Thionyl Chloride → Chloro-iododibenzoylbenzene

HRID 78393

Reaction equation

HRID 78393 reaction equation
Cl[C:2]1[CH:3]=[C:4]([C:12]([OH:14])=O)[C:5]([I:11])=[C:6]([CH:10]=1)C(O)=O.O=S(Cl)Cl.Cl[C:20]1[CH:21]=[C:22](C(Cl)=O)[C:23](I)=[C:24]([CH:28]=1)[C:25](Cl)=[O:26].[C:33]1(CCCCCCCCCCCC)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.[Al+3].[Cl-:52].[Cl-].[Cl-]>ClCCl>[Cl:52][C:6]1[CH:10]=[CH:2][C:3]([C:25](=[O:26])[C:24]2[CH:28]=[CH:20][CH:21]=[CH:22][CH:23]=2)=[C:4]([C:12](=[O:14])[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:5]=1[I:11]

Participants

7

Reactant 5

HCID 24386Thionyl ChlorideHCID 31237DodecylbenzeneHCID 6451240Aluminum(III) ChlorideHCID 672380385-Chloro-2-iodo-isophthalic acidHCID 86654794HCID 86654794, compound

Product 1

HCID 67036716Chloro-iododibenzoylbenzene

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The 5-chloro-2-iodo-isophthalic acid (product Example 1a, 3.8 g, 12 mmol) is added to SOCl2 (30 mL, excess) and the mixture is refluxed under nitrogen for 2 days. The excess SOCl2 is evaporated under reduced pressure, then the resultant oil containing the 5-chloro-2-iodo-isophthaloyl dichloride (4.2 g, 12 mmol) is dissolved in dichloromethane (50 mL). To this solution, 1-phenyldodecane (10 g, 47 mmol) and AlCl3 (4.7 g, 35 mmol) are added at 0° C. The mixture is stirred from 0° C. to room temperature overnight. After quenching with 1M HCl solution, the residue is extracted by dichloromethane. The mixture is dried over MgSO4 and purified by column chromatography (silica gel, hexane/ethyl acetate=80:1) to afford the chloro-iododibenzoylbenzene as a colorless oil. Yield 2.3 g (27%). FD-MS (8 kV): m/z=727.7. 1H NMR (250 MHz, CDCl3-d) δ ppm 0.88-0.90 (m, 6 H, CH3), 1.26-1.30 (m, 32 H, CH2), 2.69 (t, J=7.3, 4 H, CH2), 7.27-7.41 (m, 6 H, Ar), 7.75 (t, J=7.9, 4 H, Ar); 13C NMR (62.5 MHz, CD2Cl2-d2): 13C NMR (250 MHz, CD2Cl2-d2): δ ppm 14.3, 23.1, 29.7, 29.8, 29.9, 30.0, 31.4, 32.3, 36.5, 128.8, 129.4, 130.9, 132.9, 135.3, 148.2, 151.1, 195.4.

Workup

  1. temperaturethe mixture is refluxed under nitrogen for 2 days
  2. customThe excess SOCl2 is evaporated under reduced pressure
  3. customAfter quenching with 1M HCl solution
  4. extractionthe residue is extracted by dichloromethane
  5. dry with materialThe mixture is dried over MgSO4
  6. custompurified by column chromatography (silica gel, hexane/ethyl acetate=80:1)

Sources & evidence

ORD record
ord-666c8c3644634b728da3feec8dad6804
Source dataset
uspto-grants-2014_09
Patent number
US08841411B2

Linked notes

Loading…