Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: C(OC([N:8]1[C:12]2=[C:13](Cl)[N:14]=[CH:15][C:16]([C:17]([N:19]3[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]3)=[O:18])=[C:11]2[C:10]([CH3:26])=[CH:9]1)=O)(C)(C)C.[Cl:27][C:28]1[CH:29]=[C:30]([CH:32]=[CH:33][CH:34]=1)[NH2:31]>C(OCC)C>[Cl:27][C:28]1[CH:29]=[C:30]([NH:31][C:13]2[N:14]=[CH:15][C:16]([C:17]([N:19]3[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24]3)=[O:18])=[C:11]3[C:10]([CH3:26])=[CH:9][NH:8][C:12]=23)[CH:32]=[CH:33][CH:34]=1
Reactant: Cc1cn(C(=O)OC(C)(C)C)c2c(Cl)ncc(C(=O)N3CCCCC3)c12
Reactant: Nc1cccc(Cl)c1
Solvent: CCOCC
Product: Cc1c[nH]c2c(Nc3cccc(Cl)c3)ncc(C(=O)N3CCCCC3)c12

Procedure:
Prepared in a similar manner to Example 4(d) from 7-chloro-3-methyl-4-(1-piperidin-1-yl-methanoyl)-pyrrolo[2,3-c]pyridine-1-carboxylic acid tert-butyl ester (90 mg) and using 3-chloroaniline (50 ul) instead of 3-bromoaniline and heating for 15 rather than 30 minutes. Isolated by MDAP rather than trituration with diethyl ether to give the title compound (67 mg).
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.[CH3:20][C:21]([CH2:23][CH2:24][CH2:25][Cl:26])=[O:22]>>[Cl-:26].[CH3:20][C:21]([CH2:23][CH2:24][CH2:25][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)=[O:22]
Reactant: CC(=O)CCCCl
Reactant: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Product: CC(=O)CCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1
Product: [Cl-]
Yield: 82 %

Procedure:
The title compound was prepared from triphenylphosphine and 3-chloropropyl methyl ketone as described in Example 1 in a yield of 82%.
Reaction SMILES: [NH2:1][C:2]1[CH:3]=[C:4]([N:8]2[CH2:12][CH:11]([C:13]3[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[C:15]([O:21][CH:22]4[CH2:26][CH2:25][CH2:24][CH2:23]4)[CH:14]=3)[CH2:10][C:9]2=[O:27])[CH:5]=[CH:6][CH:7]=1.[CH3:28][O:29][C:30]1[CH:31]=[C:32]([S:36](Cl)(=[O:38])=[O:37])[CH:33]=[CH:34][CH:35]=1>N1C=CC=CC=1.C(Cl)Cl>[CH:22]1([O:21][C:15]2[CH:14]=[C:13]([CH:11]3[CH2:12][N:8]([C:4]4[CH:3]=[C:2]([NH:1][S:36]([C:32]5[CH:33]=[CH:34][CH:35]=[C:30]([O:29][CH3:28])[CH:31]=5)(=[O:38])=[O:37])[CH:7]=[CH:6][CH:5]=4)[C:9](=[O:27])[CH2:10]3)[CH:18]=[CH:17][C:16]=2[O:19][CH3:20])[CH2:26][CH2:25][CH2:24][CH2:23]1
Reactant: COc1cccc(S(=O)(=O)Cl)c1
Reactant: COc1ccc(C2CC(=O)N(c3cccc(N)c3)C2)cc1OC1CCCC1
Solvent: ClCCl
Solvent: c1ccncc1
Product: COc1cccc(S(=O)(=O)Nc2cccc(N3CC(c4ccc(OC)c(OC5CCCC5)c4)CC3=O)c2)c1
Temperature: 25 °C
Reaction time: 15 h
Yield: 65.2 %

Procedure:
A mixture of 1-(3-aminophenyl)-4-(3-cyclopentyloxy-4-methoxyphenyl)-pyrrolidin-2-one (15 mg, 0.04 mmol) and 3-methoxybenzenesulfonyl chloride (10 mg, 0.042 mol) in pyridine (30 μL) and CH2Cl2 (0.5 mL) was created in a dry round bottom flask. The mixture was stirred at r.t. for 15 h. After removal of solvent, the residue was purified by preparative LC-MS to give 14 mg of N-{3-[4-(3-cyclopentyloxy-4-methoxyphenyl)-2-oxo-pyrrolidin-1-yl]phenyl}-3-methoxybenzenesulfonamide. Yield: 65%.
Reaction SMILES: [Cl:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[CH:8][C:9]=2[NH:11][C:12]2[CH:17]=[CH:16][C:15]([NH2:18])=[CH:14][C:13]=2[F:19])[NH:4][CH:3]=1.[Cl:20][C:21]1[CH:26]=[C:25](Cl)[N:24]=[C:23]([NH2:28])[N:22]=1.Cl.[OH-].[Na+]>O>[Cl:20][C:21]1[N:22]=[C:23]([NH2:28])[N:24]=[C:25]([NH:18][C:15]2[CH:16]=[CH:17][C:12]([NH:11][C:9]3[CH:8]=[CH:7][N:6]=[C:5]4[NH:4][CH:3]=[C:2]([Cl:1])[C:10]=34)=[C:13]([F:19])[CH:14]=2)[CH:26]=1
Reactant: Nc1ccc(Nc2ccnc3[nH]cc(Cl)c23)c(F)c1
Reactant: Nc1nc(Cl)cc(Cl)n1
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Solvent: O
Product: Nc1nc(Cl)cc(Nc2ccc(Nc3ccnc4[nH]cc(Cl)c34)c(F)c2)n1
Temperature: 100 °C
Reaction time: 8 h

Procedure:
57 mg (210 mmol) of N1-(3-chloro-1H-pyrrolo[2,3-b]pyridin-4-yl)-2-fluorobenzene-1,4-diamine and 47 mg (290 μmol) of 4,6-dichloropyrimidine-2-amine are suspended in 5 ml of water. 290 μl (290 mmol) of 1 M hydrochloric acid are added, and the mixture is stirred at 100° C. overnight. Using 1N aqueous sodium hydroxide solution, the suspension is then adjusted to pH 10, resulting in the precipitation of crystals. The solid is filtered off and washed with water. The crude product is purified by column chromatography on silica gel (mobile phase: dichloromethane/methanol (7M ammonia) 100:1 to 10:1) and subsequent preparative RP-HPLC.
Reaction SMILES: [N:1]1[CH:6]=[CH:5][C:4]([C:7]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]([CH2:17][C:18](O)=[O:19])=[CH:9][CH:8]=2)=[CH:3][CH:2]=1.C(Cl)(=O)C(Cl)=O.[NH2:27][C:28]1[CH:29]=[C:30]2[C:34](=[CH:35][CH:36]=1)[NH:33][CH:32]=[C:31]2[CH:37]1[CH2:42][CH2:41][N:40]([CH3:43])[CH2:39][CH2:38]1.C(N(CC)CC)C>ClCCl>[CH3:43][N:40]1[CH2:41][CH2:42][CH:37]([C:31]2[C:30]3[C:34](=[CH:35][CH:36]=[C:28]([NH:27][C:18](=[O:19])[CH2:17][C:10]4[C:11]5[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=5)[C:7]([C:4]5[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=5)=[CH:8][CH:9]=4)[CH:29]=3)[NH:33][CH:32]=2)[CH2:38][CH2:39]1
Reactant: CN1CCC(c2c[nH]c3ccc(N)cc23)CC1
Reactant: O=C(O)Cc1ccc(-c2ccncc2)c2ccccc12
Agent: O=C(Cl)C(=O)Cl
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: CN1CCC(c2c[nH]c3ccc(NC(=O)Cc4ccc(-c5ccncc5)c5ccccc45)cc23)CC1
Temperature: 25 °C
Reaction time: 3 h
Yield: 15.1 %

Procedure:
A stirred suspension of 4-(pyridin-4-yl)naphth-1-ylacetic acid (D7, 0.18 g, 0.7 mmole) in dichloromethane (15 ml) was treated with oxalyl chloride (0.18 ml, 2.1 mmole), then stirred at room temperature for 3 hours, before evaporating to dryness. The solid residue was suspended in dichloromethane (15 ml), cooled to 0° C. and treated with a solution of 5-amino-3-(1-methylpiperidin-4-yl)-1H-indole (D2, 0.13 g, 0.56 mmole) in dichloromethane (15 ml). The mixture was stirred at 0° for 1 hour and then a solution of triethylamine (0.25 ml) in dichloromethane (5 ml) was added dropwise. The mixture was allowed to warm to room temperature and stir overnight, then evaporated to dryness and the residue subjected to flash chromatography on silica gel eluting with CH2Cl2/MeOH/NH4OH (100:5:0.5 to 100:10:1 gradient elution) to afford the title compound as a pale cream powder (0.04 g).
Reaction SMILES: [C:1]([C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)=[CH:5][CH:4]=1)#[N:2].N1C=CC=CC=1.[CH2:22]([O:30][C:31](Cl)=[O:32])[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29]>C1C=CC=CC=1>[C:31](=[O:32])([O:30][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])[O:15][C:12]1[CH:13]=[CH:14][C:9]([C:6]2[CH:5]=[CH:4][C:3]([C:1]#[N:2])=[CH:8][CH:7]=2)=[CH:10][CH:11]=1
Reactant: CCCCCCCCOC(=O)Cl
Reactant: N#Cc1ccc(-c2ccc(O)cc2)cc1
Solvent: c1ccncc1
Solvent: c1ccccc1
Product: CCCCCCCCOC(=O)Oc1ccc(-c2ccc(C#N)cc2)cc1

Procedure:
0.390 G. of 4'-cyano-4-hydroxy-biphenyl are dissolved in 10 ml. of absolute pyridine and reacted with 0.423 g. of chloroformic acid n-octyl ester as in Example 1. The 0.721 g. of brownish oil obtained according to the procedure described in Example 1 is dissolved in benzene and chromatographed on 40 g. of silica gel. Benzene elutes 0.620 g. of colorless crystals which are recrystallized from ether-hexane up to constant melting point and clearing point. The pure 4'-cyano-4-biphenylyl n-octyl carbonate obtained melts at 51.64° and has a clearing point of 67.7°. UV (EtOH): ε 270 = 26000.
Reaction SMILES: [NH2:1][NH2:2].[Cl:3][C:4]1[N:9]=[C:8](Cl)[C:7]([CH:11]=O)=[CH:6][N:5]=1.O>C1COCC1>[Cl:3][C:4]1[N:9]=[C:8]2[NH:1][N:2]=[CH:11][C:7]2=[CH:6][N:5]=1
Reactant: O=Cc1cnc(Cl)nc1Cl
Reactant: NN
Solvent: C1CCOC1
Solvent: O
Product: Clc1ncc2cn[nH]c2n1
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
To a stirred solution of hydrazine (Aldrich, 64 mg, 2 mmol) in THF (5 mL), 2,4-Dichloro-pyrimidine-5-carbaldehyde (Example 17, 176 mg, 1 mmol) was added and the mixture was stirred at room temperature for 30 min. The mixture was poured into water and extracted with EtOAc. The extract was dried with sodium sulfate and the solvent was removed to give an orange solid. 128 mg, 82%. MS (M+H)+, 155.
Reaction SMILES: [Cl:1][C:2]1[C:3]([C:20]#[N:21])=[C:4]([C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=2)[N:5](CCl)[C:6]=1[C:7]([F:10])([F:9])[F:8].[CH3:22][N:23]([CH3:27])[C:24](=[S:26])[SH:25].[Na].O.[CH3:30]N(C)C=O>CCCCCC>[Cl:1][C:2]1[C:3]([C:20]#[N:21])=[C:4]([C:13]2[CH:14]=[CH:15][C:16]([Cl:19])=[CH:17][CH:18]=2)[N:5]([SH:26]([CH3:30])[C:24](=[S:25])[N:23]([CH3:27])[CH3:22])[C:6]=1[C:7]([F:8])([F:10])[F:9]
Reactant: CN(C)C(=S)S
Reactant: CN(C)C=O
Reactant: N#Cc1c(Cl)c(C(F)(F)F)n(CCl)c1-c1ccc(Cl)cc1
Agent: [Na]
Solvent: CCCCCC
Solvent: O
Product: CN(C)C(=S)[SH](C)n1c(-c2ccc(Cl)cc2)c(C#N)c(Cl)c1C(F)(F)F
Temperature: 25 °C
Yield: 80 %

Procedure:
A mixture of 4-chloro-1-(chloromethyl)-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (0.7 g, 0.002 mol) and dimethyldithiocarbamic acid, sodium salt (0.57 g, 0.004 mol) in dimethyl formamide is heated at 50°-55° for 30 minutes, cooled to room temperature and poured into water. The resultant mixture is extracted with ethyl acetate. The combined extracts are washed with a saturated sodium chloride solution, dried (MgSO4) and concentrated in vacuo to give an orange oil residue. The residue is mixed with hot hexane, cooled and filtered to give an orange solid filtercake. Recrystallization of the solid from isopropanol gives the title product as a tan crystaline solid, 0.7 g (80% yield), mp 129°-131° C.
Reaction SMILES: [F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:17]([N:18]3[CH2:23][CH2:22][CH2:21][CH:20]([CH2:24][O:25][CH3:26])[CH2:19]3)=[N:16][C:15]3[C:10](=[CH:11][CH:12]=[C:13]([C:27]([O:29]C)=[O:28])[CH:14]=3)[N:9]=2)=[CH:4][CH:3]=1.[OH-].[Na+]>CO.O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:17]([N:18]3[CH2:23][CH2:22][CH2:21][CH:20]([CH2:24][O:25][CH3:26])[CH2:19]3)=[N:16][C:15]3[C:10](=[CH:11][CH:12]=[C:13]([C:27]([OH:29])=[O:28])[CH:14]=3)[N:9]=2)=[CH:4][CH:3]=1
Reactant: COCC1CCCN(c2nc3cc(C(=O)OC)ccc3nc2-c2ccc(F)cc2)C1
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: CO
Product: COCC1CCCN(c2nc3cc(C(=O)O)ccc3nc2-c2ccc(F)cc2)C1
Reaction time: 0.13 h

Procedure:
Into a 50-mL round-bottom flask, was placed a solution of methyl 2-(4-fluorophenyl)-3-(3-(methoxymethyl)piperidin-1-yl)quinoxaline-6-carboxylate (152.3 mg, 0.37 mmol, 1.00 equiv) in methanol (15 mL). This was followed by the addition of a solution of sodium hydroxide (44.7 mg, 1.12 mmol, 3.00 equiv) in water (1.5 mL) dropwise with stirring. The resulting solution was stirred for 4 h at 50° C. in an oil bath. The resulting mixture was concentrated under vacuum. The resulting solution was diluted with water. The pH value of the aqueous solution was adjusted to 3-4 with 1N hydrogen chloride. The resulting solids were collected by filtration and the crude product (240 mg) was purified by Prep-HPLC under the following conditions (AGILENT Pre-HPLC (UV-Directed)): Column, SunFire Prep C18, 19*150 mm 5 um; mobile phase, water with 0.05% TFA and CH3CN (45% CH3CN up to 60% in 8 min, hold 60% in 5 min, up to 100% in 0.1 min, hold 100% in 1.4 min); Detector, uv 220&254 nm. This resulted in 89 mg (61%) of 2-(4-fluorophenyl)-3-(3-(methoxymethyl)piperidin-1-yl)quinoxaline-6-carboxylic acid as a yellow solid.
Reaction SMILES: C1N=CN(C(N2C=NC=C2)=O)C=1.[CH3:13][O:14][C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][C:23]=1[N+:24]([O-:26])=[O:25])[C:18]([OH:20])=O.Cl.[NH:28]1[CH2:33][CH2:32][C:31](=[O:34])[CH2:30][CH2:29]1.C(N(CC)CC)C>C1COCC1.C(OCC)(=O)C>[CH3:13][O:14][C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][C:23]=1[N+:24]([O-:26])=[O:25])[C:18]([N:28]1[CH2:33][CH2:32][C:31](=[O:34])[CH2:30][CH2:29]1)=[O:20]
Reactant: O=C1CCNCC1
Reactant: COc1cc(C(=O)O)ccc1[N+](=O)[O-]
Agent: Cl
Agent: O=C(n1ccnc1)n1ccnc1
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Solvent: CCOC(C)=O
Product: COc1cc(C(=O)N2CCC(=O)CC2)ccc1[N+](=O)[O-]
Reaction time: 1 h
Yield: 60.2 %

Procedure:
CDI (9 g) added to a solution of 3-methoxy-4-nitrobenzoic acid (10 g) stirring in THF (200 ml) at RT. After 1 hour, 4-piperidone hydrochloride (6.9 g) and triethylamine (7.8 ml) were added and the mixture stirred overnight. The mixture was diluted with ethyl acetate, washed with 2N HCl (100 ml) then saturated NaHCO3 solution (200 ml) then saturated brine (200 ml). The organic layer was dried (MgSO4) and evaporated to leave a residue which was purified by column chromatography (silica, mixtures of MeOH in dichloromethane) to give the product as a yellow solid (8.5 g; MS: APCI+(M+H) 279).
Reaction SMILES: [C:1]([C:3]1[CH:8]=[C:7]([N+:9]([O-])=O)[CH:6]=[CH:5][C:4]=1[N:12]1[CH2:17][CH2:16][CH:15]([CH:18]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:19]([NH:21][CH2:22][CH3:23])=[O:20])[CH2:14][CH2:13]1)#[N:2].C(N[C:33](=[O:47])[CH:34]([C:41]1C=CC=C[CH:42]=1)[CH:35]1CCNC[CH2:36]1)C.FC1C=CC([N+]([O-])=O)=CC=1C#N.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.O>[C:1]([C:3]1[CH:8]=[C:7]([NH:9][C:33](=[O:47])[CH:34]([CH2:41][CH3:42])[CH2:35][CH3:36])[CH:6]=[CH:5][C:4]=1[N:12]1[CH2:17][CH2:16][CH:15]([CH:18]([C:19](=[O:20])[NH:21][CH2:22][CH3:23])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH2:14][CH2:13]1)#[N:2]
Reactant: CCNC(=O)C(c1ccccc1)C1CCNCC1
Reactant: CCNC(=O)C(c1ccccc1)C1CCN(c2ccc([N+](=O)[O-])cc2C#N)CC1
Agent: N#Cc1cc([N+](=O)[O-])ccc1F
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CN(C)C=O
Product: CCNC(=O)C(c1ccccc1)C1CCN(c2ccc(NC(=O)C(CC)CC)cc2C#N)CC1
Temperature: 80 °C
Yield: 86 %

Procedure:
2-[1-(2-Cyano-4-nitro-phenyl)-piperidin-4-yl]-N-ethyl-2-phenyl-acetamide. To a solution of N-ethyl-2-phenyl-2-piperidin-4-yl-acetamide (500 mg, 2 mmol) and 2-fluoro-5-nitro-benzonitrile (337 mg, 2.03 mmol) in DMF was added K2CO3 (840 mg, 6.1 mmol). The solution was heated to 80° C. for 16 h. After cooling to rt, H2O and 3:1 EtOAc/hexanes were added. The organic portion was washed three times with H2O and once with brine, dried (Na2SO4) and concentrated to provide the title compound (yellow powder, 686 mg, 86%).
Reaction SMILES: [CH3:1][O:2][CH2:3][CH:4]([OH:15])[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14].Cl[CH2:17][C:18]([O-:20])=[O:19].[Na+].[OH-].[Na+]>>[CH3:1][O:2][CH2:3][CH:4]([O:15][CH2:17][C:18]([OH:20])=[O:19])[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]
Reactant: CCCCCCCCCCC(O)COC
Reactant: O=C([O-])CCl
Agent: [Na+]
Agent: [OH-]
Product: CCCCCCCCCCC(COC)OCC(=O)O

Procedure:
108 g (0.5 mole) 1-methoxy-2-dodecanol are reacted with sodium chloroacetate (58.3 g; 0.5 mole) and powdered sodium hydroxide (20 g; 0.5 mole) as in Example 1 to yield 2-(1-Methoxymethylundecyloxy)acetic acid as a colourless oil, bp. 162° C./0.26 mbar, yield 59.0 g (43%).
Reaction SMILES: [O:1]([C:8]1[CH:13]=[CH:12][C:11]([CH:14]2[CH2:18][CH2:17][CH2:16][NH:15]2)=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.[C:26](Cl)(=[O:28])[CH3:27]>CCOCC>[C:26]([N:15]1[CH2:16][CH2:17][CH2:18][CH:14]1[C:11]1[CH:12]=[CH:13][C:8]([O:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:9][CH:10]=1)(=[O:28])[CH3:27]
Reactant: CC(=O)Cl
Reactant: c1ccc(Oc2ccc(C3CCCN3)cc2)cc1
Solvent: CCOCC
Solvent: CCN(CC)CC
Product: CC(=O)N1CCCC1c1ccc(Oc2ccccc2)cc1

Procedure:
To a solution of 10 parts of 2-(4-phenoxyphenyl) pyrrolidine in 200 parts of anhydrous ether and 4.2 parts of triethylamine, there was added a solution of 3.3 parts of acetyl chloride in 30 parts of ether. The reflux was maintained for one hour, then the reaction mixture was filtered off on cooling and the filtrate was distilled. There were obtained 13 parts of 1-acetyl-2-(4-phenoxyphenyl) pyrrolidine.
Reaction SMILES: Br.[C:2]([N:5]1[CH2:9][C:8]([CH2:12]C)([CH2:10]C)[NH:7][C:6]1=[O:14])(=[NH:4])[NH2:3].C1(C2CCCCCCCCCC=2)CCCCCCCCNN=1.[CH:37]1([CH2:40][N:41]([C:51]2[CH:56]=[CH:55][CH:54]=[C:53]([C:57]([F:60])([F:59])[F:58])[CH:52]=2)[C:42](=[O:50])[C:43]([C:48]#[N:49])=[CH:44]OCC)[CH2:39][CH2:38]1>>[C:48]([C:43]([C:42](=[O:50])[N:41]([CH2:40][CH:37]1[CH2:39][CH2:38]1)[C:51]1[CH:56]=[CH:55][CH:54]=[C:53]([C:57]([F:58])([F:60])[F:59])[CH:52]=1)=[CH:44][NH:3][C:2](=[NH:4])[N:5]1[CH2:9][C:8]([CH3:10])([CH3:12])[NH:7][C:6]1=[O:14])#[N:49]
Reactant: CCOC=C(C#N)C(=O)N(CC1CC1)c1cccc(C(F)(F)F)c1
Reactant: CCC1(CC)CN(C(=N)N)C(=O)N1
Agent: Br
Agent: C1=C(C2=NNCCCCCCCC2)CCCCCCCCC1
Product: CC1(C)CN(C(=N)NC=C(C#N)C(=O)N(CC2CC2)c2cccc(C(F)(F)F)c2)C(=O)N1
Yield: 35.4 %

Procedure:
Starting from 6.58 g (24.8 mmol) of 1-amidino-4,4-diethyl-2-oxoimidazolidine hydrobromide (comp. III: R1, R2 =C2H5 ; R3 =H as hydrobromide) and 3.87 g (26.1 mmol) of diazabicycloundecene (DBU) as auxiliary base and 7.40 g (24.8 mmol) of a compound IV (R4 =CH3 ; R5, R6 =H; R7 =C3H5) by the procedure described in Examples 82-84, 3.94 g (=36.4% yield) of pure 1-cyano-1-[N-methyl-N-(3-trifluoromethylphenyl)carbamoyl]-2-[imino(4,4-diethyl-2-oxo-1-imidazolidinyl)methylamino]ethene (comp. II: R1, R2 =C2H5 ; R3, R5, R6 =H; R4 =CH3) were obtained, melting point 184°-87°.
Reaction SMILES: S([O:6][CH3:7])(OC)(=O)=O.[OH:8][C:9](=[CH:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=1)[C:10](O)=[O:11].[C:23](=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[CH3:23][O:8][C:9](=[CH:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=1)[C:10]([O:6][CH3:7])=[O:11]
Reactant: O=C([O-])[O-]
Reactant: COS(=O)(=O)OC
Reactant: O=C(O)C(O)=Cc1cccc([N+](=O)[O-])c1
Agent: [Cs+]
Solvent: CN(C)C=O
Product: COC(=O)C(=Cc1cccc([N+](=O)[O-])c1)OC
Temperature: 25 °C
Reaction time: 8 h
Yield: 68.3 %

Procedure:
Dimethyl sulfate (13.23 g, 105 mmol) was added to a stirred mixture of 2-hydroxy-3-(3-nitrophenyl)acrylic acid (10.5 g, 50.0 mmol) and caesium carbonate (39.1 g, 120 mmol) in DMF (105 ml) to form a clear, pale yellow mixture, which was stirred at RT overnight. The resulting dark red suspension was concentrated in vacuo and the residue partitioned between water (100 ml) and dichloromethane (150 ml). The organic layer was separated, further washed with water (2×100 ml), dried over sodium sulphate and filtered through silica gel. The resulting yellow solution was evaporated to dryness in vacuo to give methyl 2-methoxy-3-(3-nitrophenyl)acrylate as a yellow solid (8.1 g, 67%). 1H NMR (δ, 250 MHz, DMSO-d6)=3.81 (3H, s), 3.83 (3H, s), 7.08 (1H, s), 7.71 (1H, dd, 7.9 & 8.2 Hz), 8.10-8.22 (2H, m), 8.66 (1H, s).
Reaction SMILES: [C:1]([C:3](=[CH2:51])[C:4]([NH:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([NH:16][C:17]2[C:18](=[O:50])[N:19]([CH3:49])[CH:20]=[C:21]([C:23]3[CH:28]=[C:27]([F:29])[CH:26]=[C:25]([N:30]4[C:35](=[O:36])[C:34]5[S:37][C:38]6[CH2:43][CH2:42][CH2:41][CH2:40][C:39]=6[C:33]=5[CH:32]=[N:31]4)[C:24]=3[CH2:44][O:45]C(=O)C)[CH:22]=2)[N:11]=1)=[O:5])#[N:2].O[Li].O>C1COCC1.O>[C:1]([C:3](=[CH2:51])[C:4]([NH:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([NH:16][C:17]2[C:18](=[O:50])[N:19]([CH3:49])[CH:20]=[C:21]([C:23]3[CH:28]=[C:27]([F:29])[CH:26]=[C:25]([N:30]4[C:35](=[O:36])[C:34]5[S:37][C:38]6[CH2:43][CH2:42][CH2:41][CH2:40][C:39]=6[C:33]=5[CH:32]=[N:31]4)[C:24]=3[CH2:44][OH:45])[CH:22]=2)[N:11]=1)=[O:5])#[N:2]
Reactant: C=C(C#N)C(=O)NCCOc1cccc(Nc2cc(-c3cc(F)cc(-n4ncc5c6c(sc5c4=O)CCCC6)c3COC(C)=O)cn(C)c2=O)n1
Agent: [Li]O
Solvent: C1CCOC1
Solvent: O
Product: C=C(C#N)C(=O)NCCOc1cccc(Nc2cc(-c3cc(F)cc(-n4ncc5c6c(sc5c4=O)CCCC6)c3CO)cn(C)c2=O)n1
Temperature: 25 °C
Reaction time: 4 h
Yield: 16 %

Procedure:
To a mixture of 117b (80 mg, 0.112 mmol) in THF (5 mL) was added LiOH.H2O (10 mg, 0.224 mmol) in H2O (5 mL) to pH 10-11. The reaction mixture was stirred at rt for 4 h and concentrated. The residue was purified by prep-HPLC to give 117 (12 mg, 16%) as white solid. The amide bond was partially cleaved under basic conditions. 1H NMR (500 MHz, CDCl3): δ8.57 (s, 1H), 8.29 (s, 1H), 7.99 (bs, 1H), 7.49 (t, J=8 Hz, 2H), 7.26-7.24 (m, 1H), 7.12 (d, J=10 Hz, 1H), 6.48 (d, J=8 Hz, 1H), 6.26 (d, J=8 Hz, 1H), 4.41 (t, J=5 Hz, 2H), 4.31 (bs, 2H), 4.00-3.98 (m, 1H), 3.72 (s, 3H), 3.63 (t, J=5.5 Hz, 1H), 3.58-2.56 (m, 1H), 2.99 (t, J=5 Hz, 2H), 2.87 (t, J=5 Hz, 2H), 2.00-1.96 (m, 4H). ESI-LCMS: m/z=668.0 [C34H30FN7O5S+H]+
Reaction SMILES: Cl.[CH3:2][O:3][C:4](=[O:9])[C@@H:5]([CH2:7][OH:8])[NH2:6].CCN(CC)CC.Cl[C:18]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(Cl)Cl>[OH:8][CH2:7][C@@H:5]([NH:6][C:18]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1)[C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)[C:4]([O:3][CH3:2])=[O:9]
Reactant: COC(=O)[C@H](N)CO
Reactant: ClC(c1ccccc1)(c1ccccc1)c1ccccc1
Agent: Cl
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: COC(=O)[C@@H](CO)NC(c1ccccc1)(c1ccccc1)c1ccccc1
Temperature: 0 °C
Reaction time: 24 h
Yield: 96.2 %

Procedure:
(S. Bhatia and J. Hajdu, Tetrahedron Lett. 1998, 29, 31-34). To a solution of D-serine methyl ester hydrochloride (20.00 g, 0.13 mol) and Et3N (35.82 mL, 0.26 mol) in CH2Cl2 (80 mL) at 0° C., was added in one portion a solution of TrCl (36.53 g, 0.13 mol) in CH2Cl2 (80 mL). The mixture was allowed to stir at 0° C. (24 h) under Ar and then successively washed with 10% aqueous citric acid (120 mL) and saturated aqueous brine (120 mL). The organic layer was dried (Na2SO4) and evaporated in vacuo to yield 45.20 g (97%) of crude desired product as a pale yellow crystalline solid. The product was used for next step without further purification: Rf=0.50 (1/1 EtOAc/hexanes); 1H NMR (CDCl3) δ 2.29 (br s, 1H), 2.98 (br s, 1H), 3.29 (s, OCH3), 3.51-3.60 (m, CHH′OH, CH), 3.64-3.74 (m, CHH′OH), 7.16-7.30 (m, 9 PhH), 7.47-7.50 (m, 6 PhH).
Reaction SMILES: Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+].[CH2:14]=[CH:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C1(=O)OC(C)CO1>C(OCC)C>[C:2]1([CH:14]=[CH:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: C=Cc1ccccc1
Reactant: Clc1ccccc1
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: CCOCC
Solvent: CC1COC(=O)O1
Product: C(=Cc1ccccc1)c1ccccc1
Temperature: 155 °C
Reaction time: 17 h

Procedure:
Under argon, a solution containing 122 mg of chlorobenzene, 106 mg of sodium carbonate, 157 mg of styrene and 1 ml of propylene carbonate stabilized 0.001 M colloid solution is heated at 155° C. with stirring in a sealed vessel for 17 h. At the end of the reaction, 2 ml of diethyl ether is added, and the mixture is filtered. The yield of isolated trans-stilbene is 15%.
Reaction SMILES: [CH3:1][NH:2][CH3:3].[C:4](=[S:6])=[S:5].[N+:7]([CH:10]=[CH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([O-:9])=[O:8]>CO>[CH3:1][N:2]([CH3:3])[C:4](=[S:6])[S:5][CH:11]([CH2:10][N+:7]([O-:9])=[O:8])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
Reactant: O=[N+]([O-])C=Cc1ccccc1
Reactant: S=C=S
Reactant: CNC
Solvent: CO
Product: CN(C)C(=S)SC(C[N+](=O)[O-])c1ccccc1

Procedure:
Similarly, gradual addition of dimethylamine (45.1 grams, 1 mole) to a methanol solution of carbon disulfide (83.6 grams, 1.1 mole) and β-nitrostyrene (149.1 grams, 1 mole) at 10°-30° C. yields α-(nitromethyl)benzyl dimethyldithiocarbamate.
Reaction SMILES: [CH3:1][CH2:2][CH:3]=[CH2:4].[C:5]1([CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>>[CH:3]([CH:11]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH2:2][CH3:1])[CH3:4]
Reactant: c1ccc(Cc2ccccc2)cc1
Reactant: C=CCC
Product: CCC(C)C(c1ccccc1)c1ccccc1

Procedure:
Using the same catalyst as that of Preparation Example 1, reaction was carried out with butene-1 and diphenylmethane to obtain sec-butyldiphenylmethane of 96 wt. % purity. The boiling point of the reaction product was 301° to 309° C. and the flash point thereof was 162° C. This reaction product is called as diarylalkane 2 (hereinafter referred to as "DAA2") and the physical properties thereof are shown in the following Table 1.