Urea → HCID 22672523、化合物

HRID 599379

反応式

HRID 599379 の反応式
[Cl:1][C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].Cl[N:13]([N+]([O-])=O)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.N([O-])=O.[Na+].NC(N)=O.[OH:31][CH2:32][CH2:33][CH2:34][N:35](C1C=CC=CC=1)[CH2:36][CH2:37][CH2:38][C:39]([O:41][CH2:42][CH3:43])=[O:40].C([O-])(=O)C.[Na+]>O.C(O)(=O)C>[Cl:1][C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[N:4]=[N:13][C:14]1[CH:19]=[CH:18][C:17]([N:35]([CH2:34][CH2:33][CH2:32][OH:31])[CH2:36][CH2:37][CH2:38][C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:16][CH:15]=1

参加物

9

反応物 6

HCID 1176UreaHCID 84922-Chloro-4-nitroanilineHCID 517045Sodium AcetateHCID 23668193Sodium NitriteHCID 44144434N-Chloro-N-phenylnitramideHCID 66716979Ethyl 4-[(3-hydroxypropyl)phenylamino]butanoate

生成物 1

HCID 22672523HCID 22672523、化合物収率 68%

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 962Water溶媒3 回

実験手順

2-Chloro-4-nitroaniline 2.5 g (10 mmol) is placed into a 125 mL flask and 6 mL of water is added. Agitation and sonication partially dissolves the yellow chloronitroaniline. Then the stirred solution is cooled with ice in a fume hood and 15.8 mL of concentrated (˜12 M) HCl is added. Most of the yellow material dissolves at this point. The flask is fitted with a dropping funnel, and a solution of 1.51 g (21.9 mmol) sodium nitrite in 3-4 mL of water is added to the dropping funnel and slowly added to the solution in the flask with stirring, over about 20 minutes. When this is complete, 0.6 g (˜21 mmol) of urea is added followed by 2.73 g of ethyl 4-[(3-hydroxypropyl)phenylamino]butanoate as a solution in 8.2 mL acetic acid. After a minute 20 g of sodium acetate in -50 mL of water is added. The mixture is allowed to stir for an hour at room temperature. Most of the product is separated as an emulsion. The mixture is partitioned between ethyl acetate and water. The organic layer is washed with NaHCO3 (3×50 ml), brine and dried over anhydrous sodium sulfate. Then the organic solvents are evaporated to a syrup. The crude product is chromatographed on silica gel (1.5×20 inches) eluting with 50% ethyl acetate/hexane. The appropriate fractions are collected, combined, evaporated (30-40 degrees), and dried in a vacuum. The product is a dark oil. The yield is approximately 68-70%. 1H NMR (DMSO-d6) δ 8.42 (d, J=2.5 Hz, aromatic proton, 1H), 8.24 (dd, J1=9 Hz, J2=2.5 Hz, aromatic proton, 1H), 7.86 (d, J=9 Hz, 2H), 7.77 (d, J=9 Hz, 1H), 6.92 (d, J=9 Hz, aromatic protons, 2H), 4.67 (t, J=6 Hz, OH, 1H), 4.07 (q, J=7 Hz, CH2O, 2H), 3.5 (m, aliphatic protons, 6H), 2.40 (t, J=7 Hz, aliphatic protons, 2H), 1.84 (m, aliphatic protons, 2H), 1.72 (m, aliphatic protons, 2H), 1.18 (t, J=7 Hz, CH3, 3H).

後処理

  1. customAgitation and sonication
  2. temperatureThen the stirred solution is cooled with ice in a fume hood and 15.8 mL
  3. concentrationof concentrated (˜12 M) HCl
  4. additionis added
  5. dissolutionMost of the yellow material dissolves at this point
  6. customThe flask is fitted with a dropping funnel
  7. additionslowly added to the solution in the flask
  8. stirringto stir for an hour at room temperature
  9. customMost of the product is separated as an emulsion
  10. customThe mixture is partitioned between ethyl acetate and water
  11. washThe organic layer is washed with NaHCO3 (3×50 ml), brine
  12. dry with materialdried over anhydrous sodium sulfate
  13. customThen the organic solvents are evaporated to a syrup
  14. customThe crude product is chromatographed on silica gel (1.5×20 inches)
  15. washeluting with 50% ethyl acetate/hexane
  16. customThe appropriate fractions are collected
  17. customevaporated (30-40 degrees)
  18. customdried in a vacuum

出典と根拠

ORDレコード
ord-8fc565fae9a044f3b8417f133637b0f1
出典データセット
uspto-grants-2011_03
特許番号
US07897736B2

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