2-(Tri-n-butylstannyl)thiophene → HCID 58129787, compound

HRID 1797767Notes

Reaction equation

HRID 1797767 reaction equation
[CH:1]1[N:9]=[C:8](Br)[C:7]2[C:3](=[N:4][S:5][N:6]=2)[C:2]=1Br.C([Sn](CCCC)(CCCC)[C:17]1[S:18][CH:19]=[CH:20][CH:21]=1)CCC>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>[S:18]1[CH:19]=[CH:20][CH:21]=[C:17]1[C:8]1[C:7]2=[N:6][S:5][N:4]=[C:3]2[C:2]([C:19]2[S:18][CH:17]=[CH:21][CH:20]=2)=[CH:1][N:9]=1

Participants

5

Reactant 2

HCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 581297894,7-Dibromo[1,2,5]thiadiazolo[3,4-c]pyridine

Product 1

HCID 58129787HCID 58129787, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
140 °C

Procedure

A 5 mL microwave tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr2, 0.556 g, 1.885 mmol), 2-(tributylstannyl)thiophene (Bu3Sn—Th, 1.477 g, 3.957 mmol), Pd(PPh3)4 (0.020 g, 0.018 mmol), toluene (3 mL), and sealed with a teflon cap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 170° C. for 36 minutes, using a Biotage microwave reactor. Upon cooling, the residue was passed through a short silica plug eluting with methylene chloride (200 mL). All volatiles were removed in vacuo to give the crude product as a red solid. The solid was slurried in MeOH (100 mL), sonicated for 10 minutes, and filtered. The solid was washed with copious amounts of MeOH and then dried under vacuum for 24 hours. The product was collected as a bright red solid. Recovered yield: 535 mg (94%). 1H NMR (CD2Cl2): δ 8.81 (s, 1H, PT-CH), 8.68 (d, 3JH-H=4 Hz, 1H, Th′—CH), 8.11 (d, 3JH-H=4 Hz, 1H, Th—CH), 7.61 (d, 3JH-H=5 Hz, 1H, Th′—CH), 7.51 (d, 3JH-H=5 Hz, 1H, Th—CH), 7.27 (dd, 3JH-H=4 Hz, 3JH-H=4 Hz 1H, Th′—CH), 7.23 (dd, 3JH-H=4 Hz, 3HH-H=4 Hz 1H, Th—CH), 13C{1H} NMR (CD2Cl2): 155.50, 148.62, 146.91, 142.53 (s, quaternary), 141.28 (s, PT-CH), 137.18 (s, quaternary), 131.97 (s, Th′—CH), 131.00 (s, Th′—CH), 129.40 (s, Th—CH), 128.61 (s, Th—CH), 128.38 (s, Th′—CH), 127.88 (s, Th—CH), 121.00 (s, quaternary). Anal. Calcd. for C13H7N3S3: C, 51.80; H, 2.34; N, 13.94. Found: C, 51.8; H, 2.40; N, 13.7%. UV-vis: (o-DCB) λmax=302, 470 nm, λonset=550 nm, ε=22150 cm−1M−1. PL: (o-DCB) λmax=607 nm. HRMS (EI) m/z, calcd for C13H7N3S3 (M+): 300.98; found: 301.

Workup

  1. customcap
  2. temperatureUpon cooling
  3. washeluting with methylene chloride (200 mL)
  4. customAll volatiles were removed in vacuo

Sources & evidence

ORD record
ord-a22085cd86cd4aef8337d9f10bd5c2af
Source dataset
uspto-grants-2013_01
Patent number
US08343382B2

Reaction notes

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