Dimethylamine → 2-(Dimethylamino)-6-methylpyridine-4-carboxylic acid

HRID 1908744

반응식

HRID 1908744 반응식
C([O:5][C:6](=[O:15])[C:7]1[CH:12]=[C:11]([CH3:13])[N:10]=[C:9](Cl)[CH:8]=1)(C)(C)C.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.[CH3:58][NH:59][CH3:60]>C1COCC1.Cl.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:58][N:59]([CH3:60])[C:9]1[CH:8]=[C:7]([CH:12]=[C:11]([CH3:13])[N:10]=1)[C:6]([OH:5])=[O:15]

참가 물질

7

반응물 3

HCID 674DimethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 860403662-Chloro-6-methyl-isonicotinic acid tert-butyl ester

생성물 1

HCID 179213472-(Dimethylamino)-6-methylpyridine-4-carboxylic acid

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 313Hydrochloric Acid용매HCID 8028Tetrahydrofuran용매

실험 절차

Under argon, a solution of 2-chloro-6-methyl-isonicotinic acid tert.-butyl ester (625 mg 2.75 mmol), Na tert.-butylate (396 mg, 4.10 mmol), Xantphos (173 mg, 0.30 mmol) and Pd(OAc)2 (83 mg, 0.37 mmol) in 2 M dimethylamine in THF (35 mL) is stirred at 110° C. for 18 h. The dark reaction mixture is cooled to rt, diluted with 6 N aq. HCl and extracted with diethyl ether (4×60 mL). The org. extracts are concentrated, the residue is dissolved in 6 N aq. HCl and heated to 100° C. for 18 h. The orange suspension is concentrated, dissolved in 1 N aq. NaOH (40 mL) and concentrated again. The residue is dissolved in 1 N aq. NaOH (3 mL) and methanol and separated by MPLC on RP-C18 silica gel to give 2-dimethylamino-6-methyl-isonicotinic acid (1.1 g) as a beige oil; LC-MS: tR=0.44 min, [M+H]+=181.07.

후처리

  1. customThe dark reaction mixture
  2. extractionextracted with diethyl ether (4×60 mL)
  3. concentrationextracts are concentrated
  4. dissolutionthe residue is dissolved in 6 N aq. HCl
  5. temperatureheated to 100° C. for 18 h
  6. concentrationThe orange suspension is concentrated
  7. dissolutiondissolved in 1 N aq. NaOH (40 mL)
  8. concentrationconcentrated again
  9. dissolutionThe residue is dissolved in 1 N aq. NaOH (3 mL)
  10. custommethanol and separated by MPLC on RP-C18 silica gel

출처 및 근거

ORD 기록
ord-11044660fb2f40d5aee8ec7f0366f3e2
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08598208B2

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