Ethanesulfonylchloride, 2-chloro- → Ethyl 4-{3-[(ethenylsulfonyl)amino]phenyl}-7H-pyrrolo[2,3-d]pyrimidine-5-carboxylate

HRID 882135Notes

Reaction equation

HRID 882135 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([C:8]2[C:9]3[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:15][NH:14][C:10]=3[N:11]=[CH:12][N:13]=2)[CH:5]=[CH:6][CH:7]=1.CCN(C(C)C)C(C)C.Cl[CH2:32][CH2:33][S:34](Cl)(=[O:36])=[O:35]>C(Cl)Cl>[CH:33]([S:34]([NH:1][C:2]1[CH:3]=[C:4]([C:8]2[C:9]3[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:15][NH:14][C:10]=3[N:11]=[CH:12][N:13]=2)[CH:5]=[CH:6][CH:7]=1)(=[O:36])=[O:35])=[CH2:32]

Participants

5

Reactant 3

HCID 15385Ethanesulfonylchloride, 2-chloro-HCID 81531DiisopropylethylamineHCID 71598790ethyl 4-(3-aminophenyl)-7H-pyrrolo[2,3-d]pyrimidine-5-carboxylate

Product 1

HCID 89629994Ethyl 4-{3-[(ethenylsulfonyl)amino]phenyl}-7H-pyrrolo[2,3-d]pyrimidine-5-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To ethyl 4-(3-aminophenyl)-7H-pyrrolo[2,3-d]pyrimidine-5-carboxylate (60 mg, 0.21 mmol) was added DCM (1.1 mL) and DIPEA (45 μL, 0.26 mmol) at 0° C. Then 2-chloroethanesulfonyl chloride (68 mg, 0.42 mmol) was added and the reaction was stirred vigorously for 15 hours before being quenched by pouring into a separatory funnel containing aqueous sodium hydrogen carbonate (20%). The aqueous layer was then extracted with ethyl acetate (×3) and the organic layers were combined, dried with Na2SO4, filtered, and concentrated in vacuo. The crude product was then purified using a silica column, eluting with DCM with a 10-80% of a 2% methanol/EtOAc modifying co-solvents. The product was collected and concentrated in vacuo to afford the desired product as a yellow solid. LRMS (ESI) calc'd for C17H17N4O4S [M+H]+: 373, found 373. 1H NMR (600 MHz, CDCl3) δ 10.74 (bs, 1H), 9.04 (s, 1H), 8.12 (s, 1H), 7.38-7.54 (m, 5H), 6.61 (dd, 1H, J=17.4, 10.8 Hz), 6.33 (d, 1H, J=16.2 Hz), 5.96 (d, 1H, J=10.2 Hz), 4.04 (q, 2H, J=7.2 Hz), 1.01 (t, 3H, J=7.2 Hz).

Workup

  1. custombefore being quenched
  2. additionby pouring into a separatory funnel
  3. additioncontaining aqueous sodium hydrogen carbonate (20%)
  4. extractionThe aqueous layer was then extracted with ethyl acetate (×3)
  5. dry with materialdried with Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product was then purified
  9. washeluting with DCM with a 10-80% of a 2% methanol/EtOAc modifying co-solvents
  10. customThe product was collected
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-91810290a04843e49fae88999e55a52f
Source dataset
uspto-grants-2015_03
Patent number
US08993756B2

Reaction notes

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