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Hydrochloric Acid → HCID 22475266, 화합물

HRID 1860696
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HRID 1860696 반응식
C[O:2][C:3]1[CH:4]=[C:5]([C:9]23[CH2:18][C:17]4[CH:19]=[CH:20][CH:21]=[CH:22][C:16]=4[CH2:15][C:14]2([CH3:23])[CH2:13][N:12](C)[CH2:11][CH2:10]3)[CH:6]=[CH:7][CH:8]=1.CN([P+](ON1N=NC2C=CC=CC1=2)(N(C)C)N(C)C)C.F[P-](F)(F)(F)(F)F.C(N(CC)CC)C.[C:59]1([CH2:65][C:66](O)=O)[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1.CSC.B.Cl>C(OCC)C.O1CCCC1.CO.C1(C)C=CC=CC=1>[OH:2][C:3]1[CH:4]=[C:5]([C:9]23[CH2:18][C:17]4[CH:19]=[CH:20][CH:21]=[CH:22][C:16]=4[CH2:15][C:14]2([CH3:23])[CH2:13][N:12]([CH2:66][CH2:65][C:59]2[CH:60]=[CH:61][CH:62]=[CH:63][CH:64]=2)[CH2:11][CH2:10]3)[CH:6]=[CH:7][CH:8]=1
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참가 물질

11

반응물 6

HCID 313Hydrochloric AcidHCID 999Phenylacetic AcidHCID 8471TriethylamineHCID 151348Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphateHCID 12423031(Dimethyl sulfide)trihydroboronHCID 22475286HCID 22475286, 화합물

생성물 1

HCID 22475266
HCID 22475266, 화합물
수율 14.7%

시약·촉매·용매 4

HCID 887Methanol용매HCID 1140Toluene용매HCID 3283Diethyl Ether용매2회HCID 8028Tetrahydrofuran용매2회

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온도
80 °C

실험 절차

To 300 mg (0.93 mmol) intermediate (10) was added 5 mL dry toluene followed by heating to 80° C. To this was added 0.23 mL (1.86 mmol) distilled phenylchloroformate dropwise via syringe. A precipitate formed, and the mixture was heated at reflux for 5 h. The mixture was cooled to room temperature and washed 3 times with 1N NaOH and dried over sodium sulfate. 1H NMR of the crude mixture indicated that no starting material was present (no N-methyl signal at 2.25 ppm). The crude mixture was then dissolved in 4 mL glacial acetic acid and 4 mL 48% HBr. This was heated at reflux for 18 h followed by addition of water and methyl t-butyl ether (MTBE). The aqueous layer was removed and extracted two more times with MTBE to remove phenol. The aqueous layer was then pH adjusted to 10 using 50% NaOH and saturated sodium bicarbonate and extracted 3 times with 3:1 methylene chloride:tetrahydrofuran (THF) and the organic layer dried over sodium sulfate. Following removal of solvent, this highly polar material was dissolved in 15 mL THF, and to this was added 442 mg (1 mmol) BOP reagent, 0.4 mL triethylamine (2.2 mmol), and 136 mg (1 mmol) phenyl acetic acid. This was stirred for 3 h and then diluted with ethyl ether, 40 mL, and washed sequentially with 15 mL water, 1N HCl, saturated sodium bicarbonate, and brine. The solution was dried over sodium sulfate and the solvent removed on a rotary evaporator. The material was then dissolved in chloroform and filtered through silica gel to remove highly colored polar impurities to give 142 mg relatively clean material. 1H NMR of this crude material indicated the presence of rotamers typical of piperidine amides and urethanes. Reduction of this compound was accomplished by dissolving in dry THF followed by addition of 1.16 mL of 2M borane dimethylsulfide in THF. After heating for 3 h, the mixture was cooled to room temperature, and 2 mL methanol was added and stirred for 1 h. After this time, 1.16 mL 1N HCl in ether was added and stirred for 1 h. The solvent was then removed on a rotary evaporator and the crude mixture dissolved in chloroform, saturated sodium bicarbonate, and water. The pH was adjusted to 10 and the organic layer washed 3 times with water and then dried over sodium sulfate. The crude residue was chromatographed on silica gel using 0-10% MeOH in chloroform as eluent, and this material was crystallized from MeOH/ether as its HCl salt to give 55.8 mg of the desired material (0.137 mmol) or 2.2% overall yield. MP ° C. 255-265 (dec). Anal. Calcd for C28H32NOCl.0.5H2O: C, 75.91; H, 7.51; N, 3.16. Found: C, 75.93; H, 7.53; N, 3.17. 1H NMR (DMSO) δ 10.06 (br s, 1H); 9.34 (s, 1H); 7.30 (dd, 2H, J=8.1 Hz, 8.1 Hz); 7.22 (m, 5H); 7.15 (dd, 1H, J=7.7 Hz, 7.7 Hz); 7.08 (d, 1H, J=7.7 Hz); 6.63 (s, 1H); 6.62 (d, 1H, J=8.1 Hz); 6.55 (d, 1H, J=8.1 Hz); 3.59 (d, 1H, J=18.9 Hz); 3.50 (d, 1H, J=12.1 Hz); 3.32 (m, 4H); 3.11 (ddd, 1H, J=5.1 Hz, 12.1 Hz, 12.1 Hz); 3.02 (ddd, 1H, J=5.1 Hz, 12.1 Hz, 12.1 Hz); 2.87 (m, 3H); 2.50 (d, 1H, J=17.4); 2.42 (d, 1H, J=17.4); 1.62 (d, 1H, J=14.3); 1.08 (s, 3H). 13C NMR (DMSO) δ 156.72, 146.44, 137.23, 135.45, 133.38, 128.63, 128.59, 128.56, 128.52, 128.19, 126.71, 126.39, 125.72, 117.55, 114.33, 113.51, 57.27, 57.18, 48.22, 39.46, 38.66, 35.40, 35.21, 29.45, 28.59, 23.06.

후처리

  1. additionTo this was added 0.23 mL (1.86 mmol)
  2. distillationdistilled phenylchloroformate dropwise via syringe
  3. customA precipitate formed
  4. temperaturethe mixture was heated
  5. temperatureat reflux for 5 h
  6. temperatureThe mixture was cooled to room temperature
  7. washwashed 3 times with 1N NaOH
  8. dry with materialdried over sodium sulfate
  9. dissolutionThe crude mixture was then dissolved in 4 mL glacial acetic acid
  10. temperatureThis was heated
  11. temperatureat reflux for 18 h
  12. additionfollowed by addition of water and methyl t-butyl ether (MTBE)
  13. customThe aqueous layer was removed
  14. extractionextracted two more times with MTBE
  15. customto remove phenol
  16. extractionextracted 3 times with 3:1 methylene chloride
  17. dry with materialtetrahydrofuran (THF) and the organic layer dried over sodium sulfate
  18. customremoval of solvent
  19. dissolutionthis highly polar material was dissolved in 15 mL THF
  20. washwashed sequentially with 15 mL water, 1N HCl, saturated sodium bicarbonate, and brine
  21. dry with materialThe solution was dried over sodium sulfate
  22. customthe solvent removed on a rotary evaporator
  23. dissolutionThe material was then dissolved in chloroform
  24. filtrationfiltered through silica gel
  25. customto remove highly colored polar impurities
  26. customto give 142 mg relatively clean material
  27. temperatureAfter heating for 3 h
  28. temperaturethe mixture was cooled to room temperature
  29. stirringstirred for 1 h
  30. stirringstirred for 1 h
  31. customThe solvent was then removed on a rotary evaporator
  32. dissolutionthe crude mixture dissolved in chloroform
  33. washthe organic layer washed 3 times with water
  34. dry with materialdried over sodium sulfate
  35. customThe crude residue was chromatographed on silica gel using 0-10% MeOH in chloroform as eluent
  36. customthis material was crystallized from MeOH/ether as its HCl salt

출처 및 근거

ORD 기록
ord-1a5d680041da46c7a7b98668c126a7aa
출처 데이터셋
uspto-grants-2003_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06531481B2

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