Hydrochloric Acid → 4-(4-Carboxymethyl-Phenylazo)-Phenylacetic Acid

HRID 31161

反応式

HRID 31161 の反応式
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([OH:11])=[O:10])=[CH:4][CH:3]=1.Cl.[N:13]([O-])=O.[Na+].[C:17]1([CH2:23][C:24]([OH:26])=[O:25])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[OH-].[Na+]>O>[C:9]([CH2:8][C:5]1[CH:4]=[CH:3][C:2]([N:1]=[N:13][C:20]2[CH:21]=[CH:22][C:17]([CH2:23][C:24]([OH:26])=[O:25])=[CH:18][CH:19]=2)=[CH:7][CH:6]=1)([OH:11])=[O:10]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 999Phenylacetic Acid3 回HCID 145334-Aminophenylacetic acid2 回HCID 14798Sodium Hydroxide2 回HCID 23668193Sodium Nitrite2 回

生成物 1

HCID 98827184-(4-Carboxymethyl-Phenylazo)-Phenylacetic Acid収率 37%

試薬・触媒・溶媒 1

HCID 962Water溶媒2 回

反応条件

温度
0 °C

実験手順

4-Aminophenylacetic acid (3.75 g, 24.8 mmol) was suspended in water (75 mL) and concentrated hydrochloric acid (8 mL) was added. The solution was cooled to 0° C. in an ice bath with rapid stirring. Sodium nitrite (1.80 g, 26,1 mmol) in water (20 mL) was added dropwise to the 4-aminophenylacetic acid solution with rapid stirring. Care was taken to keep the temperature between 0-5° C. at all times, especially during the NaNO2 addition. The reaction was stirred for an additional 20 min. In the meantime, phenylacetic acid (10.1 g, 74.4 mmol) was dissolved in an aqueous NaOH solution (4.50 g, 113 mmol NaOH in 100 mL H2O). The solution was vigorously stirred at 17° C. and at pH 13.3. The diazonium salt solution was added dropwise to the phenylacetic acid solution. It is of utmost importance to keep the temperature of the phenylacetic acid solution between 17-18° C. and the pH between 13.2-13.3 at all times, especially during the diazonium salt addition. The temperature was regulated by the addition of ice and the pH regulated by the addition of 8 M NaOH. After addition was complete, the solution was allowed to warm to room temperature and stirred for an additional 30 min. The reaction mixture was suction filtered to remove any undissolved particulates or unwanted side products. The filtrate was acidified with aqueous HCl (10 mL conc. HCl in 20 mL H2O) which produced a dark red precipitate. The precipitate was collected by suction filtration and washed several times with cold H2O, until the filtrate was clear. The collected solid was air dried overnight to give the desired compound as a red solid in 37% yield: IR (KBr), 3030 (br), 1696, 1658, 1452, 1414, 1201,850, 675 cm−1 FABMS m/z 299 (M+H)+, 320 (M+Na); 1H NMR (DMSO-d6), δ 3.47 (s, 4H), 7.33 (4H, d, J=8.1 Hz), 7.84 (4H, d, J=8.4 Hz).

後処理

  1. custombetween 0-5° C.
  2. stirringThe solution was vigorously stirred at 17° C. and at pH 13.3
  3. custombetween 17-18° C.
  4. additionThe temperature was regulated by the addition of ice
  5. additionAfter addition
  6. temperatureto warm to room temperature
  7. stirringstirred for an additional 30 min
  8. filtrationfiltered
  9. customto remove any undissolved particulates or unwanted side products
  10. customproduced a dark red precipitate
  11. filtrationThe precipitate was collected by suction filtration
  12. washwashed several times with cold H2O
  13. customdried overnight

出典と根拠

ORDレコード
ord-0bb66ea4e2f4407aa650b64e351c1cfe
出典データセット
uspto-grants-2008_09
特許番号
US07425578B2

関連ノート

読み込み中…