Water → Phenol

HRID 4466

Reaction equation

HRID 4466 reaction equation
[CH3:1][C@@H:2]1[NH:37][C:35](=[O:36])[C@@H:34]2[N:38]([CH3:41])[C:39](=[O:40])[C@@H:18]([CH2:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][C:27]4[CH:32]=[C:31]([CH2:33]2)[CH:30]=[CH:29][C:28]=4[OH:42])=[CH:22][CH:21]=3)[N:17]([CH3:43])[C:15](=[O:16])[C@@H:14]([CH3:44])[NH:13][C:11](=[O:12])[C@H:10]([CH2:45][C:46]2[CH:51]=[CH:50][C:49]([O:52][CH3:53])=[CH:48][CH:47]=2)[N:9]([CH3:54])[C:7](=[O:8])[C@H:6]([CH3:55])[NH:5][C:3]1=[O:4].[CH3:56][C@@H:57]1[NH:92][C:90](=[O:91])[C@@H:89]2[N:93]([CH3:96])[C:94](=[O:95])[C@@H:73]([CH2:74][C:75]3[CH:80]=[CH:79][C:78]([O:81][C:82]4[CH:87]=[C:86]([CH2:88]2)[CH:85]=[CH:84][C:83]=4[OH:97])=[CH:77][CH:76]=3)[N:72]([CH3:98])[C:70](=[O:71])[C@@H:69]([CH3:99])[NH:68][C:66](=[O:67])[C@H:65]([CH2:100][C:101]2[CH:106]=[CH:105][C:104]([O:107][CH3:108])=[CH:103][CH:102]=2)[N:64]([CH3:109])[C:62](=[O:63])[C@H:61]([CH3:110])[NH:60][C:58]1=[O:59].[CH3:111][C@@H:112]1[NH:147][C:145](=[O:146])[C@@H:144]2[N:148]([CH3:151])[C:149](=[O:150])[C@@H:128]([CH2:129][C:130]3[CH:135]=[CH:134][C:133]([O:136][C:137]4[CH:142]=[C:141]([CH2:143]2)[CH:140]=[CH:139][C:138]=4[OH:152])=[CH:132][CH:131]=3)[N:127]([CH3:153])[C:125](=[O:126])[C@@H:124]([CH3:154])[NH:123][C:121](=[O:122])[C@H:120]([CH2:155][C:156]2[CH:161]=[CH:160][C:159]([O:162][CH3:163])=[CH:158][CH:157]=2)[N:119]([CH3:164])[C:117](=[O:118])[C@H:116]([CH3:165])[NH:115][C:113]1=[O:114].[CH3:166][C@@H:167]1[NH:202][C:200](=[O:201])[C@@H:199]2[N:203]([CH3:206])[C:204](=[O:205])[C@@H:183]([CH2:184][C:185]3[CH:190]=[CH:189][C:188]([O:191][C:192]4[CH:197]=[C:196]([CH2:198]2)[CH:195]=[CH:194][C:193]=4[OH:207])=[CH:187][CH:186]=3)[N:182]([CH3:208])[C:180](=[O:181])[C@@H:179]([CH3:209])[NH:178][C:176](=[O:177])[C@H:175]([CH2:210][C:211]2[CH:216]=[CH:215][C:214]([O:217][CH3:218])=[CH:213][CH:212]=2)[N:174]([CH3:219])[C:172](=[O:173])[C@H:171]([CH3:220])[NH:170][C:168]1=[O:169].[OH2:221].O.O.O.O.O>C(O)(=O)C.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O>[CH3:1][C@@H:2]1[NH:37][C:35](=[O:36])[C@@H:34]2[N:38]([CH3:41])[C:39](=[O:40])[C@@H:18]([CH2:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][C:27]4[CH:32]=[C:31]([CH2:33]2)[CH:30]=[CH:29][C:28]=4[OH:42])=[CH:22][CH:21]=3)[N:17]([CH3:43])[C:15](=[O:16])[C@@H:14]([CH3:44])[NH:13][C:11](=[O:12])[C@H:10]([CH2:45][C:46]2[CH:51]=[CH:50][C:49]([O:52][CH3:53])=[CH:48][CH:47]=2)[N:9]([CH3:54])[C:7](=[O:8])[C@H:6]([CH3:55])[NH:5][C:3]1=[O:4].[CH3:56][C@@H:57]1[NH:92][C:90](=[O:91])[C@@H:89]2[N:93]([CH3:96])[C:94](=[O:95])[C@@H:73]([CH2:74][C:75]3[CH:80]=[CH:79][C:78]([O:81][C:82]4[CH:87]=[C:86]([CH2:88]2)[CH:85]=[CH:84][C:83]=4[OH:97])=[CH:77][CH:76]=3)[N:72]([CH3:98])[C:70](=[O:71])[C@@H:69]([CH3:99])[NH:68][C:66](=[O:67])[C@H:65]([CH2:100][C:101]2[CH:106]=[CH:105][C:104]([O:107][CH3:108])=[CH:103][CH:102]=2)[N:64]([CH3:109])[C:62](=[O:63])[C@H:61]([CH3:110])[NH:60][C:58]1=[O:59].[CH3:111][C@@H:112]1[NH:147][C:145](=[O:146])[C@@H:144]2[N:148]([CH3:151])[C:149](=[O:150])[C@@H:128]([CH2:129][C:130]3[CH:135]=[CH:134][C:133]([O:136][C:137]4[CH:142]=[C:141]([CH2:143]2)[CH:140]=[CH:139][C:138]=4[OH:152])=[CH:132][CH:131]=3)[N:127]([CH3:153])[C:125](=[O:126])[C@@H:124]([CH3:154])[NH:123][C:121](=[O:122])[C@H:120]([CH2:155][C:156]2[CH:161]=[CH:160][C:159]([O:162][CH3:163])=[CH:158][CH:157]=2)[N:119]([CH3:164])[C:117](=[O:118])[C@H:116]([CH3:165])[NH:115][C:113]1=[O:114].[CH3:166][C@@H:167]1[NH:202][C:200](=[O:201])[C@@H:199]2[N:203]([CH3:206])[C:204](=[O:205])[C@@H:183]([CH2:184][C:185]3[CH:190]=[CH:189][C:188]([O:191][C:192]4[CH:197]=[C:196]([CH2:198]2)[CH:195]=[CH:194][C:193]=4[OH:207])=[CH:187][CH:186]=3)[N:182]([CH3:208])[C:180](=[O:181])[C@@H:179]([CH3:209])[NH:178][C:176](=[O:177])[C@H:175]([CH2:210][C:211]2[CH:216]=[CH:215][C:214]([O:217][CH3:218])=[CH:213][CH:212]=2)[N:174]([CH3:219])[C:172](=[O:173])[C@H:171]([CH3:220])[NH:170][C:168]1=[O:169].[OH2:221].[OH2:4].[OH2:4].[OH2:4].[OH2:4].[C:23]1([OH:26])[CH:24]=[CH:25][CH:20]=[CH:21][CH:22]=1

Participants

6

Reactant 2

HCID 962WaterHCID 11979419Bouvardin, 5-(N-methyl-L-tyrosine)-

Product 2

HCID 996PhenolHCID 11979419Bouvardin, 5-(N-methyl-L-tyrosine)-

Reagents, catalysts & solvents 2

HCID 18616Cupric nitrateCatalystHCID 176Acetic AcidSolvent2×

Procedure

In 3 ml of acetic acid, 100 mg of TPC-A was dissolved and a solution of copper nitrate (40 mg) in 3 ml of acetic acid was added under stirring. When the color change of the reaction solution from blue to green took place under the continuation of stirring, water was added to cease the reaction and the product was extracted with ethyl acetate. After washing the extract with saturated sodium chloride solution and drying the extract over anhydrous magnesium sulfate, the extract was subjected to distillation to remove solvent, in vacuo and the product was recrystallized from methanol to obtain nitro compound of TPC-A at α-position of phenol thereof (108 mg) as yellow needle crystal having m.p. of 244°-250° C. (decomp) and [α]D22 of -232° (CHCl3).

Workup

  1. stirringof stirring
  2. customthe reaction
  3. extractionthe product was extracted with ethyl acetate
  4. washAfter washing the
  5. extractionextract with saturated sodium chloride solution
  6. customdrying the
  7. extractionextract over anhydrous magnesium sulfate
  8. distillationthe extract was subjected to distillation
  9. customto remove solvent
  10. customin vacuo and the product was recrystallized from methanol

Sources & evidence

ORD record
ord-a80267a6bf2b4049a16df416b032a024
Source dataset
uspto-grants-1988_02
Patent number
US04725578

Linked notes

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