Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl ester → HCID 89573839, compound

HRID 2176081Notes

Reaction equation

HRID 2176081 reaction equation
NC1C=CC=CC=1[S:8][C:9]1[CH:28]=[CH:27][C:26]2C3=C4[C:25]5[C:16]([C:17](=[O:53])[N:18]([C:41]6[C:46]([CH:47]([CH3:49])[CH3:48])=[CH:45][CH:44]=[CH:43][C:42]=6[CH:50]([CH3:52])[CH3:51])[C:19](=[O:40])[C:20]=5C=C3OC3C=CC(C(C)(C)C)=CC=3)=[CH:15][C:14]([O:54][C:55]3[CH:60]=[CH:59][C:58]([C:61]([CH3:64])([CH3:63])[CH3:62])=[CH:57][CH:56]=3)=[C:13]4[C:12]3=[CH:65][CH:66]=[CH:67][C:10]=1[C:11]=23.N([O-])=O.[Na+].CC(O[CH2:76][C:77]1[C:90]2[C:85](=[CH:86][CH:87]=[CH:88][CH:89]=2)C(COC(C)=O)=C2[C:78]=1[CH:79]=CC=C2)=O>O>[C:61]([C:58]1[CH:57]=[CH:56][C:55]([O:54][C:78]2[C:77]3[C:90]4[CH:89]=[CH:88][C:87]5[S:8][C:9]6[C:10](=[CH:11][CH:26]=[CH:27][CH:28]=6)[C:67]6=[CH:66][CH:65]=[C:12]([C:13]7[C:76]=3[C:25]3[C:16](=[CH:15][C:14]=7[O:54][C:55]7[CH:60]=[CH:59][C:58]([C:61]([CH3:63])([CH3:64])[CH3:62])=[CH:57][CH:56]=7)[C:17](=[O:53])[N:18]([C:41]7[C:42]([CH:50]([CH3:51])[CH3:52])=[CH:43][CH:44]=[CH:45][C:46]=7[CH:47]([CH3:48])[CH3:49])[C:19](=[O:40])[C:20]=3[CH:79]=2)[C:85]=4[C:86]=56)=[CH:60][CH:59]=1)([CH3:64])([CH3:62])[CH3:63]

Participants

5

Reactant 3

HCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl esterHCID 23668193Sodium NitriteHCID 89573705HCID 89573705, compound

Product 1

HCID 89573839HCID 89573839, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

Compound 8-bromo-5,12-bis(4-(tert-butyl)phenoxy)-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (3.0 g), 2-aminobenzenthiol (0.48 g, 10% excess) and anhydrous potassium carbonate (0.24 g) were added to 30 mL of N-methyl-2-pyrrolidinone (NMP). The solution was heated rapidly and refluxed for 30 min. After a minute the liquor was added to 2% aqueous hydrochloride acid (250 ml) and after standing overnight, filtered and dried at 105° C. to give a red-blue solid of 8-((2-aminophenyl)thio)-5,12-bis(4-(tert-butyl)phenoxy)-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (2.06 g) with a nominal yield of 60.0%. 8-((2-aminophenyl)thio)-5,12-bis(4-(tert-butyl)phenoxy)-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (2.06 g) was dissolved in warm glacial acetic (12 mL) and concentration hydrochloride acid (1.3 mL) giving a fine suspension. The suspension was cooled to 0° C. and a solution of sodium nitrite (0.16 g) in water (3.6 mL) added and stirred continuously till clear. The prepared solution was added to a boiling solution of hydrated cupric sulphate (2.6 g) in water (60 mL) with good stirring within 1 hour. After boiling a further 1 hour, the solution was cooled, filtered and a blue-red solid was given. The solid was washed with a warm solution of sodium hydroxide (20 mL, 3%) three times and purified on Chromatography Column to eliminate by-products. The blue solid of 5,15-bis(4-(tert-butyl)phenoxy)-2-(2,6-diisopropylphenyl)-1H-thioxantheno[2′,1′,9′:10,5,6]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (0.69 g) was given with a nominal yield of 34.2%. MS: base peak 884.

Workup

  1. concentrationconcentration hydrochloride acid (1.3 mL)
  2. customgiving a fine suspension
  3. stirringwith good stirring within 1 hour
  4. temperaturethe solution was cooled
  5. filtrationfiltered
  6. washThe solid was washed with a warm solution of sodium hydroxide (20 mL, 3%) three times
  7. custompurified on Chromatography Column

Sources & evidence

ORD record
ord-8c4e6938e2b94459a0714d8d437b21b0
Source dataset
uspto-grants-2015_06
Patent number
US09062207B2

Reaction notes

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