Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [F:1][C:2]([F:22])([F:21])[C:3]1[CH:4]=[C:5]([C:9]2[CH:14]=[C:13]([CH:15]([F:17])[F:16])[N:12]3[N:18]=[CH:19][CH:20]=[C:11]3[N:10]=2)[CH:6]=[CH:7][CH:8]=1.C([O-])(=O)C.[Na+].[I:28]Cl>C(O)(=O)C.O>[I:28][C:20]1[CH:19]=[N:18][N:12]2[C:13]([CH:15]([F:16])[F:17])=[CH:14][C:9]([C:5]3[CH:6]=[CH:7][CH:8]=[C:3]([C:2]([F:21])([F:1])[F:22])[CH:4]=3)=[N:10][C:11]=12
Reactant: FC(F)c1cc(-c2cccc(C(F)(F)F)c2)nc2ccnn12
Reactant: ClI
Agent: CC(=O)[O-]
Agent: [Na+]
Solvent: CC(=O)O
Solvent: O
Product: FC(F)c1cc(-c2cccc(C(F)(F)F)c2)nc2c(I)cnn12
Temperature: 25 °C
Reaction time: 16 h
Yield: 95 %

Procedure:
To a stirred solution of 5-(3-trifluoromethyl-phenyl)-7-difluoromethyl-pyrazolo[1,5-a]pyrimidine (6.35 g, 20.3 mmol) in acetic acid (30 mL) was added at room temperature sodium acetate (1.88 g, 22.9 mmol) and drop wise a solution of iodine monochloride (3.72 g, 22.9 mmol) in acetic acid (10 mL). The reaction mixture was stirred at room temperature for 16 h, diluted slowly with water (300 mL), stirred at room temperature for 30 min, the precipitate was filtered off, washed with water and dried to give 3-iodo-7-difluoromethyl-5-(3-trifluoromethyl-phenyl)-pyrazolo[1,5-a]pyrimidine (8.47 g, 95%) as a yellow solid. MS (EI) 439.0 [(M)+]; mp 130° C.
Reaction SMILES: Cl[C:2]1[C:3]2[S:12][CH:11]=[CH:10][C:4]=2[N:5]=[C:6]([CH2:8][Cl:9])[N:7]=1.O.[NH2:14][NH2:15]>O1CCCC1>[Cl:9][CH2:8][C:6]1[N:7]=[C:2]([NH:14][NH2:15])[C:3]2[S:12][CH:11]=[CH:10][C:4]=2[N:5]=1
Reactant: ClCc1nc(Cl)c2sccc2n1
Reactant: NN
Solvent: C1CCOC1
Solvent: O
Product: NNc1nc(CCl)nc2ccsc12
Temperature: 5 °C
Reaction time: 15 h

Procedure:
3. 8.2 g of 4-chloro-2-(chloromethyl)thieno[3,2-d]pyrimidine are dissolved in 500 ml of absolute tetrahydrofuran. The solution is cooled to 5° C. 7 ml of hydrazine hydrate are added dropwise within 5 min., whereby a solution results and the temperature rises to 15° to 20° C. The reaction mixture is stirred at room temperature for 15 h. and then evaporated in a vacuum. The residue is stirred with 100 ml of saturated aqueous sodium hydrogen carbonate solution for 30 min. and then filtered off. The crystals are washed neutral with water and dried in a vacuum. 14.7 g of 2-(chloromethyl)-4-hydrazinothieno[3,2-d]-pyrimidine are obtained. A further 1.0 g of 2-(chloromethyl)-4-hydrazinothieno[3,2-d]pyrimidine are obtained by extracting the filtrate with chloroform.