Aniline → HCID 57733418, 화합물

HRID 1920734노트

반응식

HRID 1920734 반응식
[Cl:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([CH:11]([C:15]([O:17][CH3:18])=[O:16])[C:12](=O)[CH3:13])[C:3]=1[C:4]([OH:6])=O.[NH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C(O[Si](OCC)(OCC)OCC)C.Cl.C(N=C=NCCCN(C)C)C.ON1C2C=CC=CC=2N=N1>CO.O.CN(C)C=O>[CH3:18][O:17][C:15]([C:11]1[C:7]2[C:3](=[C:2]([Cl:1])[CH:10]=[CH:9][CH:8]=2)[C:4](=[O:6])[N:19]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:12]=1[CH3:13])=[O:16]

참가 물질

9

반응물 5

HCID 6115AnilineHCID 6517TetraethoxysilaneHCID 757711-HydroxybenzotriazoleHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 57733406HCID 57733406, 화합물

생성물 1

HCID 57733418HCID 57733418, 화합물수율 87%

시약·촉매·용매 3

HCID 887Methanol용매HCID 962Water용매HCID 6228Dimethylformamide용매

실험 절차

A mixture of 2-chloro-6-(1-methoxycarbonyl-2-oxo-propyl)-benzoic acid (4 g, 15 mmol), aniline (1.369 ml, 15 mmol) and tetraethoxysilane (6.65 ml, 30 mmol) in methanol (20 ml) was sealed and heated under microwave irradiation at +150° C. for 20 min. The obtained solution was diluted with water (150 ml) and extracted with ethyl acetate (2×300 ml). The combined organic solution was dried (MgSO4) and evaporated. The obtained crude enamine (2-chloro-6-(1-methoxycarbonyl-2-phenylamino-propenyl)-benzoic acid) was dissolved in dimethylformamide (80 ml) followed by addition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC, 4.3 g, 22.5 mmol) and 1-hydroxybenzotriazole (HOBT, 3.04 g, 22.5 mmol). It was stirred for 16 hours and partitioned between water (250 ml), diethyl ether (250 ml) and ethyl acetate (150 ml). The organic phase was washed with 0.5 M NaOH (2×100 ml), brine (2×200 ml), dried (MgSO4) and evaporated to give 4.25 g of brown oil, which was used in the next step without further purification. Yield 87%. LC-MS (m/z) 328.0 (MH+); tR=1.36. 1H NMR (500 MHz, CDCl3): 2.02 (s, 3H), 3.98 (s, 3H), 7.23 (d, 2H), 7.44-7.55 (m, 6H).

후처리

  1. customwas sealed
  2. temperatureheated under microwave irradiation at +150° C. for 20 min
  3. extractionextracted with ethyl acetate (2×300 ml)
  4. dry with materialThe combined organic solution was dried (MgSO4)
  5. customevaporated
  6. customThe obtained crude enamine (2-chloro-6-(1-methoxycarbonyl-2-phenylamino-propenyl)-benzoic acid)
  7. custompartitioned between water (250 ml), diethyl ether (250 ml) and ethyl acetate (150 ml)
  8. washThe organic phase was washed with 0.5 M NaOH (2×100 ml), brine (2×200 ml)
  9. dry with materialdried (MgSO4)
  10. customevaporated

출처 및 근거

ORD 기록
ord-71efba058c514d459a879a837144e178
출처 데이터셋
uspto-grants-2012_05
특허 번호
US08173639B2

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