O-A,And then under high temperature conditions for rearrangement reaction,To give 2-hydroxy-3-allylbenzaldehyde,As shown in Scheme 6,The specific preparation method is as follows: O-hydroxybenzaldehyde (290 g, 2.38 mol) was dissolved in 500 ml of DMF,K2CO3 (493 g, 3.57 mol) was added,Followed by the dropwise addition of 3-bromopropene (346 g, 2.86 mol)60 reaction 15h,Filter,The filtrate was poured into 500 mL of CH2Cl2,The organic phase was washed successively with 5percent aqueous NaOH,Saturated salt water and washed,Anhydrous Na2SO4 dried,Concentrated under reduced pressure,To give 317 g of a yellow oil,Yield 82.3percent.317 g (1.96 mol) of 2-allyloxybenzaldehyde was reacted at 200 ° C for 4 h,And distilled under reduced pressure to give 200 g of 3-allyl-2-hydroxybenzaldehyde as a yellow oil,Yield 63percent
80%
With sodium hydride In tetrahydrofuran; N,N-dimethyl-formamide at 25℃; for 4 h;
It was prepared from2-allyloxybenzaldehyde, by addition of chloroform followed by reaction withethyl chloroformate.(a) 2-Allyloxybenzaldehyde: Itwas prepared by the allylation of salicylaldehyde with allyl bromide accordingto the method reported in literature3 with some modifications. A solution of allylbromide (3.6 g, 0.03 mol) in 5 mL dry THF was added dropwise to astirred mixture of salisylaldehyde (2.44 g, 0.02 mol) and sodium hydride [1.0 g(60 percent in oil), 0.04 mol] in 40 mL dry THF and 5 mL DMF at room temperature 25C. After completion of reaction (4 h), the reaction mixture was filtered toremove the inorganic solid residue. The solid on the filter paper was washedwith more THF (3 × 10 mL). The combined organic filtrate was evaporared on arotavapor. The concentrated reaction product was diluted with 30 mL diethylether and washed successively with 5 percent aq NaOH solution (3 × 10 mL) followed bywater (3 × 10 mL). The organic layer was dried over anhydrous sodium sulphatefor 4-5 h and filtered. Evaporation of the filtrate under reduced pressure on arotavapor afforded 2-allyloxybenzaldehyde (2.58 g, 80 percent) as a light yellow liquid.
78.9%
With potassium carbonate; potassium iodide In acetonitrileReflux
In a 50 ml round-bottom flask by adding salicyldehyde (0.61g, 5 . 0mmoL), 35.0 ml acetonitrile, 3-bromopropylene (0.72g, 6 . 0mmol), potassium carbonate (2.07g, 15 . 0mol), a catalytic amount of potassium iodide, reflux reaction. After the end of the detection reaction TLC, solvent evaporation to dryness, separating by silica gel column, to obtain 0.64g oily, yield 78.9percent. 1 HNMR (300MHz, CDCl 3): δ 10.54 (s, 1H), 6.98-7.84 (m, 4H), 6.07 (m, 1H), 5.46 (dd, 1H, J = 16.8,1 . 5Hz,), 5.34 (d, 1H, J = 10.8,1 . 5Hz), 4.66 (d, 2H, J = 5.2Hz).
70%
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 12 h;
General procedure: The bromoalkene (11.0 mmol) was added to a suspension of K2CO3 (14.4 mmol) and 3,5-di-tert-butyl-2-hydroxybenzaldehyde (11.0 mmol) in DMF (50 mL) and stirred at room temperature for 12 h. The mixture was diluted with CH2Cl2 (25 mL) and washed twice with water, dried using Na2SO4 (anhydrous) and concentrated under reduced pressure. The crude product was purified by flash chromatography (SiO2: hexane/EtOAc, 15:1 unless indicated otherwise).
Reference：
[1] European Journal of Medicinal Chemistry, 2010, vol. 45, # 11, p. 5265 - 5277
[2] Angewandte Chemie - International Edition, 2009, vol. 48, # 51, p. 9690 - 9692
[3] Angewandte Chemie - International Edition, 2011, vol. 50, # 26, p. 5932 - 5937
[4] Chemistry - A European Journal, 2013, vol. 19, # 47, p. 15852 - 15855
[5] Tetrahedron Letters, 1995, vol. 36, # 11, p. 1845 - 1848
[6] European Journal of Medicinal Chemistry, 1997, vol. 32, # 1, p. 71 - 82
[7] ACS Medicinal Chemistry Letters, 2013, vol. 4, # 9, p. 852 - 857
[8] Patent: WO2014/202697, 2014, A1, . Location in patent: Page/Page column 18; 19
[9] European Journal of Organic Chemistry, 2015, vol. 2015, # 6, p. 1341 - 1354
[10] Journal of Organic Chemistry, 2015, vol. 80, # 9, p. 4683 - 4696
[11] Advanced Synthesis and Catalysis, 2015, vol. 357, # 14-15, p. 3040 - 3046
[12] Synthetic Communications, 1996, vol. 26, # 17, p. 3201 - 3215
[13] Patent: WO2010/91382, 2010, A1, . Location in patent: Page/Page column 31
[14] Angewandte Chemie - International Edition, 2013, vol. 52, # 15, p. 4198 - 4202[15] Angew. Chem., 2013, vol. 125, # 15, p. 4292 - 4296,5
[16] Chemical Communications, 2013, vol. 49, # 99, p. 11665 - 11667
[17] Patent: WO2014/164428, 2014, A1, . Location in patent: Page/Page column 99; 100
[18] Journal of Medicinal Chemistry, 2015, vol. 58, # 9, p. 4046 - 4065
[19] Organic Preparations and Procedures International, 1996, vol. 28, # 2, p. 217 - 221
[20] Journal of the Chinese Chemical Society, 2008, vol. 55, # 4, p. 923 - 932
[21] European Journal of Organic Chemistry, 2015, vol. 2015, # 21, p. 4689 - 4698
[22] Tetrahedron Asymmetry, 1995, vol. 6, # 6, p. 1295 - 1300
[23] Synthesis, 2006, # 19, p. 3261 - 3269
[24] Tetrahedron, 1993, vol. 49, # 36, p. 8179 - 8194
[25] Green Chemistry, 2012, vol. 14, # 12, p. 3429 - 3435
[26] Bulletin of the Chemical Society of Japan, 1982, vol. 55, # 8, p. 2450 - 2455
[27] Synlett, 2007, # 13, p. 2011 - 2016
[28] Tetrahedron, 2017, vol. 73, # 31, p. 4671 - 4683
[29] Journal of the American Chemical Society, 2009, vol. 131, # 40, p. 14190 - 14191
[30] European Journal of Organic Chemistry, 2015, vol. 2015, # 34, p. 7602 - 7611
[31] Organic Letters, 2009, vol. 11, # 14, p. 2972 - 2975
[32] Organic and Biomolecular Chemistry, 2011, vol. 9, # 20, p. 7196 - 7206
[33] Tetrahedron, 2017, vol. 73, # 5, p. 542 - 549
[34] Journal of Organic Chemistry, 2008, vol. 73, # 14, p. 5633 - 5635
[35] Journal of the American Chemical Society, 2014, vol. 136, # 34, p. 12166 - 12173
[36] Tetrahedron Letters, 2015, vol. 56, # 11, p. 1338 - 1343
[37] Tetrahedron, 2016, vol. 72, # 25, p. 3567 - 3578
[38] Tetrahedron, 1995, vol. 51, # 40, p. 10923 - 10928
[39] Tetrahedron Letters, 2010, vol. 51, # 51, p. 6700 - 6703
[40] Archiv der Pharmazie, 2014, vol. 347, # 12, p. 936 - 949
[41] Patent: CN104230845, 2017, B, . Location in patent: Paragraph 0542; 0543; 0544
[42] Tetrahedron Letters, 2014, vol. 55, # 31, p. 4342 - 4345
[43] Patent: CN103923060, 2016, B, . Location in patent: Paragraph 0101; 0102
[44] Journal of Organic Chemistry, 2016, vol. 81, # 19, p. 9046 - 9074
[45] Chemical Communications, 2012, vol. 48, # 27, p. 3303 - 3305
[46] Tetrahedron, 2017, vol. 73, # 43, p. 6118 - 6137
[47] Justus Liebigs Annalen der Chemie, 1913, vol. 401, p. 44
[48] Angewandte Chemie, 1980, vol. 92, # 1, p. 48 - 49
[49] Journal of the Chemical Society, Chemical Communications, 1993, # 11, p. 959 - 960
[50] Journal of Organic Chemistry, 1993, vol. 58, # 8, p. 2068 - 2074
[51] Journal of the Chemical Society, Chemical Communications, 1992, # 11, p. 823 - 824
[52] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1995, # 11, p. 1373 - 1380
[53] Journal of Organic Chemistry, 1998, vol. 63, # 3, p. 864 - 866
[54] Synlett, 1998, # 7, p. 746 - 747
[55] Journal of the Chemical Society - Perkin Transactions 1, 1998, # 11, p. 1825 - 1832
[56] Journal of Medicinal Chemistry, 1998, vol. 41, # 22, p. 4261 - 4272
[57] Chemistry - A European Journal, 2002, vol. 8, # 3, p. 664 - 672
[58] Tetrahedron Letters, 2004, vol. 45, # 41, p. 7727 - 7728
[59] Synthetic Communications, 2008, vol. 38, # 14, p. 2392 - 2403
[60] Journal of Organic Chemistry, 2009, vol. 74, # 16, p. 6092 - 6104
[61] Tetrahedron Letters, 2009, vol. 50, # 27, p. 3889 - 3891
[62] Synthesis, 2010, # 23, p. 4043 - 4050
[63] Synthesis, 2011, # 20, p. 3277 - 3286
[64] Synthesis, 2011, # 22, p. 3716 - 3722
[65] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 3, p. 1375 - 1379
[66] Synlett, 2012, vol. 23, # 6, p. 867 - 872
[67] Journal of the American Chemical Society, 2012, vol. 134, # 40, p. 16492 - 16495,4
[68] Organic Process Research and Development, 2007, vol. 11, # 3, p. 399 - 405
[69] European Journal of Medicinal Chemistry, 2014, vol. 79, p. 350 - 368
[70] Journal of Medicinal Chemistry, 2014, vol. 57, # 20, p. 8445 - 8458
[71] Tetrahedron Letters, 2014, vol. 55, # 44, p. 6060 - 6064
[72] Chemistry - A European Journal, 2015, vol. 21, # 22, p. 8237 - 8241
[73] Chemical Communications, 2016, vol. 52, # 18, p. 3661 - 3664
[74] Tetrahedron, 2015, vol. 71, # 40, p. 7758 - 7781
[75] Organic Letters, 2016, vol. 18, # 2, p. 308 - 311
[76] Bioorganic and Medicinal Chemistry, 2016, vol. 24, # 6, p. 1331 - 1345
[77] Angewandte Chemie - International Edition, 2014, vol. 53, # 42, p. 11285 - 11288[78] Angew. Chem., 2014, vol. 126, # 42, p. 11467 - 11470,4
[79] Chemical Communications, 2016, vol. 52, # 22, p. 4179 - 4182
[80] Molecular Diversity, 2016, vol. 20, # 3, p. 639 - 657
[81] Organic Letters, 2017, vol. 19, # 5, p. 1008 - 1011
[82] Organic Letters, 2017, vol. 19, # 9, p. 2422 - 2425
[83] Chemical Communications, 2017, vol. 53, # 44, p. 6021 - 6024
[84] Advanced Synthesis and Catalysis, 2017, vol. 359, # 14, p. 2390 - 2395
[85] Chemistry - A European Journal, 2017, vol. 23, # 62, p. 15704 - 15712
[86] Organic Letters, 2018, vol. 20, # 15, p. 4566 - 4570
[87] Organic Letters, 2018, vol. 20, # 19, p. 6157 - 6160
[88] European Journal of Organic Chemistry, 2018, vol. 2018, # 39, p. 5445 - 5455
3
[ 89-95-2 ]
[ 106-95-6 ]
[ 28752-82-1 ]
Reference：
[1] Organic Letters, 2003, vol. 5, # 25, p. 4915 - 4918
[2] Tetrahedron, 2007, vol. 63, # 2, p. 337 - 346
[3] Russian Journal of Organic Chemistry, 2007, vol. 43, # 1, p. 77 - 82
[4] Australian Journal of Chemistry, 2000, vol. 53, # 10, p. 835 - 844
[5] Organic Letters, 2004, vol. 6, # 2, p. 205 - 208
[6] Tetrahedron, 2005, vol. 61, # 32, p. 7746 - 7755
[7] Tetrahedron, 2005, vol. 61, # 42, p. 9996 - 10006
[8] Advanced Synthesis and Catalysis, 2006, vol. 348, # 9, p. 1101 - 1109
[9] Journal of Organic Chemistry, 2007, vol. 72, # 4, p. 1373 - 1378
4
[ 26906-01-4 ]
[ 28752-82-1 ]
Reference：
[1] Journal of the American Chemical Society, 2014, vol. 136, # 34, p. 12166 - 12173
[2] Organic Letters, 2011, vol. 13, # 8, p. 1908 - 1911
[3] Synthetic Communications, 2000, vol. 30, # 21, p. 3941 - 3945
[4] Journal of the Korean Chemical Society, 2012, vol. 56, # 5, p. 539 - 541
5
[ 19244-42-9 ]
[ 28752-82-1 ]
Reference：
[1] Chemical Communications, 2012, vol. 48, # 27, p. 3303 - 3305
[2] Journal of Molecular Catalysis B: Enzymatic, 2013, vol. 90, p. 118 - 122
6
[ 936-72-1 ]
[ 28752-82-1 ]
Reference：
[1] Journal of the American Chemical Society, 2002, vol. 124, # 10, p. 2245 - 2258
[2] Journal of the American Chemical Society, 2001, vol. 123, # 13, p. 3183 - 3185
7
[ 111801-75-3 ]
[ 28752-82-1 ]
Reference：
[1] Journal of Molecular Catalysis B: Enzymatic, 2013, vol. 90, p. 118 - 122
Reference：
[1] Journal of the Chemical Society, 1965, vol. 65, p. 1829 - 1843
21
[ 28752-82-1 ]
[ 24019-66-7 ]
Yield
Reaction Conditions
Operation in experiment
63%
at 200℃; for 4 h;
The o-hydroxybenzaldehyde is first reacted with 3-bromopropene,To give intermediate O-A,And then under high temperature conditions for rearrangement reaction,To give 2-hydroxy-3-allylbenzaldehyde,As shown in Scheme 6,The specific preparation method is as follows: O-hydroxybenzaldehyde (290 g, 2.38 mol) was dissolved in 500 ml of DMF,K2CO3 (493 g, 3.57 mol) was added,Followed by the dropwise addition of 3-bromopropene (346 g, 2.86 mol)60 reaction 15h,Filter,The filtrate was poured into 500 mL of CH2Cl2,The organic phase was washed successively with 5percent aqueous NaOH,Saturated salt water and washed,Anhydrous Na2SO4 dried,Concentrated under reduced pressure,To give 317 g of a yellow oil,Yield 82.3percent.317 g (1.96 mol) of 2-allyloxybenzaldehyde was reacted at 200 ° C for 4 h,And distilled under reduced pressure to give 200 g of 3-allyl-2-hydroxybenzaldehyde as a yellow oil,Yield 63percent
Reference：
[1] Tetrahedron Letters, 1995, vol. 36, # 11, p. 1845 - 1848
[2] European Journal of Medicinal Chemistry, 1997, vol. 32, # 1, p. 71 - 82
[3] Archiv der Pharmazie, 2014, vol. 347, # 12, p. 936 - 949
[4] Patent: WO2010/91382, 2010, A1, . Location in patent: Page/Page column 31
[5] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2010, vol. 49, # 11, p. 1552 - 1555
[6] Patent: CN104230845, 2017, B, . Location in patent: Paragraph 0541; 0542; 0543; 0544
[7] Journal of Medicinal Chemistry, 2015, vol. 58, # 9, p. 4046 - 4065
[8] Bioorganic and Medicinal Chemistry Letters, 2005, vol. 15, # 3, p. 527 - 530
[9] Tetrahedron, 2005, vol. 61, # 32, p. 7746 - 7755
[10] Tetrahedron, 2005, vol. 61, # 42, p. 9996 - 10006
[11] Journal of Organic Chemistry, 2009, vol. 74, # 16, p. 6092 - 6104
[12] Synlett, 2012, vol. 23, # 6, p. 867 - 872
[13] Tetrahedron Letters, 2015, vol. 56, # 11, p. 1338 - 1343
[14] Bioorganic and Medicinal Chemistry, 2016, vol. 24, # 6, p. 1331 - 1345
[15] Organic Letters, 2017, vol. 19, # 5, p. 1008 - 1011
22
[ 28752-82-1 ]
[ 315183-21-2 ]
Reference：
[1] Journal of Medicinal Chemistry, 2015, vol. 58, # 9, p. 4046 - 4065
The o-hydroxybenzaldehyde is first reacted with 3-bromopropene,To give intermediate O-A,And then under high temperature conditions for rearrangement reaction,To give 2-hydroxy-3-allylbenzaldehyde,As shown in Scheme 6,The specific preparation method is as follows: O-hydroxybenzaldehyde (290 g, 2.38 mol) was dissolved in 500 ml of DMF,K2CO3 (493 g, 3.57 mol) was added,Followed by the dropwise addition of 3-bromopropene (346 g, 2.86 mol)60 reaction 15h,Filter,The filtrate was poured into 500 mL of CH2Cl2,The organic phase was washed successively with 5% aqueous NaOH,Saturated salt water and washed,Anhydrous Na2SO4 dried,Concentrated under reduced pressure,To give 317 g of a yellow oil,Yield 82.3%.317 g (1.96 mol) of 2-allyloxybenzaldehyde was reacted at 200 C for 4 h,And distilled under reduced pressure to give 200 g of 3-allyl-2-hydroxybenzaldehyde as a yellow oil,Yield 63%
at 200℃; for 3h;
2-(3-methylbut-2-enyloxy)benzaldehyde 1aa (1g) was heated > 200 0C for 3h. After completion of reaction (TLC), the crude product was purified by column chromatography (hexane) to afford the desired product 1p as color solid in 30% yield. The compound was well characterised by spectral data.
3-[2-(prop-2-en-1-yloxy)phenyl]-3,4-dihydro-1H-isochromen-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54%
With bis(cyclopentadienyl)titanium dichloride; zinc In tetrahydrofuran at 20℃;
54%
Stage #1: 2-(allyloxy)benzaldehyde; 2-ethoxycarbonylbenzyl bromide With titanocene(III) chloride In tetrahydrofuran at 20℃; for 13h;
Stage #2: With sulfuric acid; water In tetrahydrofuran
diethyl 2-methyl-4-(2-allyloxyphenyl)-6-diethoxymethyl-1,4-dihydropyridine-3,5-dicarboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With acetic acid; In benzene;
(1) To a mixture of 2-allyloxybenzaldehyde (8.11 g) and <strong>[10495-09-7]ethyl 4,4-diethoxyacetoacetate</strong> (12.00 g) in benzene (about 31 ml) was added acetic acid (0.36 g) and to the resultant mixture was added each one third portion of piperidine (0.51 g) in benzene (about 4 ml) with an interval of 20 minutes. After refluxing for 2.5 hours the mixture was cooled to room temperature and benzene (50 ml) was added thereto. The resultant mixture was washed three times with water and dried over magnesium sulfate. Removing of the solvent, a red oil was gained and to this oil was added ethyl 3-aminocrotonate (8.56 g). The resultant mixture was warmed at 55 to 60 C. for 6.5 hours under stirring and further for 2 hours at 72 to 75 C. and finally for 2.5 hour at 105 to 107 C. The reaction mixture was subjected to column chromatography on silica gel with an eluent to give an oil (19.38 g) from the elude. The oil (3.0 g) was further purified on silica gel column chromatography with an eluent (benzene:ethyl acetate=20:1) to give an oil (1.77 g) of diethyl 2-methyl-4-(2-allyloxyphenyl)-6-diethoxymethyl-1,4-dihydropyridine-3,5-dicarboxylate
With acetic acid; In benzene;
(1) To a mixture of 2-allyloxybenzaldehyde (8.11 g) and <strong>[10495-09-7]ethyl 4,4-diethoxyacetoacetate</strong> (12.00 g) in benzene (about 31 ml) was added acetic acid (0.36 g) and to the resultant mixture was added each one third portion of piperidine (0.51 g) in benzene (about 4 ml) with an interval of 20 minutes. After refluxing for 2.5 hours the mixture was cooled to room temperature and benzene (50 ml) was added thereto. The resultant mixture was washed three times with water and dried over magnesium sulfate. Removing of the solvent, a red oil was gained and to this oil was added ethyl 3-aminocrotonate (8.56 g). The resultant mixture was warmed at 55 to 60 C. for 6.5 hours under stirring and further for 2 hours at 72 to 75 C. and finally for 2.5 hour at 105 to 107 C. The reaction mixture was subjected to column chromatograhy on silica gel with an eluent to give an oil (19.38 g) from the elude. The oil (3.0 g) was further purified on silica gel column chromatography with an eluent (benzene: ethyl acetate = 20: 1) to give an oil (1.77 g) of diethyl 2-methyl-4-(2-allyloxyphenyl)-6-diethoxymethyl-1,4-dihydropyridine-3,5-dicarboxylate
With ethylenediamine diacetic acid; In acetonitrile; at 20℃; for 0.166667h;Sonication;
General procedure: To a solution of benzofuran-3(2H)-one 2 or 5 (0.6 mmol) in acetonitrile (5 mL) was added ethylenediamine diacetate (EDDA) (10 mol %) followed by an arylaldehyde (0.6 mmol). The reaction mixture was stirred at room temperature either under ultrasound irradiation or in the absence of ultrasound for the time indicated in Table 1. After completion of the reaction the solid precipitated was filtered and crystallized from ethanol or methanol to afford the desired product.
92.8%
With ethylenediamine diacetic acid; In acetonitrile; at 20℃; for 1.3h;Inert atmosphere;
General procedure: To a solution of 7-methoxy benzofuran-3(2H)-one, 2a (0.101 g, 0.61 mmol) in acetonitrile(5 mL) was added ethylenediamine diacetate (EDDA) (0.011 g, 10% mol) followed byO-allylated salicylaldehyde, 2b (0.1 g, 0.61 mmol). The reaction mixture was stirred for1.3 h at room temperature. The precipitate was collected by filtration and crystallized fromethanol to afford the pure compound, 3b as yellow solid (yield: 92.8%); mp: 145C-147C; 1H NMR (400 MHz, CDCl3): delta 8.36 (d, J = 8.1 Hz, 1H), 7.54 (s, 1H), 7.40-7.32 (m, 2H),7.17-7.06 (m, 3H), 6.92 (d, J = 8.4 Hz, 1H), 6.15-6.05 (m, 1H), 5.44 (d, J = 17.2 Hz,1H), 5.32 (d, J = 10.49 Hz, 1H), 4.65 (d, J = 5.13 Hz, 2H), 4.03 (s, 3H); 13C NMR(100 MHz, CDCl3): delta 184.7, 157.8, 155.6, 146.9, 145.9, 132.8, 132.2, 131.3, 123.7, 123.2,121.5, 121.1, 118.5, 117.8, 115.8, 112.0, 107.7, 69.3, 56.3; IR (KBr)vmax 3055, 1697, 1649,1277, 1239, 950, 906 cm-1; MS (ES mass): m/z 308.9 (M+1, 100%); HRMS: calcd, forC19H17O4: 309.1127, found 309.1118.
4,6,4',6'-di-O-(2-allyloxybenzylidene)-α,α-D-trehalose[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
With Amberlyst 15 In N,N-dimethyl-formamide; benzene for 48h; Reflux;
2.2. Synthesis of 4,6,4',6'-di-O-(x-allyloxybenzylidene)-α,α-D-trehalose(2-; 3- or 4-AllTD)
General procedure: Trehalose acetals were synthesized based on a method previouslydescribed for the synthesis of 4,6,4',6'-di-O-(4-allyloxybenzylidene)-α,α-D-trehalose with some modifications[40]. The acetalization reaction was carried out using a two-neckround-bottom flask equipped with a DeaneStark trap, thermometerand reflux condenser. 30 mL of anhydrous benzene, 3.2 mL of2-, 3- or 4-allyloxybenzaldehyde and 1.13 g of Amberlyst 15 wereadded to a solution of 2.7 g (7.9 mmol) of dried trehalose in 15 mL of anhydrous DMF. The reaction was carried under reflux for 48 h.After this time, the catalyst was filtered off and benzene wasremoved under reduced pressure. A solution of the product in N,N-dimethylformamide(DMF) was treated several times with aqueous NaHCO3 and deionized water. The precipitate was washed threetimes with diethyl ether (30 mL) in order to remove x-allyloxybenzaldehyde.White powder was dried under a vacuum for 24 h.
1-(2-(allyloxy)phenyl)-3-methylbut-2-en-1-ol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
Stage #1: 2-methyl-1-propenylbromide With magnesium In tetrahydrofuran for 4h; Reflux;
Stage #2: 2-(allyloxy)benzaldehyde In tetrahydrofuran at 0 - 20℃; for 0.5h;
1-(2-(Allyloxy)phenyl)-3-methylbut-2-en-1-ol (3b): A mixture of 1-bromo-2-methyl-propene (405 mg, 3.00 mmol, 3.0 equiv.), Mg turnings (72 mg, 3.00 mmol, 3.0 equiv.) and THF (10mL) was heated to reflux for 4 h. The mixture was cooled to 0 °C and a solution of 1a (162 mg,1.00 mmol) in THF (5 mL) was added dropwise and stirring was continued for 0.5 h at ambient temperature. The mixture was diluted with ethylacetate (50 mL) and brine (10 mL). The aqueous layer was extracted three times with ethylacetate (30 mL for each extraction). The organic layer was dried with MgSO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica to give 3b (145 mg, 0.67 mmol, 67 %). 1H NMR (300 MHz, C6D6) δ 7.56 (dd, J = 7.5, 1.6 Hz, 1H), 7.05 (td, J = 7.8, 1.8 Hz, 1H), 6.92(td, J = 7.4, 0.9 Hz, 1H), 6.53 (d, J = 8.2 Hz, 1H), 5.87 (d, J = 7.8 Hz, 1H), 5.72 (ddt, J = 17.2,10.4, 5.2 Hz, 1H), 5.60 (ddd, J = 8.6, 2.7, 1.3 Hz, 1H), 5.15 (ddd, J = 17.3, 3.2, 1.6 Hz, 1H),4.99 (ddd, J = 10.5, 2.8, 1.4 Hz, 1H), 4.06 (dt, J = 5.1, 1.4 Hz, 2H), 2.27 (s, 1H), 1.68 (d, J =1.0 Hz, 3H), 1.58 (d, J = 1.1 Hz, 3H); 13C NMR (75 MHz, C6D6) δ 155.9, 133.8, 133.6, 133.5,128.6, 128.1, 127.6, 121.4, 117.1, 112.0, 68.8, 67.3, 25.8, 18.4; IR (ATR) ν 3392 (bw), 1600(w), 1488 (s), 1452 (s), 997 (m); HRMS (EI) calcd. for C14H18O2+ [M+]: 218.1307, found:218.1301.
3-p-methylphenacyl-2,3-dihydrochromen-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
With bis(1-methyl-1-phenylethyl)peroxide In benzene for 24h; Inert atmosphere; UV-irradiation; Sealed tube;
6 Example 6
To a 50 mL photoreactor, 2-propenyloxybenzaldehyde (0.1 mmol) was added in sequence.4,4'-dimethyl substituted benzoin (0.4 mmol), dicumyl peroxide (DCP) (0.4 mmol),After dry benzene (15 mL), deoxygenated by bubbling with nitrogen ball 0.5h, then, the reaction system was sealed,Place in 350nm UV light for 24h.After the reaction is completed, the reaction solvent is concentrated and spin-dried by a rotary evaporator.Then use a 40:1 volume ratio of petroleum ether:ethyl acetate as the eluent.Purification by silica gel column chromatography gave the corresponding 3-p-methylphenacyl-2,3-dihydrochromen-4-one having the structure: purity 98.2%, yield 64%.
With dipotassium peroxodisulfate In water; dimethyl sulfoxide at 100℃; for 24h; Schlenk technique; Sealed tube; chemoselective reaction;
62%
With dipotassium peroxodisulfate In water; acetonitrile at 70℃; for 8h; Schlenk technique; Sealed tube;
1 Example 1
Add 1 mmol of allyl salicylaldehyde in a clean and dry 20 mL Schlenk pressure-resistant reaction tube.1.5 mmol of sodium trifluoromethylsulfinate, 3 mmol of potassium persulfate,Further, 1.5 mL of acetonitrile and 2.5 mL of water were added as a solvent, and the reaction tube was sealed and placed in an oil bath at 70 ° C to heat the reaction for 8 hours.After the reaction was completed, ethyl acetate was added to extract the reaction mixture, and the organic phase was dried by a rotary evaporator.The residue obtained was treated with petroleum ether and ethyl acetate as eluents.The title product was obtained as a colorless oily liquid, eluted from silica gel column, yield 62%.
3-(((4-fluorophenyl)sulfonyl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With dipotassium peroxodisulfate; silver nitrate; In water; dimethyl sulfoxide; at 100℃; for 24h;Sealed tube; Inert atmosphere;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-(allyloxy)benzaldehyde (0.2 mmol), Sodium benzene sulfinate (2.0 equiv.), AgNO3 (20 mol%), K2S2O8 (3.0 equiv.), DMSO:H2O=1:1 (2 ml). The reaction vessel was carried 100. After completion, it was diluted with ethyl acetate, washed with water. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
3-(((4-bromophenyl)sulfonyl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
69%
With dipotassium peroxodisulfate; silver nitrate In water; dimethyl sulfoxide at 100℃; for 24h; Sealed tube; Inert atmosphere;
2. Typical procedure for the synthesis of 3-((phenylsulfonyl)methyl)chroman-4-one
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-(allyloxy)benzaldehyde (0.2 mmol), Sodium benzene sulfinate (2.0 equiv.), AgNO3 (20 mol%), K2S2O8 (3.0 equiv.), DMSO:H2O=1:1 (2 ml). The reaction vessel was carried 100. After completion, it was diluted with ethyl acetate, washed with water. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
3-(((2-chlorophenyl)sulfonyl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
With dipotassium peroxodisulfate; silver nitrate; In water; dimethyl sulfoxide; at 100℃; for 24h;Sealed tube; Inert atmosphere;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-(allyloxy)benzaldehyde (0.2 mmol), Sodium benzene sulfinate (2.0 equiv.), AgNO3 (20 mol%), K2S2O8 (3.0 equiv.), DMSO:H2O=1:1 (2 ml). The reaction vessel was carried 100. After completion, it was diluted with ethyl acetate, washed with water. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
3-(((4-chlorophenyl)sulfonyl)methyl)-3H,4H-benzopyran-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
With dipotassium peroxodisulfate; iron(III) chloride hexahydrate; at 60℃; for 8h;Sealed tube;
Add 1mmol1mmol <strong>[14752-66-0]sodium p-chlorobenzenesulfinate</strong>, 2mmol potassium persulfate, 0.05mmol FeCl3·6H2O, and 2ml eutectic solvent into the reactor respectively, and heat it for 8 hours at 60 under air condition; after the reaction, perform column chromatography After separation, the following P2 compound was obtained
62%
With dipotassium peroxodisulfate; silver nitrate; In water; dimethyl sulfoxide; at 100℃; for 24h;Sealed tube; Inert atmosphere;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-(allyloxy)benzaldehyde (0.2 mmol), Sodium benzene sulfinate (2.0 equiv.), AgNO3 (20 mol%), K2S2O8 (3.0 equiv.), DMSO:H2O=1:1 (2 ml). The reaction vessel was carried 100. After completion, it was diluted with ethyl acetate, washed with water. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
3-((thiophen-2-ylsulfonyl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
36%
With dipotassium peroxodisulfate; silver nitrate; In water; dimethyl sulfoxide; at 100℃; for 24h;Sealed tube; Inert atmosphere;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-(allyloxy)benzaldehyde (0.2 mmol), Sodium benzene sulfinate (2.0 equiv.), AgNO3 (20 mol%), K2S2O8 (3.0 equiv.), DMSO:H2O=1:1 (2 ml). The reaction vessel was carried 100. After completion, it was diluted with ethyl acetate, washed with water. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
3-((di-o-tolylphosphoryl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54%
With dipotassium peroxodisulfate; In water; dimethyl sulfoxide; at 80℃; for 18h;Inert atmosphere; Green chemistry;
General procedure: Under nitrogen, a reaction tube equipped with a magnetic stirring bar was charged with 2-(allyloxy)benzaldehyde (1, 0.30 mmol), and diphenylphosphine oxide (DPPO, 2, 1.5 equiv), K2S2O8 (3.0 equiv), and DMSO/H2O 4:1 (5.0 mL), respectively. The mixture was allowed to react at 80 C for 18 h. When the reaction was completed, the mixture was charged in 30 mL water and extracted with CH2Cl2 (15 mL, 3 times). The CH2Cl2 layers were combined and dried over Na2SO4, and further purified by column chromatography on silica gel (eluent, petroleum ether/ethyl acetate 1:1 or CH2Cl2/MeOH 20:1) to afford the desired product 3.
3-((bis(4-(tert-butyl)phenyl)phosphoryl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With dipotassium peroxodisulfate In water; dimethyl sulfoxide at 80℃; for 18h; Inert atmosphere; Green chemistry;
3. General procedures for the preparation of products.
General procedure: Under nitrogen, a reaction tube equipped with a magnetic stirring bar was charged with 2-(allyloxy)benzaldehyde (1, 0.30 mmol), and diphenylphosphine oxide (DPPO, 2, 1.5 equiv), K2S2O8 (3.0 equiv), and DMSO/H2O 4:1 (5.0 mL), respectively. The mixture was allowed to react at 80 °C for 18 h. When the reaction was completed, the mixture was charged in 30 mL water and extracted with CH2Cl2 (15 mL, 3 times). The CH2Cl2 layers were combined and dried over Na2SO4, and further purified by column chromatography on silica gel (eluent, petroleum ether/ethyl acetate 1:1 or CH2Cl2/MeOH 20:1) to afford the desired product 3.
3-((bis(4-fluorophenyl)phosphoryl)methyl)chroman-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
With dipotassium peroxodisulfate; In water; dimethyl sulfoxide; at 80℃; for 18h;Inert atmosphere; Green chemistry;
General procedure: Under nitrogen, a reaction tube equipped with a magnetic stirring bar was charged with 2-(allyloxy)benzaldehyde (1, 0.30 mmol), and diphenylphosphine oxide (DPPO, 2, 1.5 equiv), K2S2O8 (3.0 equiv), and DMSO/H2O 4:1 (5.0 mL), respectively. The mixture was allowed to react at 80 C for 18 h. When the reaction was completed, the mixture was charged in 30 mL water and extracted with CH2Cl2 (15 mL, 3 times). The CH2Cl2 layers were combined and dried over Na2SO4, and further purified by column chromatography on silica gel (eluent, petroleum ether/ethyl acetate 1:1 or CH2Cl2/MeOH 20:1) to afford the desired product 3.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
