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Hydrochloric Acid → HCID 178433880、化合物

HRID 386369
ノート
印刷プレビュー

反応式

HRID 386369 の反応式
[NH2:1][C:2]1[C:3]([OH:17])=[C:4]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([OH:16])=[O:15])[CH:9]=2)[CH:5]=[CH:6][CH:7]=1.Cl.N([O-])=O.[Na+].S(=O)(=O)(O)[NH2:24].[CH3:28][C:29]1[CH:30]=[C:31]([N:36]2[C:40]([OH:41])=[CH:39][C:38]([CH3:42])=[N:37]2)[CH:32]=[CH:33][C:34]=1[CH3:35]>O.C(N(CC)CC)C.CO>[CH3:35][C:34]1[CH:33]=[CH:32][C:31]([N:36]2[N:37]=[C:38]([CH3:42])/[C:39](=[N:24]/[NH:1][C:2]3[CH:7]=[CH:6][CH:5]=[C:4]([C:8]4[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([OH:16])=[O:15])[CH:9]=4)[C:3]=3[OH:17])/[C:40]2=[O:41])=[CH:30][C:29]=1[CH3:28]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

9

反応物 5

HCID 313Hydrochloric Acid2 回HCID 5987Sulfamic AcidHCID 114923323-(3-Amino-2-hydroxyphenyl)benzoic acidHCID 23668193Sodium NitriteHCID 178429255HCID 178429255、化合物

生成物 1

HCID 178433880HCID 178433880、化合物

試薬・触媒・溶媒 3

HCID 887
Methanol
溶媒
HCID 962Water溶媒2 回
HCID 8471Triethylamine溶媒

反応条件

温度
22 °C

実験手順

Crystalline 3′-amino-2′-hydroxybiphenyl-3-carboxylic acid form II (50 g, 218 mmol, PXRD pattern at FIG. 34) (Supplier: Topharman Shangai Co., Ltd; Batch No: BPCA: 090921BPCA) was added to a solvent mixture of methanol (1 L) and hydrochloric acid, 4 M (137 mL) in a 1 L reactor with stirring at room temperature (cca 22° C.). The resulting solution was stirred for ½ h and then cooled to 0-5° C. A refrigerated solution of sodium nitrite (15 g, 217 mmol) in water (50 mL) was added to the reaction mixture over 20 min (maintaining the reaction temperature below 10° C.) and the stirring was continued for 1 h. A Solution of sulfamic acid (2.22 g, 23 mmol) in water (50 mL) was added to the reaction mixture and stirred for 1 h at 5° C. The resulting reaction mixture was heated to room temperature and triethylamine (cca 80 mL) was added to adjust to pH 7-8. Crystalline 1-(3,4-dimethylphenyl)-3-methyl-1H-pyrazol-5-ol (“pyrazole”) form II (44 g, 218 mmol, PXRD pattern at FIG. 33) (Supplier: Topharman Shangai Co., Ltd; Batch No: 090805PYRAZOL) was added in one portion to the reaction mixture and stirred for 2 h at room temperature, maintaining the pH 7-8. Hydrochloric acid (4 M, cca 40 mL) was added to adjust the pH to 1.8 over 20 minutes with stirring. The precipitated solid was filtered, washed with mixture of MeOH:water (1:1, 60 mL) and dried at 40° C./5 bar for about 18 h to yield 100 g (90%) of EBP as a bright orange powder. PXRD analysis provided the diffractogram as shown in FIG. 20. DSC analysis provided the thermogram as shown in FIG. 21

後処理

  1. stirringThe resulting solution was stirred for ½ h
  2. temperaturecooled to 0-5° C
  3. temperaturemaintaining the reaction temperature below 10° C.) and the stirring
  4. stirringstirred for 1 h at 5° C
  5. customThe resulting reaction mixture
  6. temperaturewas heated to room temperature
  7. stirringstirred for 2 h at room temperature
  8. temperaturemaintaining the pH 7-8
  9. customover 20 minutes
  10. stirringwith stirring
  11. filtrationThe precipitated solid was filtered
  12. washwashed with mixture of MeOH:water (1:1, 60 mL)
  13. customdried at 40° C./5 bar for about 18 h
  14. customto yield 100 g (90%) of EBP as a bright orange powder
  15. customPXRD analysis provided the diffractogram
  16. customDSC analysis provided the thermogram

出典と根拠

ORDレコード
ord-d3da9b006d124b59b9f2bb5b141bcc67
出典データセット
uspto-grants-2013_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08372822B2

反応ノート

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