Potassium Bromide → (1S,2R)-4'-(4-Chlorophenyl)-2',3',9'-trimethylspiro[cyclopropane-1,6'-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepine]-2-carbaldehyde

HRID 1772336Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1772336
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:14]3[C:15]([CH3:19])=[C:16]([CH3:18])[S:17][C:13]=3[N:12]3[C:20]([CH3:23])=[N:21][N:22]=[C:11]3[C@@:10]3([CH2:25][C@H:24]3[CH2:26][OH:27])[N:9]=2)=[CH:4][CH:3]=1.CC1(C)N([O])C(C)(C)CC(OC)C1.[Br-].[K+].Cl[O-].[Na+]>C(Cl)Cl.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-]>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[C:14]3[C:15]([CH3:19])=[C:16]([CH3:18])[S:17][C:13]=3[N:12]3[C:20]([CH3:23])=[N:21][N:22]=[C:11]3[C@@:10]3([CH2:25][C@H:24]3[CH:26]=[O:27])[N:9]=2)=[CH:6][CH:7]=1

Komponenten

7

Edukt 4

HCID 253877Potassium BromideHCID 103134354-methoxy-TEMPOHCID 23665760Sodium HypochloriteHCID 57404763((1S,2R)-4'-(4-chlorophenyl)-2',3',9'-trimethylspiro[cyclopropane-1,6'-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepin]-2-yl)methanol

Produkt 1

HCID 86706921(1S,2R)-4'-(4-Chlorophenyl)-2',3',9'-trimethylspiro[cyclopropane-1,6'-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepine]-2-carbaldehyde

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 21218Trioctylmethylammonium chlorideKatalysatorHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of ((1S,2R)-4′-(4-chlorophenyl)-2′,3′,9′-trimethylspiro[cyclopropane-1,6′-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepine]-2-yl)methanol (300 mg, 0.752 mmol) in DCM (5 mL), a solution of 4-methoxy TEMPO (0.0135M in DCM) (1 mL, 0.0135 mmol), a solution of Aliquat 336 (0.074M in DCM) (0.5 mL, 0.037 mmol) and a solution of potassium bromide (0.25M in water) (0.3 mL, 0.075 mmol) were mixed and cooled to 0° C. before a solution of sodium hypochlorite (0.35M in water; buffered with NaHCO3 to pH˜8.6) was slowly added. After 30 min of vigorous stirring at 0° C., the aqueous layer was extracted with DCM. 2-Methyl-2-butene (0.5 mL) was added to the organic layer, before it was concentrated to dryness. The residue was used in the next step without purification. LRMS (M+H)+: 397 m/z.

Aufarbeitung

  1. additionwas slowly added
  2. extractionthe aqueous layer was extracted with DCM
  3. addition2-Methyl-2-butene (0.5 mL) was added to the organic layer, before it
  4. concentrationwas concentrated to dryness
  5. customThe residue was used in the next step without purification

Quellen und Nachweise

ORD-Eintrag
ord-404dd0861bb34194a78c2dd89fa11df4
Quelldatensatz
uspto-grants-2016_02
Patentnummer
US09249161B2

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