Dichloromethane → HCID 69628775, compound

HRID 1281412Notes

Reaction equation

HRID 1281412 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][O:20][CH3:21])=[C:13](Br)[CH:12]=1)[CH3:8].C(O[C:27](=O)[C:28]1[CH:33]=[CH:32][C:31](OCOC)=[CH:30][CH:29]=1)C.[CH3:39][C:40]1[CH:41]=[C:42](B(O)O)[CH:43]=C[CH:45]=1.[CH2:49](Cl)Cl.CCO[C:55]([CH3:57])=O>O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O1CCOCC1>[CH2:7]([O:9][C:10](=[O:23])[C:11]1[CH:16]=[C:15]([C:42]2[CH:41]=[C:40]([CH3:45])[CH:39]=[C:55]([CH3:57])[CH:43]=2)[C:14]([O:18][CH2:19][O:20][CH3:21])=[C:13]([C:32]2[CH:31]=[C:30]([CH3:49])[CH:29]=[C:28]([CH3:27])[CH:33]=2)[CH:12]=1)[CH3:8]

Participants

10

Reactant 6

HCID 6344DichloromethaneHCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 27339503-Tolylboronic acidHCID 22282372Ethyl 4-(methoxymethoxy)benzoateHCID 54329281HCID 54329281, compound

Product 1

HCID 69628775HCID 69628775, compoundYield 23%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of K2CO3 (11.39 g, 82.41 mmol) in 41 mL H2O was added 280 mL dioxane, a 2:1 mixture of 3-bromo-4-methoxymethoxy-5-iodobenzoic acid ethyl ester and 3,5-dibromo.4-methoxymethoxybenzoic acid ethyl ester (4.85 g, 13.74 mmol) and 3-methylphenyl boronic acid (4.1 g, 27.47 mmol) at room temperature. The reaction was degassed and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with CH2Cl2 (224 mg, 0.248 mmol) was added. The reaction was stirred for 2d then more of the catalyst was added (56 mg, 0.0687 mmol). The reaction was stirred for one more day and the reaction was worked up as in Step 1 of Example 135 to give crude material that was subjected to flash column chromatography (5% EtOAc:95% Hexanes). The major product from the column was further purified by prep HPLC to give 1.44 g, 23% of a white solid. 1H NMR (CDCl3) a 1.33 (t, J=8.18 Hz, 3H); 2.37 (s, 12H); 2.69 (s, 3H), 4.33-4.40 (m, 4H); 6.97 (s, 2H); 7.20 (m, 4H); 7.97 (s, 2H).

Workup

  1. customat room temperature
  2. customThe reaction was degassed
  3. additionmore of the catalyst was added (56 mg, 0.0687 mmol)
  4. customto give crude material that
  5. customThe major product from the column was further purified by prep HPLC

Sources & evidence

ORD record
ord-14a67030d5b3480480eedfcc65eb7ec7
Source dataset
uspto-grants-2002_09
Patent number
US06451827B2

Reaction notes

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