Glutaric anhydride → 5-(5-Nitrothiazol-2-ylamino)-5-oxopentanoic acid

HRID 2207270

反応式

HRID 2207270 の反応式
[C:1]1(=[O:8])[O:7][C:5](=[O:6])[CH2:4][CH2:3][CH2:2]1.[NH2:9][C:10]1[S:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][N:14]=1>CN(C1C=CN=CC=1)C.C(Cl)Cl.CCOC(C)=O>[N+:15]([C:12]1[S:11][C:10]([NH:9][C:5](=[O:6])[CH2:4][CH2:3][CH2:2][C:1]([OH:7])=[O:8])=[N:14][CH:13]=1)([O-:17])=[O:16]

参加物

6

反応物 2

HCID 7940Glutaric anhydrideHCID 84862-Amino-5-Nitrothiazole

生成物 1

HCID 149670755-(5-Nitrothiazol-2-ylamino)-5-oxopentanoic acid収率 54%

試薬・触媒・溶媒 3

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

Glutaric anhydride (1.0 g, 8.8 mmol), TEA (1.35 ml, 9.6 mmol) and cat. DMAP were dissolved in CH2Cl2 (7 mL). 2-Amino-5-nitrothiazole (1.4 g, 9.64 mmol) was then added and the solution was held at ambient temperature. After 18 hours, the solution was diluted with EtOAc (50 mL) and extracted with 1M NaOH (3×30 mL). The combined aqueous layers were washed with EtOAc (20 mL) then acidified with 12M HCl and subsequently extracted with EtOAc (5×20 mL). The combined organics were washed with brine (2×20 mL), dried (MgSO4), filtered and concentrated to dryness to yield 5-(5-nitrothiazol-2-ylamino)-5-oxopentanoic acid (1.13 g, 54%) as an orange solid. 1H NMR (300 MHz, DMSO-d6) δ 12.59 (bs, 1H), 8.59 (s, 1H), 2.57 (t, J=7.4 Hz, 2H), 2.28 (t, J=7.3 Hz, 2H), 1.82 (quint., J=7.3 Hz, 2H); 13C NMR (75 MHz, DMSO-d6) δ 174.0, 172.8, 161.8, 142.8, 141.7, 34.1, 32.7, 19.6; HRMS (ESI) calcd for [C8H9N3O5S+H]+260.0336. found 260.0344. Method B with 5-(5-nitrothiazol-2-ylamino)-5-oxopentanoic acid (30 mg, 0.12 mmol) afforded the title compound VPC161276 (23 mg, 46%) as an orange solid. 1H NMR (300 MHz, DMSO-d6) δ 8.61 (s, 2H), 2.61 (t, J=7.2 Hz, 4H), 1.97 (quint., J=7.0 Hz, 2H); 13C NMR (75 MHz, DMSO-d6) δ 172.8, 162.0, 142.8, 141.5, 34.0, 19.3; HRMS (ESI) calcd for [C11H10N6O6S2+H]+ 387.0176. found 387.0185.

後処理

  1. customwas held at ambient temperature
  2. extractionextracted with 1M NaOH (3×30 mL)
  3. washThe combined aqueous layers were washed with EtOAc (20 mL)
  4. extractionsubsequently extracted with EtOAc (5×20 mL)
  5. washThe combined organics were washed with brine (2×20 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated to dryness

出典と根拠

ORDレコード
ord-ff6797ddc6d44d4da6ba6589f76510bd
出典データセット
uspto-grants-2016_06
特許番号
US09376430B2

関連ノート

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