Toluene → 2-(Phenoxymethyl)morpholine

HRID 977077

반응식

HRID 977077 반응식
S(O)([O:4][CH2:5][CH2:6][NH2:7])(=O)=O.O1[CH:11]([CH2:12][O:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH2:10]1.[OH-].[Na+].C1(C)C=CC=CC=1>O.CO>[O:13]([CH2:12][CH:11]1[O:4][CH2:5][CH2:6][NH:7][CH2:10]1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

참가 물질

7

반응물 4

HCID 1140Toluene2회HCID 14798Sodium Hydroxide2회HCID 31217Phenyl glycidyl etherHCID 70223Aminoethyl sulfate

생성물 1

HCID 220117952-(Phenoxymethyl)morpholine수율 62.3%

시약·촉매·용매 2

HCID 887Methanol용매HCID 962Water용매2회

반응 조건

온도
40 °C

실험 절차

2-Aminoethyl hydrogen sulphate (49 g, 0.347 mol) was added in portions to a mixture of (±)-1,2-epoxy-3-phenoxypropane (11.2 ml, 0.083 mol), sodium hydroxide (26.4 g, 0.66 mol) in water (50 ml) and methanol (20 ml). After addition the reaction mixture was stirred at 40° C. (oil bath temperature) for 2 hours. The reaction mixture was cooled, sodium hydroxide pellets (20.65 g, 0.516 mol) and toluene (80 ml) were added, then the reaction mixture stirred, whilst heating at 65° C. (oil bath temperature) for 7.5 hours. The reaction mixture was cooled, toluene (40 ml) and water (140 ml) were added. The toluene phase was extracted with 2M hydrochloric acid (2×60 ml). The acid extracts were combined, 40% sodium hydroxide solution added to pH=11, then extracted with toluene (2×60 ml). The combined organics were dried (sodium sulphate) then evaporated to give a colourless gum (10 g) which was purified by column chromatography on silica, using neat ethyl acetate to remove the lipophilic impurities then ethyl acetate/methanol/ammonia (9:1:0.1) to elute the required product as a colourless oil (7.0 g, 44%). Rf 0.22 in dichloromethane/methanol (9:1) on silica plates MS CI+, m/z=194 for (M+H)+. 1H NMR (360 MHz, CDCl3) δ2.54-2.85 (2H, m), 2.92 (1H, ddd, J1 =2, J2 =J3 =12 Hz), 3.05 (1H, dd, J1 =2, J2 =12 Hz), 3.67 (1H, ddd, J1 =2, J2 =J3=12 Hz), 3.83-4.03 (4H, m), 6.88-6.97 (3H, m), 7.23-7.30 (2H, m).

후처리

  1. additionAfter addition the reaction mixture
  2. temperatureThe reaction mixture was cooled
  3. stirringthe reaction mixture stirred
  4. temperaturewhilst heating at 65° C. (oil bath temperature) for 7.5 hours
  5. temperatureThe reaction mixture was cooled
  6. extractionThe toluene phase was extracted with 2M hydrochloric acid (2×60 ml)
  7. addition40% sodium hydroxide solution added to pH=11
  8. extractionextracted with toluene (2×60 ml)
  9. dry with materialThe combined organics were dried (sodium sulphate)
  10. customthen evaporated

출처 및 근거

ORD 기록
ord-bf16b9ff48eb43e8beca7494c4422d05
출처 데이터셋
uspto-grants-1997_03
특허 번호
US05614518

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