Toluene → HCID 66611755, compound

HRID 1748948Notes

Reaction equation

HRID 1748948 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]([C:8]1[N:9](C(C2SC=CC=2)=O)[S:10][NH:11][CH:12]=1)=O.[C:20]1(C)C=[CH:24][CH:23]=[CH:22][CH:21]=1.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:36])=CC=1.[CH2:49]([CH:51]([CH2:69][CH2:70][CH2:71][CH3:72])[CH2:52][O:53][C:54](=[O:68])[C:55]#[C:56][C:57]([O:59][CH2:60][CH:61]([CH2:66][CH3:67])[CH2:62][CH2:63][CH2:64][CH3:65])=[O:58])[CH3:50]>CC(C)=O>[CH2:49]([CH:51]([CH2:69][CH2:70][CH2:71][CH3:72])[CH2:52][O:53][C:54]([C:55]1[C:56]([C:57]([O:59][CH2:60][CH:61]([CH2:66][CH3:67])[CH2:62][CH2:63][CH2:64][CH3:65])=[O:58])=[C:20]([C:21]2[S:36][CH:24]=[CH:23][CH:22]=2)[C:12]2=[N:11][S:10][N:9]=[C:8]2[C:6]=1[C:2]1[S:1][CH:5]=[CH:4][CH:3]=1)=[O:68])[CH3:50]

Participants

6

Reactant 4

HCID 1140TolueneHCID 87949Lawesson's reagentHCID 66611778HCID 66611778, compoundHCID 86688383HCID 86688383, compound

Product 1

HCID 66611755HCID 66611755, compoundYield 11%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A mixture of [4-(thiophene-2-carbonyl)-[2,1,3]thiadiazol-3-yl]-thiophen-2-yl-methanone (1.7 g, 6 mmol), anhydrous toluene (70 cm3) and Lawesson's reagent (3.8 g, 9.5 mmol) is stirred at room temperature for 2 hours. But-2-ynedioic acid bis-(2-ethyl-hexyl)ester (3.4 g, 10 mmol) is then added and the reaction mixture heated at reflux for 17 hours. Acetone (50 cm3) is added, the mixture pre-absorbed onto silica and purified by column chromatography (40-60 petrol:ethyl acetate; 1:0 to 3:1) to give 4,7-di-thiophen-2-yl-benzo[2,1,3]thiadiazole-5,6-dicarboxylic acid bis-(2-ethyl-hexyl)ester as a yellow/green oil (380 mg, 11%). 1H NMR (300 MHz, CDCl3) 0.71-0.99 (12H, m, CH3), 1.03-1.47 (16H, m, CH2), 1.50-1.75 (2H, m, CH), 3.94-4.15 (4H, m, OCH2), 7.18 (2H, dd, ArH, J 3.6, 5.0), 7.41 (2H, dd, ArH, J 1.2, 3.6), 7.58 (2H, dd, ArH, J 1.2, 5.0); 13C NMR (300 MHz, CDCl3) 10.9, 14.1, 23.0, 23.3, 28.9, 30.0, 38.4, 68.9, 126.0, 127.3, 128.7, 129.6, 132.8, 135.3, 153.7, 167.9.

Workup

  1. temperaturethe reaction mixture heated
  2. temperatureat reflux for 17 hours
  3. customthe mixture pre-absorbed onto silica
  4. custompurified by column chromatography (40-60 petrol:ethyl acetate; 1:0 to 3:1)

Sources & evidence

ORD record
ord-a885f9b7bd384d34b9bfdfa9abcc46a6
Source dataset
uspto-grants-2015_10
Patent number
US09153784B2

Reaction notes

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