* 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.
Step 2: 5-Bromo-3-(tert-butyl)-2-hydroxybenzaldehyde (7b) To a solution of compound 7a (3.0 g, 17 mmol) in AcOH (15 mL) was added Br2 (2.95 g, 18 mmol) dropwise at rt and the mixture was stirred for 3 h. TLC (PE:EA = 50:1) showed the reaction was complete. The reaction mixture was quenched with aq. NaHSO3 (50 mL) and extracted with Et2O. The organic layer was concentrated under reduced pressure to give crude compound 7b (3.2 g, 73percent) as white solid.
73%
With bromine In acetic acid at 20℃; for 3 h;
Step 2: 5-Bromo-3-(terf-butyl)-2-hvdroxybenzaldehvde (P7b)To a solution of compound P7a (3.0 g, 17 mmol) in AcOH (15 mL) was added Br2 (2.95 g, 18 mmol) dropwise at rt and the mixture was stirred for 3 h, quenched with aq. NaHS03 (50 mL) and extracted with Et20. The organic layer was concentrated to give crude compound P7b (3.2 g, 73percent) as white solid.
64%
at 20℃; for 6 h;
To a stirred solution of 3-tert-butylsalicylaldehyde (5.13 g, 28.8 mmol) in acetic acid (15 mL) was added a solution of bromine (1.65 mL, 32.25 mmol) in acetic acid (7.0 mL) dropwise within 20 min. The reaction mixture was stirred at room temperature for 3 h. Analytical HPLC analysis after 3 h shows the desired product -72percent and the unreacted starting material -28percent. A second batch of bromine (0.5 mL) in acetic acid (3 mL) was added and the reaction mixture was stirred at room temperature for another 3 h. Analytical HPLC analysis of the reaction mixture after 3 h (6 h total) shows the desired product -85percent and still shows the starting material -15percent. After 6 h of stirring, the reaction mixture was diluted with dichloromethane (50 mL) and the organic layer was washed with 39percent sodium bisulfite solution (1 x 10 mL), water, saturated aHC03 and brine. The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to give the desired product as a pale yellow crystalline solid (7.2421 g). Purification by silica-gel flash chromatography on silica gel column and elution with 0-5percent ethyl acetate in n-heptane afforded the desired product as a pale yellow crystalline solid (4.792 g, 64percent yield). LC-MS analysis of the product in negative mode shows the desired product's mass: m/z 255 (79BrM+-H) and m/z 257 (81BrM+-H). GC-MS analysis of the product in CI mode (Methane) shows the desired product's mass: m/z 256 (79BrM+) and m/z 258 (81BrM+), calc'd. for CnH13Br02: 257.124. XH NMR (400 MHz, CDC13): δ 1.39 (s, 9H, t-Bu-), 7.50 (s, 1H, H-4), 7.56 (s, 1H, H-6), 9.79 (s, 1H, -CHO), 11.70 (s, 1H, -OH). 1H NMR of the isolated product was identical with that of a previously reported sample of the product (Girsch et al, 2007).
85 %Chromat.
With ammonium metavanadate; perchloric acid; tetrabutylammomium bromide; dihydrogen peroxide In chloroform; water at 20℃; for 0.333333 h;
General procedure: NH4VO3 (5 molpercent) and H2O2 (200 molpercent) were placed in a flask. After complete dissolution of the catalyst, TBAB (3 mmol) was added and the mixture was stirred at room temperature. Then, Et2O (10 ml) and aromatic substrate (1 mmol) were added to the mixture. Finally, by slow drip, 1 ml of 1N HClO4 solution was added. After adding the acid, the colour of the reaction changed from yellow to red due to the formation of oxomonoperoxovanadium. Conversion was followed by TLC and determined by GC. The phases were separated and the aqueous phase was extracted with CH2Cl2 (15 ml x3). The organic phases were pooled, washed with brine, dried over Na2SO4 and filtered. The solvent was removed under reduced pressure and the resulting crude product was purified by column chromatography with Hex:AcOEt.
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4
[ 50-00-0 ]
[ 10323-39-4 ]
[ 153759-58-1 ]
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5
[ 88-18-6 ]
[ 153759-58-1 ]
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[3] Organic Letters, 2011, vol. 13, # 1, p. 26 - 29
[4] Polymer, 2010, vol. 51, # 5, p. 994 - 997
[5] Patent: EP2511263, 2012, A1,
[6] Patent: WO2012/139775, 2012, A1,
[7] Tetrahedron, 2012, vol. 68, # 48, p. 9954 - 9961,8
[8] Science China Chemistry, 2014, vol. 57, # 1, p. 107 - 113
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(R,R)-N,N'-bis(5-bromo-3-tert-butylsalicylidene)-1,2-cyclohexanediamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With potassium carbonate; In tetrahydrofuran; ethanol; water; at 80℃; for 2h;
WORKING EXAMPLE I; Synthesis of (VII) Where R is Br, [(R,R)-(salen-8)CoOAc]First (R,R)-N,N'-bis(5-bromo-3-tert-butyl-salicylidene)-1,2-cyclohexanediamine, [(R,R)-(salen-8)H2], was synthesized as follows:Under an atmosphere of nitrogen, to an aqueous solution of (R,R)-1,2-diaminocyclohexane L-tartrate (1.321 g, 5.0 mmol) and K2CO3 (1.382 g, 10.0 mmol) in water (10 mL) was added ethanol (50 mL). The mixture was heated to 80 C., and to it was dropwise added <strong>[153759-58-1]5-bromo-3-tert-butyl-2-hydroxybenzaldehyde</strong>, prepared by a modification of the methods described in Cavazzini, M., et al., Eur. J. Org. Chem. (2001), 4639-4649 and Lam, F., et al., J. Org. Chem. 61, 8414-8418 (1996) (2.571 g, 10.0 mmol) in THF (10 mL), resulting a yellow solution. After the mixture was stirred for 2 h and cooled down to room temperature, water (150 mL) was added to precipitate yellow crude title compound. The precipitate was redissolved in diethyl ether (100 mL) and washed with brine (100 mL), water (100 mL), and dried over anhydrous Na2SO4, and then concentrated. A yellow crystalline product was obtained after recrystallization from ethanol. Yield: 2.60 g, 88%. 1H NMR (CDCl3, 500 MHz) delta 13.80 (s, 2H), 8.18 (s, 2H), 7.31 (d, 4J=2.0 Hz, 2H), 7.09 (d, 4J=2.0 Hz, 2H), 3.33 (br, 2H), 2.00 (br, 2H), 1.90 (br, 2H), 1.75 (M, 2H), 1.47 (m, 2H), 1.38 (s, 18H), 13C NMR (CDCl3, 125 MHz) delta 24.40, 39.31, 159.57, 164.68, LRMS (EI) Cald. 592, found 592.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 120℃; for 3h;Inert atmosphere;
General procedure: A schlenk tube charged with bis(pinacolato)diboron (2 g, 7.9 mmol), Pd(dppf)Cl2 (200 mg, 0.24 mmol) and KOAc (2 g, 20 mmol) was maintained under argon by successive vacuum-argon cycles. Thoroughly degassed 1,4-dioxane (9 mL) was introduced in the schlenk and the mixture was stirred for 10 min. Then 5-bromo-3-tert-butyl-2-hydroxy-benzaldehyde 1 (1.8 g, 7.1 mmol) diluted in 9 mL of degassed 1,4-dioxane was introduced. The mixture was heated at 120 C for 3 h. The suspension was filtered on Celite, washed with CH2Cl2 and the solvents were removed under reduced pressure. The residue was purified by silica gel chromatography (pentane/ether 95/5) to afford the expected product (76%, 1.65 g, 5.4 mmol) as a white solid. 1H NMR (250 MHz, CDCl3): delta 12.00 (s, 1H), 9.91 (s, 1H), 7.93-7.89 (m, 2H), 1.44 (s, 9H), 1.36 (s, 12H); 13C NMR (90 MHz, CDCl3): delta 197.5, 163.6, 140.0, 139.9, 137.4, 120.4, 83.9, 34.8, 29.2, 24.8.
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