Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [C:1]([C:4]([C@@H:17]1[CH2:21][CH2:20][NH:19][CH2:18]1)([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)(=[O:3])[NH2:2].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C.[CH:40](=O)[CH2:41][CH2:42][CH2:43][C:44]#[CH:45]>ClCCl>[C:1]([C:4]([C@@H:17]1[CH2:21][CH2:20][N:19]([CH2:45][CH2:44][CH2:43][CH2:42][C:41]#[CH:40])[CH2:18]1)([C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)(=[O:3])[NH2:2]
Reactant: C#CCCCC=O
Reactant: NC(=O)C(c1ccccc1)(c1ccccc1)[C@@H]1CCNC1
Agent: CC(=O)O[BH-](OC(C)=O)OC(C)=O
Agent: [Na+]
Solvent: ClCCl
Solvent: CC(=O)O
Product: C#CCCCCN1CC[C@@H](C(C(N)=O)(c2ccccc2)c2ccccc2)C1
Temperature: 25 °C
Reaction time: 8 h
Yield: 81.5 %

Procedure:
To a stirred solution of (S)-3-(1-carbamoyl-1,1-diphenylmethyl)pyrrolidine (64.4 g, 0.23 mol); sodium triacetoxyborohydride (50.9 g, 0.24 mol) and acetic acid (13 mL, 0.23 mol) in dichloromethane (511 mL) at room temperature, was added a solution of hex-5-yn-1-al (26.14 g, 0.27 mol) in dichloromethane (256 mL). The reaction mixture stirred at room temperature overnight (ca. 8 hours) and then the reaction mixture was quenched by addition of concentrated hydrochloric acid (30 mL) and stirring was continued for 1 hour at room temperature. The mixture was then diluted with water (750 mL) and made basic to pH 5 using 10 N sodium hydroxide (18 mL). The layers were separated and the organic layer was washed with 1 N sodium hydroxide (200 mL). The organic layer was dried over magnesium sulfate (10 g); filtered and then concentrated in vacuo to afford 67.6 g of the title intermediate as a yellow gummy solid (83% yield).
Reaction SMILES: C(N(CC)CC)C.[OH:8][C:9]1[N:13]=[C:12]([O:14][CH2:15][CH3:16])[S:11][N:10]=1.[CH:17]([N:19]=[C:20]=[O:21])=[CH2:18]>C(OC(C)C)(C)C>[CH:17]([NH:19][C:20]([N:10]1[C:9](=[O:8])[N:13]=[C:12]([O:14][CH2:15][CH3:16])[S:11]1)=[O:21])=[CH2:18]
Reactant: C=CN=C=O
Reactant: CCOc1nc(O)ns1
Solvent: CCN(CC)CC
Solvent: CC(C)OC(C)C
Product: C=CNC(=O)n1sc(OCC)nc1=O
Temperature: 20 °C
Reaction time: 0.5 h
Yield: 69.8 %

Procedure:
1 ml of triethylamine was added to a solution of 14.6 g of 3-hydroxy-5-ethoxy-1,2,4-thiadiazole in 250 ml of isopropyl ether and after 5 minutes, 8 g of vinyl isocyanate were added. The mixture was stirred for 30 minutes at 20° C and was vacuum filtered and the recovered precipitate was washed, dried and crystallized from ethyl acetate to obtain 15 g of 2-(N-vinylcarbamoyl)-5-ethoxy-1,2,4-thiadiazole-3-one melting at 123° C.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:14]([C:15]3[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=3)=[N:13][NH:12][C:11](=[O:23])[C:10]=2[C:24]#[N:25])=[CH:5][CH:4]=1.[CH2:26](Cl)[CH:27]([CH3:29])[CH3:28]>>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:14]([C:15]3[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=3)=[N:13][N:12]([CH2:26][CH:27]([CH3:29])[CH3:28])[C:11](=[O:23])[C:10]=2[C:24]#[N:25])=[CH:5][CH:4]=1
Reactant: CC(C)CCl
Reactant: COc1ccc(-c2n[nH]c(=O)c(C#N)c2-c2ccc(OC)cc2)cc1
Product: COc1ccc(-c2nn(CC(C)C)c(=O)c(C#N)c2-c2ccc(OC)cc2)cc1
Yield: 71.8 %

Procedure:
Using 5,6-bis(4-methoxyphenyl)-4-cyano-2H-pyridazin-3-one and isobutyl chloride as starting materials, the procedures of Example 1 were repeated likewise, whereby the title compound was obtained in a yield of 71.8%.
Reaction SMILES: [N:1]1([C:7]2[N:12]=[CH:11][NH:10][C:9](=[O:13])[CH:8]=2)[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[N+:14]([C:17]1[CH:18]=[C:19]([CH:22]=[CH:23][CH:24]=1)[CH:20]=O)([O-:16])=[O:15]>>[N+:14]([C:17]1[CH:18]=[C:19]([CH:22]=[CH:23][CH:24]=1)[CH2:20][N:4]1[CH2:5][CH2:6][N:1]([C:7]2[N:12]=[CH:11][NH:10][C:9](=[O:13])[CH:8]=2)[CH2:2][CH2:3]1)([O-:16])=[O:15]
Reactant: O=c1cc(N2CCNCC2)nc[nH]1
Reactant: O=Cc1cccc([N+](=O)[O-])c1
Product: O=c1cc(N2CCN(Cc3cccc([N+](=O)[O-])c3)CC2)nc[nH]1

Procedure:
6-[4-(3-Nitro-benzyl)-piperazin-1-yl]-3H-pyrimidin-4-one was prepared using Procedure A from 6-piperazin-1-yl-3H-pyrimidin-4-one (Intermediate 4) and 3-nitrobenzaldehyde. Mass spectrum (ES) MH+=316.
Reaction SMILES: [CH3:1][C:2]([C:5]1[C:10]([OH:11])=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[N:8]=[C:7]([C:16](O)=[O:17])[N:6]=1)([CH3:4])[CH3:3].CN(C)C=O.C(Cl)(=O)C(Cl)=O.Cl.[CH3:31][NH:32][O:33][CH3:34].CN1CCCCC1>ClCCl>[CH3:15][C:12]([C:9]1[C:10]([OH:11])=[C:5]([C:2]([CH3:4])([CH3:1])[CH3:3])[N:6]=[C:7]([C:16]([N:32]([O:33][CH3:34])[CH3:31])=[O:17])[N:8]=1)([CH3:14])[CH3:13]
Reactant: CNOC
Reactant: CC(C)(C)c1nc(C(=O)O)nc(C(C)(C)C)c1O
Agent: Cl
Agent: O=C(Cl)C(=O)Cl
Solvent: CN1CCCCC1
Solvent: ClCCl
Solvent: CN(C)C=O
Product: CON(C)C(=O)c1nc(C(C)(C)C)c(O)c(C(C)(C)C)n1
Reaction time: 2 h
Yield: 65.7 %

Procedure:
A mixture of 8.4 g (33 mmol) of 4,6-bis(1,1-dimethylethyl)-5-hydroxy-2-pyrimidinecarboxylic acid and 0.50 mL (0.47 g, 6.5 mmol) of N,N-dimethylformamide in 120 mL of dichloromethane was cooled in ice and treated dropwise with a solution of 4.9 mL (7.1 g, 56 mmol) of oxalyl chloride in 18 mL of dichloromethane. The mixture was stirred with ice cooling for 2 hours, then filtered, and evaporated. The residual crude acid chloride was redissolved in 85 mL of dichloromethane and added dropwise to an ice-cooled mixture of 4.0 g (41 mmol) of N,O-dimethylhydroxylamine hydrochloride and 15 mL (12.2 g, 123 mmol) of 1-methylpiperidine in 150 mL of dichloromethane. The mixture was stirred at room temperature for 16 hours, then washed with 0.4N hydrochloric acid, brine, 5% aqueous sodium bicarbonate, and brine again. The organic layer was dried (anhydrous sodium sulfate) and evaporated, and the residue recrystallized from ethyl acetate/hexane to yield 6.4 g (65%) of the amide product, mp 140° C.-142° C.
Reaction SMILES: Br[C:2]1[O:6][C:5]([CH3:7])=[C:4]([CH:8]=[O:9])[CH:3]=1.[OH:10][C:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.C(=O)([O-])[O-].[Na+].[Na+].COCCOC>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.O>[OH:10][C:11]1[CH:16]=[CH:15][C:14]([C:2]2[O:6][C:5]([CH3:7])=[C:4]([CH:8]=[O:9])[CH:3]=2)=[CH:13][CH:12]=1
Reactant: OB(O)c1ccc(O)cc1
Reactant: Cc1oc(Br)cc1C=O
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: COCCOC
Solvent: O
Product: Cc1oc(-c2ccc(O)cc2)cc1C=O
Reaction time: 8 h
Yield: 78.7 %

Procedure:
A mixture of 5-bromo-2-methylfuran-3-carbaldehyde (1.9 g), 4-hydroxyphenylboronic acid (1.7 g), tetrakis(triphenylphosphine)palladium(0) (0.6 g), 2N aqueous sodium carbonate solution (12 mL) and 1,2-dimethoxyethane (50 mL) was stirred overnight with refluxing under an argon atmosphere. The reaction mixture was poured into water, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (0% ethyl acetate/hexane to 35% ethyl acetate/hexane) to give the title compound (1.6 g, 35%) as a yellow crystal.
Reaction SMILES: [CH3:1][C:2]1[CH:3]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH2:4][CH2:5][C:6](=O)[CH:7]=1.[SH:14][CH2:15][CH2:16][C:17](O)=[O:18].C1(C)C=CC(S(O)(=O)=O)=CC=1.N1C=CC=CC=1.FC(F)(F)C(OC(=O)C(F)(F)F)=O.CS(O)(=O)=O>C1(C)C=CC=CC=1>[CH3:1][C:2]1[C:7]2[C:17](=[O:18])[CH2:16][CH2:15][S:14][C:6]=2[CH2:5][CH2:4][C:3]=1[C:9]([O:11][CH2:12][CH3:13])=[O:10]
Reactant: O=C(O)CCS
Reactant: CCOC(=O)C1CCC(=O)C=C1C
Agent: CS(=O)(=O)O
Agent: Cc1ccc(S(=O)(=O)O)cc1
Solvent: c1ccncc1
Solvent: Cc1ccccc1
Solvent: O=C(OC(=O)C(F)(F)F)C(F)(F)F
Product: CCOC(=O)C1=C(C)C2=C(CC1)SCCC2=O
Temperature: 25 °C
Yield: 36 %

Procedure:
A mixture of ethyl 2-methyl-4-oxo-2-cyclohexenecarboxylate (2.0 kg, 91.2%, 10.98 moles), β-mercaptopropionic acid (1.165 kg, 10.98 moles), p-toluenesulfonic acid (ptsa) monohydrate (0.710 kg, 3.73 moles) and pyridine (0.304 kg, 3.84 moles) in toluene is heated to reflux temperature, heated at reflux temperatures for 7 hours using a Dean Stark trap for removal of water, allowed to cool to room temperature over a 17 hour period, cooled to 5° C., treated with trifluoroacetic anhydride (TFAA) (2.306 kg, 10.98 moles) at 50°-12° C., treated with methanesulfonic acid (0.053 kg, 0.55 moles), allowed to warm to room temperature, held at room temperature until reaction is complete by HPLC analysis and quenched with water. The phases are separated. The organic phase is washed with water and distilled to remove the toluene. The remaining pot residue is treated with isopropyl alcohol (1.89 kg), cooled to 45° C., treated with heptane (1.65 kg), and cooled to room temperature. The resultant mixture is filtered and the filtercake is washed sequentially with a 1:1 isopropanol:heptane mixture (0.735 kg) and heptane (1.37 kg). The washed filtercake is dried in vacuo to give the title product as a white crystalline solid, 0.931 kg (36% yield) 98.4% purity, identified by HPLC analysis.
Reaction SMILES: [CH2:1]([NH:17][C:18]1[CH:19]=[C:20]([C:23]([OH:25])=[O:24])[S:21][CH:22]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16].[OH-].[Na+].I[CH2:29][CH:30]([OH:33])[CH2:31][OH:32].CN(C)P(N(C)C)(N(C)C)=O>O.CCOCC>[CH2:1]([NH:17][C:18]1[CH:19]=[C:20]([C:23]([O:25][CH2:29][CH:30]([OH:33])[CH2:31][OH:32])=[O:24])[S:21][CH:22]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16]
Reactant: CCCCCCCCCCCCCCCCNc1csc(C(=O)O)c1
Reactant: OCC(O)CI
Agent: [Na+]
Agent: [OH-]
Solvent: CCOCC
Solvent: O
Solvent: CN(C)P(=O)(N(C)C)N(C)C
Product: CCCCCCCCCCCCCCCCNc1csc(C(=O)OCC(O)CO)c1

Procedure:
A solution of 7.34 g. of 4-(hexadecylamino)-2-thiophenecarboxylic acid, 4.80 g. of 25% aqueous sodium hydroxide, and 12.6 g. of 3-iodo-1,2-propanediol in 50 ml. of hexamethylphosphoramide is stirred for 24 hours at ambient temperature, diluted with 100 ml. of ether and stirred for 5 days at ambient temperature. The mixture is treated with water and extracted with ether. The dried extracts are evaporated to yield 2,3-dihydroxypropyl 4-(hexadecylamino)-2-thiophenecarboxylate as a white solid.
Reaction SMILES: [CH2:1]([OH:5])[CH2:2][CH:3]=[CH2:4].[H-].[Na+].Cl[C:9]1[C:13]([C:14]2[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=2)=[N:12][S:11][N:10]=1.O>O1CCCC1>[CH2:1]([O:5][C:9]1[C:13]([C:14]2[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=2)=[N:12][S:11][N:10]=1)[CH2:2][CH:3]=[CH2:4]
Reactant: C=CCCO
Reactant: Clc1nsnc1-c1cccnc1
Agent: [H-]
Agent: [Na+]
Solvent: O
Solvent: C1CCOC1
Product: C=CCCOc1nsnc1-c1cccnc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 111.4 %

Procedure:
To a solution of 3-buten-1-ol (540 mg, 7.5 mmol) and sodium hydride (180 mg, 7.5 mmol) in dry tetrahydrofuran was added a solution of 3-(3-chloro-1,2,5-thiadiazol-4-yl)pyridine (490 mg, 2.5 mmol) in dry tetrahydrofuran. The reaction mixture was stirred at room temperature for 1 h. Water was added and the mixture was extracted with ether. The ether phase was dried and evaporated to yield 650 mg of the title compound.
Reaction SMILES: [S:1]1[CH:6]=[CH:5][CH2:4][N:3]=[CH:2]1.[N+:7]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])([O-:9])=[O:8].CS>[Cl-].[Zn+2].[Cl-].CCOCC.C(O)(C)C>[N+:7]([C:10](=[C:2]1[NH:3][CH2:4][CH2:5][CH2:6][S:1]1)[C:11]([O:13][CH2:14][CH3:15])=[O:12])([O-:9])=[O:8]
Reactant: CCOC(=O)C[N+](=O)[O-]
Reactant: C1=CSC=NC1
Agent: CS
Agent: [Cl-]
Agent: [Zn+2]
Solvent: CCOCC
Solvent: CC(C)O
Product: CCOC(=O)C(=C1NCCCS1)[N+](=O)[O-]
Reaction time: 1.25 h

Procedure:
To a mixture of 235 g of 5,6-dihydro-2-methylthio)-4H-1,3-thiazine (A. F. McKay et al., J. Am. Chem. Soc., 80, 3339 (1958)) and 2 g of zinc chloride at approximately 115° in a nitrogen atmosphere, 263 g of ethyl nitroacetate (S. Zen, et al., Kogyo Kagaku Zasshi, 74, 70 (1971)) was added dropwise over a 1.5 hour period. The mixture was held at 110°-120°. When evolution of methyl mercaptan ceased after 45 minutes further stirring of the heated mixture, 1 g of zinc chloride was added and the mixture was stirred at about 115° for 1.25 hours. An additional 1 g of zinc chloride then was added and stirring of the mixture at about 115° was continued for 1.5 hours. The mixture then was poured into a cooled solution of 2/1 (volume) ether/isopropyl alcohol mixture. The crystallized product was collected, washed with ether and dried under reduced pressure to leave a tan solid, m.p. 100°-102°, which on recrystallization from methanol gave ethyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetate (1A) as a pale yellow solid, m.p. 105°-106°.
Reaction SMILES: Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[C:4](Cl)[N:3]=1.[NH3:12].[CH3:13][OH:14]>>[NH2:12][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[C:4]([O:14][CH3:13])[N:3]=1
Reactant: CO
Reactant: O=[N+]([O-])c1ccc(Cl)nc1Cl
Reactant: N
Product: COc1ccc([N+](=O)[O-])c(N)n1
Temperature: 20 °C
Yield: 56.45 %

Procedure:
2,6-Dichloro-3-nitropyridine, 25.0 gm (0.129 mole) was dissolved in methanol (50.0 ml) at room temperature. To the solution thus obtained, 25.0% aqueous ammonia solution 12.2 ml (0.179 mole) was charged at room temperature. The resulting mixture was heated to 35°–40° C. for 2.0 hrs. The reaction was monitored by TLC. After the completion of the reaction, the mixture was cooled to 20° C. The solid obtained was washed, filtered with methanol and dried to yield 12.50 gm of 2-amino-6-methoxy-3-nitro pyridine (56.45%) with the HPLC purity of 99.3%: Melting point 192°–195° C.; 1HNMR: (DMSO D6) δ6.75–6.77 ppm (d, 1H), δ8.38–8.40 (d, 1H).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:24]=[CH:25][C:26]=1[O:27][CH3:28])[C:6]([CH:8]([CH2:14][CH2:15][C:16](=O)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:9]([O:11][CH2:12][CH3:13])=[O:10])=O.C([O-])(=O)C.[NH4+:33].C(O)(=O)C>O>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:6]2[N:33]=[C:16]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[CH:15]=[CH:14][C:8]=2[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:24]=[CH:25][C:26]=1[O:27][CH3:28]
Reactant: CCOC(=O)C(CCC(=O)c1ccccc1)C(=O)c1ccc(OC)c(OC)c1
Reactant: [NH4+]
Agent: CC(=O)[O-]
Solvent: O
Solvent: CC(=O)O
Product: CCOC(=O)c1ccc(-c2ccccc2)nc1-c1ccc(OC)c(OC)c1
Yield: 62 %

Procedure:
A mixture of ethyl 2-(3,4-dimethoxybenzoyl)-5-oxo-5-phenylvalerate (compound no. 314; 7.7 g; 0.02 mole), ammonium acetate (3.1 g; 0.04 mole) and acetic acid (30 ml) is heated to reflux temperature for 4 hours. The reaction medium is poured into water (300 ml): an oil is released. The latter is extracted with ethyl acetate (200 ml). The organic solution is washed with water (3×100 ml), then dried over anhydrous magnesium sulphate and concentrated under reduced pressure. A light brown oil (4.5 g; yield: 62%) is obtained which corresponds to ethyl 2-(3,4-dimethoxyphenyl)-6-phenylnicotinate.
Reaction SMILES: C(Cl)(=[O:3])N.[CH2:5]([NH:12][C:13](=[N:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[S:14][CH2:15][CH3:16])[CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11].[CH2:25]1[CH2:29][O:28][CH2:27][CH2:26]1>>[CH2:18]([N:17]([C:29]([O:28][CH2:27][C:26]#[CH:25])=[O:3])[C:13](=[N:12][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11])[S:14][CH2:15][CH3:16])[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24]
Reactant: CCCCCCCN=C(NCCCCCCC)SCC
Reactant: C1CCOC1
Reactant: NC(=O)Cl
Product: C#CCOC(=O)N(CCCCCCC)C(=NCCCCCCC)SCC
Temperature: 45 °C

Procedure:
Then a solution of 15 ml dry THF and 5.44 g of the 1,3-diheptyl-2-ethyl isothiourea carbamyl chloride was added dropwise over 10 minutes. The mixture was stirred and warmed to 45° C. for 2 hours. The reaction was cooled to 25° C. and filtered by suction on a glass frit and filter. The solvent was removed under reduced pressure. 5.0 g of a liquid (88 weight percent of theory) having a nD30 of 1.4553 was recovered. The structure was confirmed as the title compound by NMR and spectra analyses. Compound No. 648 in Table I.
Reaction SMILES: [C:1]1([P:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[F:20][C:21]1[CH:22]=[C:23]([CH:26]=[CH:27][CH:28]=1)[CH2:24][Br:25]>CCOCC>[Br-:25].[F:20][C:21]1[CH:22]=[C:23]([CH:26]=[CH:27][CH:28]=1)[CH2:24][P+:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1
Reactant: Fc1cccc(CBr)c1
Reactant: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: CCOCC
Product: Fc1cccc(C[P+](c2ccccc2)(c2ccccc2)c2ccccc2)c1
Product: [Br-]
Temperature: 25 °C
Reaction time: 8 h
Yield: 107.1 %

Procedure:
To a solution of triphenylphosphine (45.24 g, 0.12 mol) in 200 mL of ether was added 3-fluorobenzyl bromide (22.7 g, 0.12 mol). The resulting solution was allowed to stir at rt overnight. The white solid was collected by filtration and dried to give 58.0 g (85%) of the product as a white solid. mp 290-292° C. 1H NMR (CHCl3) 5.516 (d, J=14.7 Hz, 2 H), 6.725 (d, J=9.6 Hz, 1 H), 6.893 (m, 2 H), 7.084 (m, 2 H), 7.622-7.762 (m, 15 H).
Reaction SMILES: Cl[C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][CH3:11])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1.[NH3:15]>C(O)C>[NH2:15][C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][CH3:11])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1
Reactant: CNc1c([N+](=O)[O-])ccc(Cl)c1C#N
Reactant: N
Solvent: CCO
Product: CNc1c([N+](=O)[O-])ccc(N)c1C#N
Temperature: 25 °C
Yield: 95 %

Procedure:
A suspension of the above amine (30.0 g, 142 mmol) in a 5.3 M solution of ammonia in ethanol (200 mL) was heated in a sealed stainless steel reaction vessel (600 mL capacity) at 90° C. for 24 h. The reaction vessel was cooled to room temperature, then to 0° C., and opened. The product was filtered, washed with ethanol (30 mL) and dried to give 6-amino-2-methylamino-3-nitro-benzonitrile (25.94 g, 95%) as a yellow solid.
Reaction SMILES: [NH2:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:12])=[C:6]([S:8]([NH2:11])(=[O:10])=[O:9])[CH:7]=1.[CH3:13][C:14]1[C:15]([O:17][C:18](=O)[C:19]=1[CH3:20])=[O:16]>N1C=CC=CC=1>[Cl:12][C:5]1[CH:4]=[CH:3][C:2]([N:1]2[C:15](=[O:16])[C:14]([CH3:13])=[C:19]([CH3:20])[C:18]2=[O:17])=[CH:7][C:6]=1[S:8]([NH2:11])(=[O:9])=[O:10]
Reactant: Nc1ccc(Cl)c(S(N)(=O)=O)c1
Reactant: CC1=C(C)C(=O)OC1=O
Solvent: c1ccncc1
Product: CC1=C(C)C(=O)N(c2ccc(Cl)c(S(N)(=O)=O)c2)C1=O
Reaction time: 0.33 h
Yield: 93 %

Procedure:
In 3 ml of pyridine, 1 mmol of 5-amino-2-chlorobenzenesulfonamide and 1.05 mmol of 2,3-dimethylmaleic anhydride were stirred at 90°-100° C. for 9 hours. Pyridine was then distilled off from the reaction mixture, followed by the addition of 20 ml of ice water and 0.1 ml of 35% hydrochloric acid to the solid residue. After the mixture thus formed was stirred for 20 minutes, the resulting precipitate was collected by filtration and then dried in air. Yield: 93%. Its physicochemical properties are shown in Table 8.
Reaction SMILES: [C:1]([OH:6])(=O)[C:2]([CH3:4])=[CH2:3].C(OCCCl)=O.C(#N)C.[NH2:16][C:17]1[CH:22]=[CH:21][C:20]([S:23]([NH2:26])(=[O:25])=[O:24])=[CH:19][CH:18]=1>O.C(N(CC)CC)C>[NH2:26][S:23]([C:20]1[CH:19]=[CH:18][C:17]([NH:16][C:1](=[O:6])[C:2]([CH3:4])=[CH2:3])=[CH:22][CH:21]=1)(=[O:24])=[O:25]
Reactant: C=C(C)C(=O)O
Reactant: Nc1ccc(S(N)(=O)=O)cc1
Agent: O=COCCCl
Solvent: O
Solvent: CC#N
Solvent: CCN(CC)CC
Product: C=C(C)C(=O)Nc1ccc(S(N)(=O)=O)cc1
Temperature: 70 °C
Yield: 65 %

Procedure:
31.0 g of methacrylic acid, 39.1 g of chloroethyl formate, and 200 ml of acetonitrile were put in an ice water bath, and this mixture was agitated while cooling. 36.4 g of triethylamine was dropped into the mixture by a dropping funnel over about 1 hour. After the dropping was finished, the ice water bath was taken away, the mixture was agitated for 30 minutes at room temperature. 51.7 g of p-amino benzene sulfonamide was added to the reaction mixture, and the mixture was agitated for 1 hour while being heated at 70° C. After finishing the reaction, an obtained mixture was introduced into 1,000 ml of water while agitating the water, and the obtained mixture was agitated for 30 minutes. The mixture was filtrated for taking out a precipitate. After adding 500 ml of water to the precipitate to make a slurry, the slurry was filtrated, and an obtained solid was dried so as to obtain N-(p-aminosulfonyl phenyl) methacrylamide (yield 46.9 g).
Reaction SMILES: [CH3:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9]Br)=[CH:4][CH:3]=1.[N+:11]([C:14]1[CH:19]=[CH:18][C:17]([O-:20])=[CH:16][CH:15]=1)([O-:13])=[O:12].[Na+]>CN(C)C=O>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][O:20][C:17]2[CH:18]=[CH:19][C:14]([N+:11]([O-:13])=[O:12])=[CH:15][CH:16]=2)=[CH:4][CH:3]=1
Reactant: O=[N+]([O-])c1ccc([O-])cc1
Reactant: Cc1ccc(CCBr)cc1
Agent: [Na+]
Solvent: CN(C)C=O
Product: Cc1ccc(CCOc2ccc([N+](=O)[O-])cc2)cc1
Yield: 73.8 %

Procedure:
2-(4-Methylphenyl)ethyl bromide (X: X=Br) (10 g, 0.05 mole) and sodium 4-nitrophenolate (XI) (8.1 g, 0.05 mole) were added to dimethylformamide (60 ml), and the mixture was reacted at 90° C. for 5 hours. Thereafter, the reaction mixture was treated in the same manner as in Example 12 to obtain 9.5 g of 4-[2-(4-methylphenyl)ethoxy]nitrobenzene (VI) as white crystals (yield, 73.9%).
Reaction SMILES: [S].[F-:2].[K+].C1[S:8](=O)(=O)CCC1.[F:11][C:12]([F:19])([F:18])[C:13](F)=[C:14]([F:16])[F:15]>C(=O)=O.CC(C)=O>[F:2][C:14]([F:16])([F:15])[C:13]([C:12]([F:19])([F:18])[F:11])=[S:8]
Reactant: FC(F)=C(F)C(F)(F)F
Reactant: [F-]
Reactant: O=S1(=O)CCCC1
Agent: O=C=O
Agent: [K+]
Agent: [S]
Solvent: CC(C)=O
Product: FC(F)(F)C(=S)C(F)(F)F

Procedure:
Into a 500 mL flask as described in Example II was charged 32 g (1.0 mole) sulfur, 22 g (0.38 mole) of anhydrous KF and 200 mL tetramethylene sulfone. The mixture was heated to 45°-65° C. and 60 g (0.40 mole) of hexafluoropropene was fed to the reaction mixture over a 3 hour period. There was recovered 60 g (0.40 mole) of unreacted hexafluoropropene in the dry-ice-acetone trap indicating that no reaction with sulfur had taken place. No hexafluorothioacetone dimer was isolated from the reaction mixture.
Reaction SMILES: [Br:1][C:2]1[CH:10]=[CH:9][C:5]([CH:6]=[N:7][OH:8])=[CH:4][C:3]=1[CH3:11].BrN1C(=O)[CH2:16][CH2:15][C:14]1=O.ClC(C)=C.C(N(CC)CC)C>CN(C)C=O>[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]2[CH:14]=[C:15]([CH3:16])[O:8][N:7]=2)=[CH:4][C:3]=1[CH3:11]
Reactant: Cc1cc(C=NO)ccc1Br
Reactant: O=C1CCC(=O)N1Br
Agent: C=C(C)Cl
Solvent: CCN(CC)CC
Solvent: CN(C)C=O
Product: Cc1cc(-c2ccc(Br)c(C)c2)no1
Temperature: -15 °C
Reaction time: 2.5 h
Yield: 27.3 %

Procedure:
A solution of 4-bromo-3-methylbenzaldehyde oxime (D81) (2.68 g, 0.0125 mol) in dry dimethylformamide (30 ml) was treated over 15 minutes with N-bromosuccinimide (636 mg, 0.00357 mol), and reaction mixture stirred for 2.5 hours, then cooled to -15° C. 2-Chloropropene (3.45 ml, 0.0405 mol) was added in a single portion, followed by dropwise addition of triethylamine (1.35 ml, 0.0097 mol) in dry dimethylformamide (10 ml) over 0.5 hours maintaining the temp. at -10° C. The mixture was stirred at 0° C. for 1 hour, then stirred at room temperature overnight. The solvent was evaporated under reduced pressure and the residue partitioned between K2CO3 solution and chloroform. The organic phase was dried (Na2SO4) and evaporated under reduced pressure and the residue purified by chromatography on silica gel eluting with 60-80 petroleum-ether and ethyl acetate, to afford the title compound (246 mg, 8%).