4,7-Dibromo[1,2,5]thiadiazolo[3,4-c]pyridine → HCID 89286622, compound

HRID 929269Notes

Reaction equation

HRID 929269 reaction equation
[CH:1]1[N:9]=[C:8](Br)[C:7]2[C:3](=[N:4][S:5][N:6]=2)[C:2]=1[Br:11].[CH2:12]([C:24]1([CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH3:72])[C:47]2[CH:46]=[C:45]([Sn](CCCC)(CCCC)CCCC)[S:44][C:43]=2[C:26]2[S:27][C:28]([Sn:30]([CH2:39][CH2:40][CH2:41][CH3:42])([CH2:35][CH2:36][CH2:37][CH3:38])[CH2:31][CH2:32][CH2:33][CH3:34])=[CH:29][C:25]1=2)[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[Br:11][C:2]1[C:3]2[C:7](=[N:6][S:5][N:4]=2)[C:8]([C:45]2[S:44][C:43]3[C:26]4[S:27][C:28]([Sn:30]([CH2:39][CH2:40][CH2:41][CH3:42])([CH2:31][CH2:32][CH2:33][CH3:34])[CH2:35][CH2:36][CH2:37][CH3:38])=[CH:29][C:25]=4[C:24]([CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH3:72])([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[C:47]=3[CH:46]=2)=[N:9][CH:1]=1

Participants

5

Reactant 2

HCID 581297894,7-Dibromo[1,2,5]thiadiazolo[3,4-c]pyridineHCID 86713091HCID 86713091, compound

Product 1

HCID 89286622HCID 89286622, compoundYield 32.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
75 °C

Procedure

To a solution of 4,7-dibromo-pyridal[2,1,3]thiadiazole (0.28 g, 0.95 mmol) and 1a (1.04 g, 0.95 mmol) in freshly distilled toluene (10 ml) was added Pd(PPh3)4 (109.8 mg, 0.095 mmol) under nitrogen, and then capped with a rubber septum. The reaction mixture was stirred at 75° C. for 10 hours. The solvent was removed and purified by column chromatography (silica was pretreated by 10 v/v % triethylamine/hexane solution) with hexane as eluent. The column separation was repeated for 3 times to give 0.31 g of viscous purple oil, yield 30%. 1H NMR (500 MHz, CD2Cl2) δ (ppm): 8.55 (s, 1H), 8.53 (s, 1H), 7.01 (s, 1H), 1.95-1.91 (m, 4H), 1.63-1.56 (m, 6H), 1.37-1.31 (m, 6H), 1.26-1.12 (m, 42H), 1.08-0.97 (m, 4H), 0.91-0.82 (m, 15H); 13C NMR (CDCl3, 125 MHz) δ (ppm): 163.11, 160.01, 156.33, 148.10, 147.92, 145.92, 143.99, 142.26, 141.81, 140.27, 129.80, 127.62, 106.17, 37.85, 31.88, 29.96, 29.61, 29.52, 29.34, 29.31, 28.98, 27.21, 24.57, 22.66, 13.85, 13.44, 10.95.

Workup

  1. customcapped with a rubber septum
  2. customThe solvent was removed
  3. custompurified by column chromatography (silica was pretreated by 10 v/v % triethylamine/hexane solution) with hexane as eluent
  4. customThe column separation

Sources & evidence

ORD record
ord-edbc699c070249f48ffa387fbb29fb69
Source dataset
uspto-grants-2016_03
Patent number
US09293708B2

Reaction notes

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