Hydrochloric Acid → HCID 178444395, 화합물

HRID 65173

반응식

HRID 65173 반응식
[Mg].II.Br[CH2:5][C@H:6]1[CH2:11][CH2:10][C@H:9]([CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[CH2:8][CH2:7]1.Br[CH2:18][C:19]1[CH:24]=[CH:23][C:22]([C:25]2[CH:30]=[CH:29][C:28]([CH2:31][Br:32])=[CH:27][CH:26]=2)=[CH:21][CH:20]=1.Cl>O1CCCC1.[Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cu+2]>[CH2:12]([C@H:9]1[CH2:10][CH2:11][C@H:6]([CH2:5][CH2:18][C:19]2[CH:24]=[CH:23][C:22]([C:25]3[CH:30]=[CH:29][C:28]([CH2:31][CH2:5][C@H:6]4[CH2:11][CH2:10][C@H:9]([CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[CH2:8][CH2:7]4)=[CH:27][CH:26]=3)=[CH:21][CH:20]=2)[CH2:7][CH2:8]1)[CH2:13][CH2:14][CH2:15][CH3:16].[Br:32][CH2:31][C:28]1[CH:29]=[CH:30][C:25]([C:22]2[CH:23]=[CH:24][C:19]([CH2:18][CH2:5][C@H:6]3[CH2:11][CH2:10][C@H:9]([CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[CH2:8][CH2:7]3)=[CH:20][CH:21]=2)=[CH:26][CH:27]=1

참가 물질

9

반응물 5

HCID 313Hydrochloric AcidHCID 807IodineHCID 6212384,4'-Bis(bromomethyl)biphenylHCID 5462224MagnesiumHCID 178444389HCID 178444389, 화합물

생성물 2

HCID 178444393HCID 178444393, 화합물수율 9%HCID 178444395HCID 178444395, 화합물수율 22%

시약·촉매·용매 2

HCID 193501Copper;dilithium;tetrachloride촉매HCID 8028Tetrahydrofuran용매4회

반응 조건

온도
-78 °C

실험 절차

122 mg of magnesium shavings were covered with 3 ml of absolute tetrahydrofuran in a sulphonation flask under argon gasification, and, after the addition of a crystal of iodine, treated with a solution of 1.24 g of trans-1-(bromomethyl)-4-pentylcyclohexane in 7 ml of absolute tetrahydrofuran. After completion of the addition, the mixture was heated to reflux for another 30 minutes and then the mixture, cooled to -78° C., was treated with 0.7 ml of a 0.1N solution of dilithium tetrachlorocuprate in tetrahydrofuran and subsequently with a solution of 670 mg of 4,4'-bis(bromomethyl)biphenyl in 10 ml of absolute tetrahydrofuran. The yellow colouration which appeared initially disappeared after a few minutes. The mixture, warmed to -15° C., was subsequently stirred for a further 17 hours, then treated with 25 ml of 2N hydrochloric acid and extracted three times with 50 ml of diethyl ether each time. The organic phases were washed with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (1.06 g) on silica gel with hexane and subsequently with hexane/diethyl ether (19:1) as the eluent gave in sequence 1,1'-ethylene-bis(trans-4-pentylcyclohexane), 228 mg (22%) of 4,4'-bis[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl, 78 mg (9 %) of 4-(bromomethyl)-4'-[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl as well as 4,4'-bis(bromomethyl)biphenyl. A single crystallization of the 228 mg of 4,4'-bis[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl from hexane yielded 194 mg of colourless needles having a clearing point above 300° C. (further phase transitions at 68° C., 84° C., 161° C., 203° C., 221° C. and 224° C.). Rf-values (hexane): 4,4'-bis(bromomethyl)biphenyl 0.14; 4-(bromomethyl)-4'-[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl 0.24; 4,4'-bis[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl 0.40.

후처리

  1. additionAfter completion of the addition
  2. temperaturethe mixture was heated
  3. temperatureto reflux for another 30 minutes
  4. waitThe yellow colouration which appeared initially disappeared after a few minutes
  5. temperatureThe mixture, warmed to -15° C.
  6. extractionextracted three times with 50 ml of diethyl ether each time
  7. washThe organic phases were washed with 50 ml of saturated sodium chloride solution
  8. dry with materialdried over magnesium sulphate
  9. concentrationconcentrated

출처 및 근거

ORD 기록
ord-d74292f5e3e445ac84a57d79d918cf8e
출처 데이터셋
uspto-grants-1986_09
특허 번호
US04613208

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