Hydrochloric Acid → [3-(Methylamino)phenyl]boronic acid

HRID 250853

반응식

HRID 250853 반응식
C[Li].Br[C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[NH:7][CH3:8].C([Li])(C)(C)C.[B:17](OC)([O:20]C)[O:18]C.Cl>C(OCC)C.O1CCCC1>[CH3:8][NH:7][C:6]1[CH:5]=[C:4]([B:17]([OH:20])[OH:18])[CH:11]=[CH:10][CH:9]=1

참가 물질

8

반응물 5

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 70182993-Bromo-N-methylanilineHCID 178418306HCID 178418306, 화합물HCID 178418348HCID 178418348, 화합물

생성물 1

HCID 23558980[3-(Methylamino)phenyl]boronic acid수율 14%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매2회HCID 8028Tetrahydrofuran용매

반응 조건

온도
-70 °C

실험 절차

166 mL (0.242 mol, 1.2 eq) of 1.6 M methyllithium in diethyl ether are added to a solution cooled to −70° C. of 37.6 g (0.202 mol, 1 eq) of 3-bromo-N-methylaniline (prepared in Example 7c) in 300 ml of tetrahydrofuran. The reaction medium is stirred at −70° C. for one hour and 306 mL (0.444 mol, 2.2 eq) of 1.5 M tert-butyllithium in diethyl ether are then added. The reaction medium is stirred at −70° C. for 45 minutes and 103.5 mL (0.808 mol, 4 eq) of trimethyl borate are then added. The reaction medium is stirred at room temperature for one hour and then hydrolyzed by addition of ice, acidified with 1 L of 2N 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 4.2 g (14%) of 3-(methylamino)phenylboronic acid are obtained. The aqueous phase is basified 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 chromatographed on silica gel (8/2 heptane/ethyl acetate). 3.4 g (11%) of 3-(methylamino)phenylboronic acid are obtained.

후처리

  1. stirringThe reaction medium is stirred at −70° C. for 45 minutes
  2. stirringThe reaction medium is stirred at room temperature for one 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

출처 및 근거

ORD 기록
ord-20e8989d805a49b59bfede49341709c5
출처 데이터셋
uspto-grants-2011_01
특허 번호
US07863332B2

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