2-Chlorobenzaldehyde → HCID 10595300, compound

HRID 1815487Notes

Reaction equation

HRID 1815487 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](Cl)[CH:5]=[CH:4][C:3]=1[SH:9].[Br:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1S.ClC1C=CC=CC=1C=O.ClC1C=C(C=CC=1Cl)C=O.NCCCN1C([C@H](C(C(C)C)(C)C)O[SiH](C)C)CCC1=O.[C:58]([OH:68])(=[O:67])[CH:59]=[CH:60]C1C=CC=CC=1.Cl.CN(C)CCCN=C=NCC.O.ON1C2C=CC=CC=2N=N1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CN(C=O)C.CCOC(C)=O.C1COCC1>[Br:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[S:9][C:3]1[CH:4]=[CH:5][C:6](/[CH:60]=[CH:59]/[C:58]([OH:68])=[O:67])=[CH:7][C:2]=1[Cl:1]

Participants

13

Reactant 9

HCID 69962-ChlorobenzaldehydeHCID 87842-Propenoic acid, 3-phenyl-HCID 227103,4-DichlorobenzaldehydeHCID 707302,4-DichlorobenzenethiolHCID 805982-BromobenzenethiolHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 2724141Tetrabutylammonium FluorideHCID 27960291-Hydroxybenzotriazole hydrateHCID 131724785HCID 131724785, compound

Product 1

HCID 10595300HCID 10595300, compound

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

(2-Bromophenyl)[2-chloro-4-(2-carboxy-E-ethenyl)phenyl]sulfide was prepared by the procedures described in Example 1 substituting 2,4 dichlorothiophenol with 2-bromothiophenol, 2-chlorobenzaldehyde with 3,4 dichlorobenzaldehyde. 1-(3-aminopropyl)-5-((S)-thexyldimethylsilyloxymethyl)-2-pyrrolidinone (0.2818 g, 0.8959 mmol) was added to a solution of this cinnamic acid (0.3312 g, 0.8959 mmol), 1-[3-(dimethylamino)propyl]-3-ethyl carbodiimide hydrochloride (0.3435 g, 1.79 mmol), and 1-hydroxybenzotriazole hydrate (0.1816 g, 1.34 mmol) in DMF (4.0 mL). After stirring for 12 hours, the reaction mixture was diluted with EtOAc (250 mL), extracted with sat. NH4Cl (1×75 mL), extracted with H2O (2×75 mL), rinsed with brine (75 mL), and dried over Na2SO4. The resultant thexyldimethylsilyl alcohol was purified by flash chromatography (EtOAc) on silica gel (0.4974 g, 83%). Tetrabutylammonium fluoride (0.68 mL of 1.0 M solution in THF) was added dropwise to a solution of this protected alcohol (0.4544 g, 0.682 mmol) in THF (1.7 mL). After 2 hours, the reaction was diluted with EtOAc (50 mL) and extracted with sat. NH4Cl (1×25 mL), extracted with H2O (2×25 mL), rinsed with brine (25 mL), and dried over Na2SO4. Flash chromatography (EtOAc→9:1 CH2Cl2:MeOH) on silica gel yielded the title compound (0.3144 g, 88%). 1H-NMR (DMSO-d6, 300 MHz) δ 8.14 (t, J=5.5 Hz, 1H), 7.81 (m, 2H), 7.53 (dd, J=8.3, 1.7 Hz, 1H), 7.44 (dt, J=7.7, 1.5, 1H), 7.40 (dt, J=7.7, 1.8, 1H), 7.39 (d, J=15.6 Hz, 1H), 7.28 (dd, J=7.7, 1.8 Hz, 1H), 7.05 (d, J=8.1 Hz, 1H), 6.67 (d, J=15.6 Hz, 1H), 4.84 (t, J=5.1 Hz, 1H), 2.94-3.62 (m, 8H), 1.54-2.29 (m, 6H), MS(APCI) (M+H)+ at m/z 523, 525, 527, 529.

Workup

  1. extractionextracted with sat. NH4Cl (1×75 mL)
  2. extractionextracted with H2O (2×75 mL)
  3. washrinsed with brine (75 mL)
  4. dry with materialdried over Na2SO4
  5. customThe resultant thexyldimethylsilyl alcohol was purified by flash chromatography (EtOAc) on silica gel (0.4974 g, 83%)
  6. waitAfter 2 hours
  7. extractionextracted with sat. NH4Cl (1×25 mL)
  8. extractionextracted with H2O (2×25 mL)
  9. washrinsed with brine (25 mL)
  10. dry with materialdried over Na2SO4

Sources & evidence

ORD record
ord-fe14dd19e7044b59a36a4676ae61593c
Source dataset
uspto-grants-2005_04
Patent number
US06878700B1

Reaction notes

Loading…