Iodine → OcH-BINAP

HRID 1591357

反応式

HRID 1591357 の反応式
[Mg].II.Br[CH2:5][CH2:6]Br.Br[C:9]1[CH:18]=[CH:17][C:16]2[CH2:15][CH2:14][CH2:13][CH2:12][C:11]=2[C:10]=1[C:19]1[C:28]2[CH2:27][CH2:26][CH2:25][CH2:24][C:23]=2[CH:22]=[CH:21][C:20]=1Br.[C:30]1([P:36](Cl)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:37])[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>O.O1CCCC1.C1(C)C=CC=CC=1>[C:30]1([P:36]([C:9]2[CH:18]=[CH:17][C:16]3[CH2:15][CH2:14][CH2:13][CH2:12][C:11]=3[C:10]=2[C:19]2[C:28]3[CH2:27][CH2:26][CH2:25][CH2:24][C:23]=3[CH:22]=[CH:21][C:20]=2[P:36]([C:6]2[CH:5]=[CH:43][CH:38]=[CH:39][CH:40]=2)([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[O:37])([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:37])[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

参加物

9

反応物 5

HCID 807IodineHCID 78391,2-DibromoethaneHCID 73910Diphenylphosphinic chlorideHCID 5462224MagnesiumHCID 149427772,2'-Dibromo-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene2 回

生成物 1

HCID 14942778OcH-BINAP収率 64.1%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
5 °C

実験手順

Into a 1-liter four-necked flask was placed 4.26 g (0.177 mole) of magnesium. After nitrogen replacement, a small amount of iodine and 20 ml of dry tetrahydrofuran were added in this order. Thereto was then added 0.6 ml of 1,2-dibromoethane using a syringe. To the mixture in the flask, a solution separately prepared by dissolving 32.5 g (0.0774 mole) of 2,2'-dibromo-5,5',6,6',7,7',8,8'-octahydro-1,1,-binaphthyl (IV) in a mixed solvent of 330 ml of toluene and 90 ml of tetrahydrofuran was added dropwise from a dropping funnel over a period of 7 hours. During this addition, the temperature of the reaction mixture was 80° to 90° C. After the addition of the compound (IV) solution, stirring was further continued at 94° C. for 19 hours. The resulting reaction mixture was cooled to 5° C., and 34.27 g (0.148 mole) of diphenylphosphinic chloride was added thereto dropwise over a period of 30 minutes. The reaction mixture was then heated to 72° C., stirred at this temperature for 3.5 hours, and then cooled to room temperature. Thereafter, 100 ml of water was added thereto, and the resulting mixture was heated to 80° C., stirred at this temperature for 20 minutes, cooled to room temperature, and then allowed to stand for a night, whereby a white solid was deposited. This solid was collected by filtration, washed twice with 100 ml of water, further washed with 100 ml of a hexane-toluene (9:1 by volume) mixture, and then dried under a reduced pressure (0.1 mmHg) at 70° C. for 7 hours, thereby obtaining 32.8 g of the titled compound (VI).

後処理

  1. customInto a 1-liter four-necked flask was placed
  2. customTo the mixture in the flask, a solution separately prepared
  3. dissolutionby dissolving 32.5 g (0.0774 mole) of 2,2'-dibromo-5,5',6,6',7,7',8,8'-octahydro-1,1
  4. additionDuring this addition
  5. customwas 80° to 90° C
  6. customThe resulting reaction mixture
  7. waitdropwise over a period of 30 minutes
  8. temperatureThe reaction mixture was then heated to 72° C.
  9. stirringstirred at this temperature for 3.5 hours
  10. temperaturecooled to room temperature
  11. temperaturethe resulting mixture was heated to 80° C.
  12. stirringstirred at this temperature for 20 minutes
  13. temperaturecooled to room temperature
  14. waitto stand for a night
  15. filtrationThis solid was collected by filtration
  16. washwashed twice with 100 ml of water
  17. washfurther washed with 100 ml of a hexane-toluene (9:1 by volume) mixture
  18. customdried under a reduced pressure (0.1 mmHg) at 70° C. for 7 hours

出典と根拠

ORDレコード
ord-c41ee333969e45b7b885cc5de1d40cba
出典データセット
uspto-grants-1993_04
特許番号
US05206399

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