Hydrochloric Acid → ethyl 2-(5-(3-(hydroxymethyl)pyridin-2-yl)-1H-pyrazol-1-yl)acetate

HRID 1471751ノート

反応式

HRID 1471751 の反応式
[Si]([O:8][CH2:9][C:10]1[C:11]([C:16](=O)/[CH:17]=[CH:18]/[N:19](C)C)=[N:12][CH:13]=[CH:14][CH:15]=1)(C(C)(C)C)(C)C.Cl.[NH:24]([CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])N.Cl>CCO>[OH:8][CH2:9][C:10]1[C:11]([C:16]2[N:24]([CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])[N:19]=[CH:18][CH:17]=2)=[N:12][CH:13]=[CH:14][CH:15]=1

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 11593468Acetic acid, 2-hydrazinyl-, ethyl ester, hydrochloride (1:1)HCID 86690729(E)-1-(3-((tert-butyldimethylsilyloxy)methyl)pyridin-2-yl)-3-(dimethylamino)prop-2-en-1-one

生成物 1

HCID 86690789ethyl 2-(5-(3-(hydroxymethyl)pyridin-2-yl)-1H-pyrazol-1-yl)acetate収率 74.4%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
80 °C

実験手順

To (E)-1-(3-((tert-butyldimethylsilyloxy)methyl)pyridin-2-yl)-3-(dimethylamino)prop-2-en-1-one (crude, 350 mg, 1.09 mmol, 1 eq.) in EtOH (10 mL) was added ethyl 2-hydrazinylacetate hydrochloride (338 mg, 2.18 mmol, 2.0 eq.). The mixture was heated at 80° C. for 2 h, cooled to rt, added HCl (6 N, 0.5 mL), and stirred O/N. The mixture was concentrated, and diluted with a mixture of EtOAc (50 mL) and NaHCO3(sat) (10 mL). The layers were separated and the aqueous layer was extracted with EtOAc three times. The combined organic layers were dried over Na2SO4, concentrated, and purified on silica gel using EtOAc as eluent to give ethyl 2-(5-(3-(hydroxymethyl)pyridin-2-yl)-1H-pyrazol-1-yl)acetate (212 mg, 74%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.61 (dd, J=4.7, 1.6 Hz, 1H), 7.97 (dd, J=7.8, 1.4 Hz, 1H), 7.64 (d, J=1.9 Hz, 1H), 7.36 (dd, J=7.8, 4.8 Hz, 1H), 6.56 (d, J=1.9 Hz, 1H), 5.21 (s, 2H), 4.79 (d, J=5.8 Hz, 2H), 4.09 (q, J=7.1 Hz, 2H), 2.54 (t, J=6.0 Hz, 1H), 1.18 (t, J=7.1 Hz, 31-1). LRMS m/z 262.1

後処理

  1. temperaturecooled to rt
  2. concentrationThe mixture was concentrated
  3. additiondiluted with a mixture of EtOAc (50 mL) and NaHCO3(sat) (10 mL)
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc three times
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. concentrationconcentrated
  8. custompurified on silica gel

出典と根拠

ORDレコード
ord-14644d98923940b09b36899bdbb853ab
出典データセット
uspto-grants-2015_04
特許番号
US09012450B2

反応ノート

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