Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [NH2:1][CH2:2][CH2:3][CH2:4][O:5][C:6]1[CH:41]=[CH:40][C:9]([C:10]([C:12]2[CH:17]=[CH:16][C:15]([NH:18][CH2:19][CH2:20][O:21][CH2:22][CH2:23][O:24][CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][C:33]([O:35]C(C)(C)C)=[O:34])=[CH:14][CH:13]=2)=[O:11])=[CH:8][CH:7]=1>C(Cl)Cl.C(O)(C(F)(F)F)=O>[NH2:1][CH2:2][CH2:3][CH2:4][O:5][C:6]1[CH:41]=[CH:40][C:9]([C:10]([C:12]2[CH:17]=[CH:16][C:15]([NH:18][CH2:19][CH2:20][O:21][CH2:22][CH2:23][O:24][CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][C:33]([OH:35])=[O:34])=[CH:14][CH:13]=2)=[O:11])=[CH:8][CH:7]=1
Reactant: CC(C)(C)OC(=O)CCOCCOCCOCCOCCNc1ccc(C(=O)c2ccc(OCCCN)cc2)cc1
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: NCCCOc1ccc(C(=O)c2ccc(NCCOCCOCCOCCOCCC(=O)O)cc2)cc1
Reaction time: 1 h
Yield: 109.6 %

Procedure:
tert-butyl 1-((4-(4-(3-aminopropoxy)benzoyl)phenyl)amino)-3,6,9,12-tetraoxapentadecan-15-oate (3.24 g, 5.63 mmol) was dissolved in a solution of DCM:TFA (2:1, 20 ml) and stirred ca. 1 h. Upon completion, reaction was then concentrated under reduced pressure, co-evaporated with toluene, and dried on oil pump for 5 hs to yield 3.20 g of crude 1-((4-(4-(3-aminopropoxy)benzoyl)phenyl)amino)-3,6,9,12-tetraoxapentadecan-15-oic acid as yellow oil. The crude product was used without any further purification.
Reaction SMILES: [CH2:1]1[O:11][C:10]2[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][C:3]=2[O:2]1.Br[CH2:13][CH2:14][CH3:15]>>[CH2:1]1[O:11][C:10]2[CH:9]=[CH:8][C:5]([CH:6]([OH:7])[CH2:13][CH2:14][CH3:15])=[CH:4][C:3]=2[O:2]1
Reactant: O=Cc1ccc2c(c1)OCO2
Reactant: CCCBr
Product: CCCC(O)c1ccc2c(c1)OCO2

Procedure:
The title compound was prepared from 3,4-methylenedioxybenzaldehyde of formula 2 (7.5 g, 50 mmol) by subjecting it to Grignard's reaction with 1-bromopropane by the method described in example 1(i) to give 1-(3,4-methylenedioxyphenyl)-n-butanol of formula 3 (9.4 g, 97%). The secondary alcohol (7.8 g, 40 mmol) was subjected to Vilsmeier reaction with dimethyl formamide-phosphorous oxychloride as described in example 1 (ii) to furnish 2-formyl-1-(3,4-methylenedioxyphenyl)-1-butene (5.0 g, 67%). The resulting aldehyde (2.0 g, 10 mmol) was hydrogenated in presence of Pd/C in methanol to furnish after purification corresponding dihydro derivative (1.0 g, 50%) of formula 5. The dihydro derivative of formula 5 was subjected to Wittig reaction as described in example 1 (iii) followed by saponification to produce 5-(3,4-methylenedioxyphenyl)-4-ethyl-4E-pentenoic acid (0.8 g, 86%) of formula 7. The pentenoic acid (0.75 g, 3.0 mmol) of formula 9 after acid chloride formation with thionyl chloride, and reaction with piperidine was purified by column chromatography on silica gel to give 5-(3,4-methylenedioxyphenyl)-4-ethyl-2E-pentenoic acid piperidine amide of formula 1b (0.8 g, 86%).
Reaction SMILES: [NH2:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[C:5](I)[N:6]2[C:11]1[CH:16]=[CH:15][C:14]([NH:17][C:18]([NH:20][C:21]2[CH:26]=[CH:25][C:24]([Cl:27])=[C:23]([C:28]([F:31])([F:30])[F:29])[CH:22]=2)=[O:19])=[CH:13][CH:12]=1.[CH3:33][O-:34].[Na+]>CO>[NH2:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[C:5]([O:34][CH3:33])[N:6]2[C:11]1[CH:16]=[CH:15][C:14]([NH:17][C:18]([NH:20][C:21]2[CH:26]=[CH:25][C:24]([Cl:27])=[C:23]([C:28]([F:31])([F:30])[F:29])[CH:22]=2)=[O:19])=[CH:13][CH:12]=1
Reactant: C[O-]
Reactant: Nc1ncnc2c1nc(I)n2-c1ccc(NC(=O)Nc2ccc(Cl)c(C(F)(F)F)c2)cc1
Agent: [Na+]
Solvent: CO
Product: COc1nc2c(N)ncnc2n1-c1ccc(NC(=O)Nc2ccc(Cl)c(C(F)(F)F)c2)cc1
Reaction time: 14 h
Yield: 36.6 %

Procedure:
In 2 mL of methanol, 25 mg (0.04 mmol) of 1-[4-(6-amino-8-iodopurin-9-yl)phenyl]-3-(4-chloro-3-(trifluoromethyl)phenyl)urea was dissolved, and 5.6 mg (0.10 mmol) of sodium methylate was added thereto, and the mixture solution was refluxed with stirring for 14 hours. The reaction solution was concentrated and purified by a silica gel column (dichloromethane:methanol=9:1) to obtain 7 mg (34%) of a target product as a white solid.
Reaction SMILES: C(N)CC.[CH2:5]([NH:8][C:9](=[NH:11])[NH2:10])[CH2:6]C.[CH3:12][N:13](C)[CH2:14]CN>>[CH3:12][N:13]([CH3:14])[CH2:6][CH2:5][NH:8][C:9](=[NH:11])[NH2:10]
Reactant: CCCNC(=N)N
Reactant: CN(C)CCN
Solvent: CCCN
Product: CN(C)CCNC(=N)N

Procedure:
By the same procedure, using propylamine the corresponding N'-propyl guanidine is prepared. Using 2-(dimethylamino)ethylamine the corresponding N'-(2- dimethylaminoethyl) guanidine is prepared.
Reaction SMILES: [N+:1]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:11](=[O:14])OC)=[CH:6][CH:5]=1)([O-:3])=[O:2].[NH2:15][CH2:16][C:17]1[CH:18]=[N:19][CH:20]=[CH:21][CH:22]=1.O>C1(C)C=CC=CC=1.CO>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([NH:10][C:11]([NH:15][CH2:16][C:17]2[CH:18]=[N:19][CH:20]=[CH:21][CH:22]=2)=[O:14])=[CH:8][CH:9]=1)([O-:3])=[O:2]
Reactant: COC(=O)Nc1ccc([N+](=O)[O-])cc1
Reactant: NCc1cccnc1
Solvent: Cc1ccccc1
Solvent: CO
Solvent: O
Product: O=C(NCc1cccnc1)Nc1ccc([N+](=O)[O-])cc1
Reaction time: 4 h

Procedure:
11.77 g (0.06 mole) of methyl N-(4-nitrophenyl)carbamate, 5.4 g (0.05 mole) of 3-aminomethyl-pyridine, 18.7 g (0.065 mole) of Genamin SH 302 D (a mixture of N,N-dimethyl-C16-18 alkylamines sold by the firm Hoechst AG) and 200 ml of toluene are introduced into the apparatus described in Example 4, and the mixture is boiled for 4 hours. During this period 15 ml of a mixture of water, methanol and toluene accumulate in the trap. The separated solid is filtered off, washed twice with 10 ml of hot toluene, and the resulting mixture is used as reaction medium in the above reaction. The mother liquor is recycled 10 times. The results of the individual cycles are summarized in Table 1.