4-Iodobenzoic acid → HCID 14054779, compound

HRID 1724111Notes

Reaction equation

HRID 1724111 reaction equation
I[C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][CH:3]=1.[CH:11](O)(C)C.C(=O)=O.C([Mg]Cl)(C)C.[CH3:23][O:24][C:25](=[O:34])[C:26]1[CH:31]=[CH:30][C:29]([CH:32]=[O:33])=[CH:28][CH:27]=1>C1COCC1.O.CO>[CH3:11][O:8][C:6]([C:5]1[CH:9]=[CH:10][C:2]([CH:32]([C:29]2[CH:30]=[CH:31][C:26]([C:25]([O:24][CH3:23])=[O:34])=[CH:27][CH:28]=2)[OH:33])=[CH:3][CH:4]=1)=[O:7]

Participants

8

Reactant 4

HCID 120854-Iodobenzoic acidHCID 15294Methyl 4-FormylbenzoateHCID 86586944Isopropanol carbon dioxideHCID 178418918HCID 178418918, compound

Product 1

HCID 14054779HCID 14054779, compoundYield 71%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-25 °C

Procedure

(Andersen, K. E.; Mane, R. B.; Desai, U. V.; Hebbalkar, G. D. Collection Czechoslovak Chem. Commun. 1988, 53, 646-657.) 4-Iodobenzoic acid 3 (5.00 g, 19.1 mmol) is dissolved in anhydrous THF (60 ml), the solution is cooled to an internal temperature of −30° C. in a bath of iso-propanol/dry-ice, and i-PrMgCl (2 M in THF; 10.5 ml, 21.0 mmol) is slowly added dropwise, in order to keep the internal temperature at between −20° C. and −30° C. After the reaction mixture is stirred for an additional 40 min at a temperature of −25° C., a solution of 4-formylbenzoic acid methylester (16; 4.07 g, 24.8 mmol) in anhydrous THF (25 ml) is added dropwise, in order to keep the internal temperature at below −20° C. The mixture is stirred for an additional 30 min at −25° C. and is thawed over night to RT. Subsequently, methanol (30 ml) is added, the mixture is poured into water (500 ml), and extracted with Et2O. The organic phases are unified, washed with a saturated solution of NaCl, and dried over MgSO4. The solvent is removed, and the crude product as obtained is crystallized from chloroform/petroleum ether, in order to obtain 4.05 g (71%) of compound 5 as a colorless solid. Melting point 116° C. (Andersen, K. E.; Mane, R. B.; Desai, U. V.; Hebbalkar, G. D. Collection Czechoslovak Chem. Commun. 1988, 53, 646-657.) 123° C.). The spectroscopic data of the isolated compound 5 correspond to the values as published (Andersen et al. 1988, see above).

Workup

  1. additionis slowly added dropwise, in order
  2. customat between −20° C. and −30° C
  3. customat below −20° C
  4. stirringThe mixture is stirred for an additional 30 min at −25° C.
  5. waitis thawed over night to RT
  6. extractionextracted with Et2O
  7. washwashed with a saturated solution of NaCl
  8. dry with materialdried over MgSO4
  9. customThe solvent is removed
  10. customthe crude product as obtained
  11. customis crystallized from chloroform/petroleum ether, in order

Sources & evidence

ORD record
ord-75dd70f2f6ae48ff97dbbb47e1354bf5
Source dataset
uspto-grants-2009_02
Patent number
US07485742B2

Reaction notes

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