Hydrochloric Acid → 3-(1-Methyl-3-pentylureido)phenylboronic acid

HRID 390638Notes

Reaction equation

HRID 390638 reaction equation
C[Li].Br[C:4]1[CH:5]=[C:6]([N:10]([CH3:19])[C:11]([NH:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[O:12])[CH:7]=[CH:8][CH:9]=1.C([Li])(C)(C)C.[B:25](OC)([O:28]C)[O:26]C.Cl>C(OCC)C.CCCCC.O1CCCC1>[CH3:19][N:10]([C:6]1[CH:5]=[C:4]([B:25]([OH:28])[OH:26])[CH:9]=[CH:8][CH:7]=1)[C:11]([NH:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[O:12]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 672727941-(3-Bromophenyl)-1-methyl-3-pentylureaHCID 178418306HCID 178418306, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 672732723-(1-Methyl-3-pentylureido)phenylboronic acidYield 39%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

150 mL (0.24 mol) of methyllithium at 1.6M in diethyl ether are added to a solution cooled to −70° C. of 123 g (0.41 mol) of 1-(3-bromophenyl)-1-methyl-3-pentylurea in 1.21 of tetrahydrofuran. The reaction medium is stirred at −70° C. for 1 hour and 530 mL (0.91 mol) of a 1.7M solution of tert-butyllithium in pentane are added. The reaction medium is stirred at −70° C. for 45 minutes and 115 mL (0.91 mol) of trimethyl borate are then added. The reaction medium is stirred at room temperature for 1 hour and then hydrolyzed by addition of ice, acidified with 1 l of 2 N hydrochloric acid and extracted with ethyl acetate. The organic phases are combined, washed with water and dried over magnesium sulfate. The solvent is evaporated off and the residue is purified by chromatography on a column of silica eluted with a 1/1 heptane/ethyl acetate mixture and crystallization from a heptane/ethyl acetate mixture. 42 g (39%) of 3-(1-methyl-3-pentylureido)phenylboronic acid are obtained in the form of a pink solid.

Workup

  1. stirringThe reaction medium is stirred at −70° C. for 45 minutes
  2. stirringThe reaction medium is stirred at room temperature for 1 hour
  3. additionhydrolyzed by addition of ice
  4. extractionextracted with ethyl acetate
  5. washwashed with water
  6. dry with materialdried over magnesium sulfate
  7. customThe solvent is evaporated off
  8. customthe residue is purified by chromatography on a column of silica
  9. washeluted with a 1/1 heptane/ethyl acetate mixture and crystallization from a heptane/ethyl acetate mixture

Sources & evidence

ORD record
ord-cffb2ae9cf304aaeacb046a0a6eab615
Source dataset
uspto-grants-2013_02
Patent number
US08383652B2

Reaction notes

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