Hydrochloric Acid → HCID 89573705, compound

HRID 2176080Notes

Reaction equation

HRID 2176080 reaction equation
Br[C:2]1[CH:21]=[CH:20][C:19]2[C:16]3=[C:17]4[C:18]5[C:9]([C:10](=[O:46])[N:11]([C:34]6[C:39]([CH:40]([CH3:42])[CH3:41])=[CH:38][CH:37]=[CH:36][C:35]=6[CH:43]([CH3:45])[CH3:44])[C:12](=[O:33])[C:13]=5[CH:14]=[C:15]3[O:22][C:23]3[CH:28]=[CH:27][C:26]([C:29]([CH3:32])([CH3:31])[CH3:30])=[CH:25][CH:24]=3)=[CH:8][C:7]([O:47][C:48]3[CH:53]=[CH:52][C:51]([C:54]([CH3:57])([CH3:56])[CH3:55])=[CH:50][CH:49]=3)=[C:6]4[C:5]3=[CH:58][CH:59]=[CH:60][C:3]=1[C:4]=23.[NH2:61][C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][C:63]=1[SH:68].C(=O)([O-])[O-].[K+].[K+].Cl>CN1CCCC1=O>[NH2:61][C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][C:63]=1[S:68][C:2]1[CH:21]=[CH:20][C:19]2[C:16]3=[C:17]4[C:18]5[C:9]([C:10](=[O:46])[N:11]([C:34]6[C:39]([CH:40]([CH3:42])[CH3:41])=[CH:38][CH:37]=[CH:36][C:35]=6[CH:43]([CH3:45])[CH3:44])[C:12](=[O:33])[C:13]=5[CH:14]=[C:15]3[O:22][C:23]3[CH:28]=[CH:27][C:26]([C:29]([CH3:32])([CH3:31])[CH3:30])=[CH:25][CH:24]=3)=[CH:8][C:7]([O:47][C:48]3[CH:53]=[CH:52][C:51]([C:54]([CH3:57])([CH3:56])[CH3:55])=[CH:50][CH:49]=3)=[C:6]4[C:5]3=[CH:58][CH:59]=[CH:60][C:3]=1[C:4]=23

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 87132-AminothiophenolHCID 11430Potassium CarbonateHCID 86684984HCID 86684984, compound

Product 1

HCID 89573705HCID 89573705, compoundYield 65.3%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

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. temperatureThe solution was heated rapidly
  2. temperaturerefluxed for 30 min
  3. filtrationfiltered
  4. customdried at 105° C.

Sources & evidence

ORD record
ord-b045bdbca73d47168c1ac61a8656d1bd
Source dataset
uspto-grants-2015_06
Patent number
US09062207B2

Reaction notes

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