Triphenylphosphine → 5-bromo-4-chloro-7-[2-(4-morpholinyl)ethyl]-7H-pyrrolo[2,3-d]pyrimidine

HRID 1910025노트

반응식

HRID 1910025 반응식
[Br:1][C:2]1[C:10]2[C:5]([NH:6][CH:7]=[N:8][C:9]=2[Cl:11])=[N:4][CH:3]=1.[N:12]1([CH2:18][CH2:19]O)[CH2:17][CH2:16][O:15][CH2:14][CH2:13]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>O1CCCC1>[Br:1][C:2]1[C:10]2[C:9]([Cl:11])=[N:8][CH:7]=[N:6][C:5]=2[N:4]([CH2:19][CH2:18][N:12]2[CH2:17][CH2:16][O:15][CH2:14][CH2:13]2)[CH:3]=1

참가 물질

6

반응물 4

HCID 11776TriphenylphosphineHCID 611632-MorpholinoethanolHCID 5462977Diethyl azodicarboxylateHCID 178478408HCID 178478408, 화합물

생성물 1

HCID 866636825-bromo-4-chloro-7-[2-(4-morpholinyl)ethyl]-7H-pyrrolo[2,3-d]pyrimidine수율 82.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To 5-bromo-4-chloro-1H-pyrrolo[2,3-d]pyrimidine (200 mg, 0.860 mmol), 2-(4-morpholinyl)ethanol (0.316 mL, 2.58 mmol) and triphenylphosphine (451 mg, 1.721 mmol) was added Tetrahydrofuran (THF) (5 mL). To the reaction was then added by dropwise DEAD (0.272 mL, 1.721 mmol). The solution was then let stir overnight at room temperature. The reaction was then concentrated and diluted with water (10 ml) then extracted by EtOAc (3×10 ml). The organics were combined, washed with brine, dried over MgSO4, filtered and concentrated. The yellow crude residue was then loaded onto a 25 g Biotage SNAP column and purified with 0 to 8% MeOH in DCM gradient over 30 minutes to afford 5-bromo-4-chloro-7-[2-(4-morpholinyl)ethyl]-7H-pyrrolo[2,3-d]pyrimidine (245 mg, 82% yield) as a light yellow solid. LC-MS (ES) m/z=347.2 [M+H]+1H NMR (400 MHz, DMSO-d6) δ 8.67 (s, 1H), 8.05 (s, 1H), 4.39 (t, J=6.19 Hz, 2H), 3.48 (t, J=4.29 Hz, 4H), 2.71 (t, J=6.32 Hz, 2H), 2.42 (br. s., 4H).

후처리

  1. concentrationThe reaction was then concentrated
  2. additiondiluted with water (10 ml)
  3. extractionthen extracted by EtOAc (3×10 ml)
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified with 0 to 8% MeOH in DCM gradient over 30 minutes

출처 및 근거

ORD 기록
ord-14041ea8140b431699d5ec0c2b0b4366
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08598156B2

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