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 1772336Notes

Reaction equation

HRID 1772336 reaction equation
[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

Participants

7

Reactant 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

Product 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

Reagents, catalysts & solvents 2

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-404dd0861bb34194a78c2dd89fa11df4
Source dataset
uspto-grants-2016_02
Patent number
US09249161B2

Reaction notes

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