Dichloromethane → HCID 54365473, compound

HRID 1743456Notes

Reaction equation

HRID 1743456 reaction equation
C([O-])([O-])=O.[K+].[K+].[CH2:7]([O:9][C:10](=[O:23])[C:11]1[CH:16]=[C:15](I)[C:14]([O:18][CH2:19][CH2:20][OH:21])=[C:13]([Br:22])[CH:12]=1)[CH3:8].[CH3:24][O:25][C:26]1[CH:27]=[C:28](B(O)O)[CH:29]=[CH:30][CH:31]=1.C(Cl)Cl.B(O)O>O.O1CCOCC1>[CH2:7]([O:9][C:10](=[O:23])[C:11]1[CH:16]=[C:15]([C:30]2[CH:29]=[CH:28][CH:27]=[C:26]([O:25][CH3:24])[CH:31]=2)[C:14]([O:18][CH2:19][CH2:20][OH:21])=[C:13]([Br:22])[CH:12]=1)[CH3:8]

Participants

8

Reactant 5

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 61668Boronic AcidHCID 2734370(3-Methoxyphenyl)boronic acidHCID 113389853-Bromo-4-(2-hydroxyethoxy)-5-iodobenzoic acid ethyl ester

Product 1

HCID 54365473HCID 54365473, compoundYield 10%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of K2CO3 (4.99 g, 36.1 mmol) in 18 mL H2O was added 3-bromo-4-(2-hydroxyethoxy)-5-iodobenzoic acid ethyl ester (5.0 g, 12.04 mmol), 145 mL dioxane, and 3-methoxyphenylboronic acid (1.83 g, 12.04 mmol) at room temperature. This mixture was stirred for 5 min then it was degassed. Then [1,1i-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with CH2Cl2 (49 mg, 0.06 mmol) was added. The reaction was stirred for three hours then 98 mg, 0.12 mmol of the catalyst was added and the reaction was allowed to stir for 3 d after which point 182 mg, 1.2 mmol of the boronic acid was added. The reaction was stirred for an additional 7 d before being worked up as in Step 1 of Example 135. There yielded 475 mg, 10% of the monoarylated product; 1H NMR (CDCl3) δ 1.38 (t, J=8.18 Hz, 3H); 1.83 (bs, 1H); 3.41 (t, J=5.43 Hz, 2H); 3.75 (t, J=5.43 Hz, 2H); 4.84 (s, 3H); 4.37 (q, J=8.18 Hz, 2H); 6.94 (dd, J=8.18 Hz, 2.72 Hz, 1H); 7.06–7.14 (m, 2H); 7.35 (t, J=8.18 Hz, 1H); 7.99 (d, J=2.73 Hz, 1H); 8.22 (d, J=2.73 Hz, 1H); 1.3 g, 25% of the bisarylated product and 2.1 g, 42% of recovered SM after the crude material was subjected to prep HPLC.

Workup

  1. customit was degassed
  2. stirringThe reaction was stirred for three hours
  3. stirringto stir for 3 d after which
  4. additionwas added
  5. stirringThe reaction was stirred for an additional 7 d

Sources & evidence

ORD record
ord-15ef4df51b27414aaec22c9e2ef69048
Source dataset
uspto-grants-2006_03
Patent number
US07008636B2

Reaction notes

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