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Structure of 410528-62-0

Chemical Structure| 410528-62-0

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Product Details of [ 410528-62-0 ]

CAS No. :410528-62-0
Formula : C15H20Br2
M.W : 360.13
SMILES Code : CC1(C)CCC(C)(C)C2=C1C=C(Br)C(CBr)=C2

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Application In Synthesis of [ 410528-62-0 ]

* 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.

  • Downstream synthetic route of [ 410528-62-0 ]

[ 410528-62-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 119999-22-3 ]
  • [ 410528-62-0 ]
YieldReaction ConditionsOperation in experiment
65% With sodium bromate; sodium hydrogensulfite; In water; ethyl acetate; for 16.5h; Compound 10 (6.60 g, 23.5 mmol) was dissolved in 50 mL of EtOAc and a solution of NaBrO3 (10.6 g, 70.5 mmol) in 40 mL of H2O was added. While the mixture was stirring rapidly, a solution of NaHSO3 (7.33 g, 70.5 mmol) in 75 mL of H2O was added dropwise over 30 min. The reaction was allowed to stir for 16 h. The mixture was poured into 200 mL of Et2O and the layers were separated. The aqueous was extracted with Et2O (250 mL). The combined organics were washed with 100 mL of sat. aq. Na2S2O3, dried with MgSO4, filtered, and the solvents removed under vacuum to yield an oily solid. The product was purified by silica gel column chromatography (elution in hexane) to yield a white solid (5.50 g, 65%). mp = 68-70C; 1H NMR (400 MHz, CDCl3) delta 7.47 (s, 1H), 7.37 (s, 1H), 4.58 (s, 2H), 1.67 (s, 4H), 1.27 (m, 12H); 13C NMR (100 MHz, CDCl3): delta 147.9, 145.1, 133.8, 131.3, 129.6, 121.3, 34.7, 34.3, 34.1, 33.9, 31.7, 31.6; IR (ATR) numax: 2956, 2929, 2860, 1595, 1482, 1077 cm-1; Anal. calcd for C15H20Br2: C, 50.03; H, 5.60. Found: C, 49.22; H, 5.62.
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; Petroleum ether; Example 21: Preparation of 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde To a solution of 12.0 g (281 mmol) of <strong>[119999-22-3]2-bromo-3-methyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene</strong> in 84 mL carbon tetrachloride was added 7.59 g (42.7 mmol) of N-bromosuccinimide and 0.310 g (1.28 mmol) of benzoyl peroxide. This was heated to reflux for 40 minutes and then cooled to room temperature. To the cooled solution was added 170 mL petroleum ether and the solution was filtered and concentrated in vacuo to give 17.3 g of 2-bromo-3-bromomethyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene which was used without further purification.
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In chloroform; for 16h;Heating / reflux; The mixture of 6-bromo-7-methyl-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (4.20 g, 15 mmol), NBS (3.20 g, 18 mmol), 2,2'-azobisisobutyronitrile (0.3 g, 1.8 mmol) and CCl4 (120 mL) was heated at reflux for 16 hours. The mixture was concentrated under reduced pressure to about 50 mL. The reaction was then filtered, and the solid was washed with Et2O (20 mL). The combined organic solution was then concentrated under vacuum to generate crude product. Crude 91.2 was generated as a brown oil and used directly in the next step without further purification.
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; 2,2'-azobis-(2,4-dimethylvaleronitrile); In cyclohexane; at 55 - 65℃; for 1h; step B-A 100 gallon glass-lined reactor was charged with 2b (28 Kg), 1,3-dibromo-5,5-dimethyl-imidazolidine-2,4-dione (22.83 Kg), 2,2'-azo-bis-(2,4-dimethyl-pentanenitrile) (Vazo 52, E. I. DuPont de Nemours) (481 g) and cyclohexane (151 Kg). The mixture was warmed to 55 C. resulting in a slow exotherm with the temperature rising to 65 C. After 1 h at 65 C. the reaction was quenched with aqueous sodium sulfite solution (19.3 Kg Na2SO3 in 166 L of H2O). The aqueous layer was drained off and the organic layer washed with water (100 L). The cyclohexane was removed by distillation at atmospheric pressure and replaced with NMP (75 Kg). The resulting solution was transferred to a dry mixture of pyrazole (6.83 Kg) and K3PO4 (21 Kg). Additional NMP (18 Kg) was added and the mixture was heated to between 105 and 120 C. for 2.5 h. The solution was transferred into 150 L of water. Toluene (98 Kg) and additional water (26 L) were added and the layers were separated after aging overnight. The aqueous layer was back extracted with toluene (52 Kg) and the combined toluene fractions were washed twice with water (100 L). The resulting toluene solution was added to p-TsOH.H2O (16 Kg). Additional toluene (33 Kg) was added and the mixture was heated to 58 C. until the solution was homogenous. The mixture was cooled to around 45 C. where crystals first appear and then to 10 C. The resulting slurry was filtered and washed with additional toluene (39 Kg). The crude product (37 Kg) was suspended in toluene (250 Kg), aqueous NaOH (9 Kg 50% NaOH and 46 Kg of H2O) was added and the mixture was heated to 40 C. The aqueous layer was removed and the toluene solution was washed with H2O (50 L). The resulting toluene solution was added to carbon (2 Kg) and aged for several hours before filtering through a CELITE pad (5 Kg). The cake is washed with additional toluene (30 Kg) and the combined toluene filtrates were added a solution of p-TsOH.H2O in MeOH (13.57 Kg p-TsOH.H2O and 25 Kg MeOH). About 50 Kg of the MeOH was removed by distillation and the remaining solution was cooled slowly to 5 C. and aged overnight. Filtration, washing with toluene (50 Kg) and vacuum drying (vacuum oven 50 C. with nitrogen bleed) afforded 24 Kg (46% overall) of the tosylate salt of 3b.

 

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