Phosphorus sulfide (P2S5) → 1,3,4,5-Tetrahydro-2H-1-benzazepine-2-thione

HRID 80527

Reaction equation

HRID 80527 reaction equation
[NH:1]1[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][CH2:3][C:2]1=O.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:14]>N1C=CC=CC=1>[NH:1]1[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][CH2:3][C:2]1=[S:14]

Participants

4

Reactant 2

HCID 14817Phosphorus sulfide (P2S5)HCID 2485801,3,4,5-Tetrahydro-2H-1-benzazepin-2-one

Product 1

HCID 125454261,3,4,5-Tetrahydro-2H-1-benzazepine-2-thione

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of Example 182A (12.435 g, 77 mmol) in pyridine (309 mL) under nitrogen was added phosphorus pentasulfide (34.3 g, 154 mmol), and the mixture was heated at 120° C. (reflux) for 2 hours. The solvent was decanted and water was added. The product was extracted with dichloromethane, pre-absorbed onto silica gel and purified by silica gel chromatography (Analogix IntelliFlash™ 280, SF10-150) eluting with 30% ethyl acetate/hexanes to obtain the title compound. 1H NMR (500 MHz, DMSO-d6) δ ppm 11.75 (s, 1H), 7.32-7.25 (m, 2H), 7.19 (td, J=7.5, 1.2, 1H), 7.10-7.00 (m, 1H), 2.63 (m, 4H), 2.20 (m, 2H); MS (ESI−) m/z 176.1 (M−H)−.

Workup

  1. temperature(reflux) for 2 hours
  2. customThe solvent was decanted
  3. additionwater was added
  4. extractionThe product was extracted with dichloromethane
  5. custompre-absorbed onto silica gel
  6. custompurified by silica gel chromatography (Analogix IntelliFlash™ 280, SF10-150)
  7. washeluting with 30% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-a22560ee744b479eba60d265586cf79a
Source dataset
uspto-grants-2014_09
Patent number
US08846663B2

Linked notes

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