Nitric Acid → (S)-5-Amino-6-nitro-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

HRID 550990

반응식

HRID 550990 반응식
[NH2:1][C:2]1[CH:3]=[C:4]2[C:25](=[CH:26][CH:27]=1)[CH2:24][C@:6]1([C:14]3[C:9](=[N:10][CH:11]=[CH:12][CH:13]=3)[N:8](COCC[Si](C)(C)C)[C:7]1=[O:23])[CH2:5]2.FC(F)(F)C(OC(=O)C(F)(F)F)=O.NC1C=CC=CC=1.FC(F)(F)C(NC1C=CC=CC=1)=O.[N+:61]([O-])([OH:63])=[O:62].FC(F)(F)C(O)=O.C(N)CN>C(Cl)Cl.O>[NH2:1][C:2]1[CH:3]=[C:4]2[C:25](=[CH:26][C:27]=1[N+:61]([O-:63])=[O:62])[CH2:24][C@:6]1([C:14]3[C:9](=[N:10][CH:11]=[CH:12][CH:13]=3)[NH:8][C:7]1=[O:23])[CH2:5]2

참가 물질

10

반응물 7

HCID 944Nitric AcidHCID 3301EthylenediamineHCID 6115AnilineHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 678812,2,2-Trifluoro-N-phenylacetamideHCID 66973634(R)-5-amino-1'-{[2-(trimethylsilyl)ethoxy]methyl}-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one2회

생성물 1

HCID 67174155(S)-5-Amino-6-nitro-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

시약·촉매·용매 2

HCID 962Water용매2회HCID 6344Dichloromethane용매2회

실험 절차

To a suspension of (R)-5-amino-1′-{[2-(trimethylsilyl)ethoxy]methyl}-1,3-dihydrospiro[indene-2,3′-pyrrolo[2,3-b]pyridin]-2′(1′H)-one (28.7 g, 75.2 mmol, described in Intermediate 3) in CH2Cl2 (100 mL) was added trifluoroacetic anhydride (106 mL, 752 mmol). The mixture was stirred for 10 min, after which time the aniline had been converted to the corresponding trifluoroacetanilide. The resulting mixture was cooled in an ice-salt bath and 15.8 M nitric acid (5.0 mL, 79 mmol) was added dropwise over 15 min, keeping the reaction temperature at 10-12° C. After the addition, the reaction mixture was stirred for 30 min, then H2O (12 mL) was carefully added, followed by trifluoroacetic acid (100 mL) and CH2Cl2 (100 mL). The mixture was allowed to warm to ambient temperature and stirring was continued for 2 h, followed by concentration to dryness in vacuo. The residue was dissolved in MeOH (200 mL) and the solution was adjusted to pH 10 by addition of 10 N NaOH. Ethylene diamine (5 mL, 75 mmol) was added and the mixture was stirred at ambient temperature for 18 h, then diluted with H2O (200 mL). The resulting solid was isolated by filtration, washed with H2O, and dried in vacuo to give the title compound. MS: m/z=297 (M+1).

후처리

  1. temperatureThe resulting mixture was cooled in an ice-salt bath
  2. customat 10-12° C
  3. additionAfter the addition
  4. stirringthe reaction mixture was stirred for 30 min
  5. stirringstirring
  6. waitwas continued for 2 h
  7. concentrationfollowed by concentration to dryness in vacuo
  8. dissolutionThe residue was dissolved in MeOH (200 mL)
  9. additionthe solution was adjusted to pH 10 by addition of 10 N NaOH
  10. stirringthe mixture was stirred at ambient temperature for 18 h
  11. customThe resulting solid was isolated by filtration
  12. washwashed with H2O
  13. customdried in vacuo

출처 및 근거

ORD 기록
ord-1c2e464fbfe74542be207d8e076f6a22
출처 데이터셋
uspto-grants-2011_05
특허 번호
US07947677B2

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