Triethylamine → HCID 178440395、化合物

HRID 1987614ノート

反応式

HRID 1987614 の反応式
Cl[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[NH:5]/[C:4](=[C:12]2/[C:13]([CH2:18][CH2:19][CH3:20])=[N:14][NH:15][C:16]/2=[O:17])/[CH:3]=1.C(OC(OC(C)(C)C)=O)(OC(C)(C)C)=O.C(N(CC)CC)C.C(OC(N1C(=O)/C(=C2\N(C(OC(C)(C)C)=O)C3C(C(Cl)=C\2)=CC=CC=3)/C(CCC)=N1)=O)(C)(C)C.[NH2:77][C:78]1[CH:83]=[CH:82][C:81]([SH:84])=[CH:80][CH:79]=1.[CH3:85][S:86](Cl)(=[O:88])=[O:87]>CN(C=O)C.CCOC(C)=O.C(O)C.O>[O:17]=[C:16]1[NH:15][N:14]=[C:13]([CH2:18][CH2:19][CH3:20])/[C:12]/1=[C:4]1/[NH:5][C:6]2[C:11]([C:2]([S:84][C:81]3[CH:82]=[CH:83][C:78]([NH:77][S:86]([CH3:85])(=[O:88])=[O:87])=[CH:79][CH:80]=3)=[CH:3]/1)=[CH:10][CH:9]=[CH:8][CH:7]=2

参加物

11

反応物 6

HCID 8471TriethylamineHCID 145104-AminothiophenolHCID 31297Methanesulfonyl chlorideHCID 90495Di-tert-butyl dicarbonateHCID 69050827(Z)-tert-butyl 2-(1-(tert-butoxycarbonyl)-5-oxo-3-propyl-1H-pyrazol-4(5H)-ylidene)-4-chloroquinoline-1 (2H)-carboxylateHCID 178440352HCID 178440352、化合物

生成物 1

HCID 178440395HCID 178440395、化合物

試薬・触媒・溶媒 4

HCID 702Ethanol溶媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
30 °C

実験手順

(Z)-4-(4-chloroquinolin-2(1H)-ylidene)-3-propyl-1H-pyrazol-5(4H)-one (1.0 g, 3.48 mmol) was stirred in DMF at ambient temperature and Di-t-butyl dicarbonate (2.28 g, 10.5 mmol) was added followed by triethylamine (2.43 mL, 17.4 mmol). After 24 hrs, the reaction mixture was diluted with EtOAc and worked up with DI water. The organic phase was washed with brine and dried over MgSO4, and concentrated to dryness and triturated with methanol. The resulting (Z)-tert-butyl 2-(1-(tert-butoxycarbonyl)-5-oxo-3-propyl-1H-pyrazol-4(5H)-ylidene)-4-chloroquinoline-1 (2H)-carboxylate (0.1 g, 0.21 mmol) was stirred in ethanol and 4-aminothiophenol (0.031 g, 0.25 mmol) was added. The reaction mixture was heated at 30° C. for 2 hrs, concentrated to dryness, and carried out to the next step without further purification. The resulting (Z)-tert-butyl 4-(4-aminophenylthio)-2-(1-(tert-butoxycarbonyl)-5-oxo-3-propyl-1H-pyrazol-4(5H)-ylidene)quinoline-1(2H)-carboxylate was dissolved in pyridine (1-2 mL) and treated with methanesulfonyl chloride (0.048 mL, 0.61 mmol). After 2-4 hr, the solvent was evaporated and the solid redissolved in dichloromethane. Trifluoroacetic acid (1.2 mL) was added dropwise. The final compound was purified by LC-MS to yield Example 26. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.73 (t, J=7.33 Hz, 3H) 1.27-1.37 (m, 2H) 2.30 (t, J=7.33 Hz, 2H) 3.14 (s, 3H) 6.80 (s, 1H) 7.43 (d, J=8.59 Hz, 2H) 7.63 (t, J=7.58 Hz, 1H) 7.72 (d, J=8.59 Hz, 2H) 7.84-7.95 (m, 2H) 8.14 (d, J=8.08 Hz, 1H) 10.34 (s, 1H); ESI-MS: m/z calc'd for C22H22N0O3S2 454.57. found 455.2 (M+H)+.

後処理

  1. washThe organic phase was washed with brine
  2. dry with materialdried over MgSO4
  3. concentrationconcentrated to dryness
  4. customtriturated with methanol
  5. concentrationconcentrated to dryness
  6. customcarried out to the next step without further purification
  7. dissolutionThe resulting (Z)-tert-butyl 4-(4-aminophenylthio)-2-(1-(tert-butoxycarbonyl)-5-oxo-3-propyl-1H-pyrazol-4(5H)-ylidene)quinoline-1(2H)-carboxylate was dissolved in pyridine (1-2 mL)
  8. waitAfter 2-4 hr
  9. customthe solvent was evaporated
  10. dissolutionthe solid redissolved in dichloromethane
  11. additionTrifluoroacetic acid (1.2 mL) was added dropwise
  12. customThe final compound was purified by LC-MS
  13. customto yield Example 26

出典と根拠

ORDレコード
ord-925090eb3a8646ca83bfe24d23bbe8ec
出典データセット
uspto-grants-2009_06
特許番号
US07550598B2

反応ノート

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