Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [Cl:1][C:2]1[C:3]2[CH2:10][C:9](=[O:11])[NH:8][C:4]=2[N:5]=[CH:6][N:7]=1.[N:12]1([CH2:18][CH2:19][NH:20][C:21]([C:23]2[NH:24][C:25]([CH:28]=O)=[CH:26][CH:27]=2)=[O:22])[CH2:17][CH2:16][O:15][CH2:14][CH2:13]1.C(N(CC)CC)C>C(O)C>[N:12]1([CH2:18][CH2:19][NH:20][C:21]([C:23]2[NH:24][C:25]([CH:28]=[C:10]3[C:3]4[C:2]([Cl:1])=[N:7][CH:6]=[N:5][C:4]=4[NH:8][C:9]3=[O:11])=[CH:26][CH:27]=2)=[O:22])[CH2:17][CH2:16][O:15][CH2:14][CH2:13]1
Reactant: O=Cc1ccc(C(=O)NCCN2CCOCC2)[nH]1
Reactant: O=C1Cc2c(Cl)ncnc2N1
Solvent: CCN(CC)CC
Solvent: CCO
Product: O=C1Nc2ncnc(Cl)c2C1=Cc1ccc(C(=O)NCCN2CCOCC2)[nH]1
Yield: 92.5 %

Procedure:
4-Chloro-5,7-dihydro-pyrrolo[2,3-d]pyrimidin-6-one (1 eq.) was condensed with 5-formyl-1H-pyrrole-2-carboxylic acid (2-morpholin-4-yl-ethyl)-amide (1 eq.) and triethylamine in ethanol at room temperature to give (92.5%) of 5-(4-chloro-6-oxo-6,7-dihydro-pyrrolo[2,3-d]pyrimidin-5-ylidenemethyl)-1H-pyrrole-2-carboxylic acid (2-morpholin4-yl-ethyl)-amide.
Reaction SMILES: O=[C:2]([CH3:20])[CH2:3][CH2:4][CH:5]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:16]([F:19])([F:18])[F:17])[C:6]([O:8][CH3:9])=[O:7].[BH4-].[Na+].[ClH:23]>CO>[Cl:23][CH:2]([CH3:20])[CH2:3][CH2:4][CH:5]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:16]([F:19])([F:18])[F:17])[C:6]([O:8][CH3:9])=[O:7]
Reactant: COC(=O)C(CCC(C)=O)c1ccccc1C(F)(F)F
Reactant: Cl
Agent: [BH4-]
Agent: [Na+]
Solvent: CO
Product: COC(=O)C(CCC(C)Cl)c1ccccc1C(F)(F)F
Reaction time: 0.5 h

Procedure:
Methyl 5-oxo-2-(2-trifluoromethylphenyl)hexanoate (728 mg) was dissolved in methanol (15.2 mL). Sodium borohydride (47.8 mg) was added under ice-cooling, and the reaction solution was stirred at the same temperature for 30 minutes. A 1 N hydrochloric acid aqueous solution was added to the reaction solution, followed by extraction with ethyl acetate. The resulting organic layer was dried over magnesium sulfate and then concentrated under reduced pressure. The resulting residue was dissolved in chloroform (15 mL). Thionyl chloride (576 μL) was added and the reaction solution was stirred at 50° C. for three hours. The reaction solution was concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (carrier: Chromatorex Si; elution solvent: heptane:ethyl acetate=19:1→heptane:ethyl acetate=1:1) to obtain methyl 5-chloro-2-(2-trifluoromethylphenyl)hexanoate (380 mg) as a diastereomer mixture. The mixture (320 mg) was dissolved in ethanol (7.8 mL). Hydrazine monohydrate (1.5 mL) was added and the reaction solution was stirred at 100° C. for 14 hours. The reaction solution was concentrated under reduced pressure. A saturated sodium bicarbonate solution was added to the residue, followed by extraction with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (carrier: Chromatorex Si; elution solvent: heptane:ethyl acetate=19:1→heptane:ethyl acetate=1:1) to obtain the title compound (380 mg).
Reaction SMILES: [C:1]1([C:7]2([N:14]3[CH2:19][CH2:18][CH:17]([N:20]4[C:24]5[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=5N[C:21]4=O)[CH2:16][CH2:15]3)[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.P(Cl)(Cl)([Cl:32])=O.[NH3:35]>>[Cl:32][C:21]1[N:20]([CH:17]2[CH2:18][CH2:19][N:14]([C:7]3([C:1]4[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=4)[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]3)[CH2:15][CH2:16]2)[C:24]2[CH:23]=[CH:28][CH:27]=[CH:26][C:25]=2[N:35]=1
Reactant: O=c1[nH]c2ccccc2n1C1CCN(C2(c3ccccc3)CCCCCC2)CC1
Reactant: N
Reactant: O=P(Cl)(Cl)Cl
Product: Clc1nc2ccccc2n1C1CCN(C2(c3ccccc3)CCCCCC2)CC1
Temperature: 25 °C
Yield: 58.7 %

Procedure:
A mixture of 4-(2-keto-1-benzimidazolinyl)piperidine (5.10 g, 23.5 mmol) and 10% HCl solution in MeOH (20 ml) was stirred at room temperature for 10 minutes. After evaporation of the solvent, the residue was triturated in Et2O to give HCl salt of 4-(2-keto-1-benzimidazolinyl)piperidine as off-white powder. To this HCl salt of 4-(2-keto-1-benzimidazolinyl)piperidine was added cycloheptanone (3.33 ml, 28.2 mmol) followed by addition of aqueous solution of KCN (1.92 g, 29.5 mmol) in water (7 ml) at room temperature. After 18 hours stirring, the resulting solid was collected by filtration, washed with water, and dried in vacuo to give 6.81 g (85.7%) of the nitrile derivative thus obtained as white powder. To a solution of this nitrile derivative (5.12 g, 15.1 mmol) in THF (40 ml) was added a solution of phenylmagnesium bromide in Et2O (3.0 M solution, 25 ml) at 0° C. Then the reaction mixture was stirred at room temperature for 18 hours. Aqueous NH4Cl solution was added to the reaction mixture and the resulting solid appeared was collected by filtration, washed with water and Et2O, and dried in vacuo at 70° C. to give 4.88 g (82.8%) of 1-[1-(1-phenylcycloheptyl)-4-piperidinyl]-1,3-dihydro-2H-1,3-benzimidazol-2-one as white powder. A mixture of 1-[1-(1-phenylcycloheptyl)-4-piperidinyl]-1,3-dihydro-2H-1,3-benzimidazol-2-one (2.316 g, 5.95 mmol) and phosphoryl chloride (15 ml, 165.5 mmol) was heated to reflux for 1.5 hours. After cooling down to room temperature, the reaction mixture was poured into ice cooled 25% ammonia solution and extracted with CH2Cl2. The extracts combined were washed with brine, dried (Na2SO4), filtered, and concentrated. The residue was purified by column chromatography (silica gel: 200 g, hexane/ethyl acetate: 4/1) to give 1.42 g(58.7%) of a colorless amorphous solid.
Reaction SMILES: [CH:1]([Mg]Br)=[CH2:2].CON(C)[C:8](=[O:17])[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[CH3:16]>C1COCC1.CCOCC>[CH3:16][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=1[CH2:9][C:8](=[O:17])[CH:1]=[CH2:2]
Reactant: C=C[Mg]Br
Reactant: CON(C)C(=O)Cc1ccccc1C
Solvent: C1CCOC1
Solvent: CCOCC
Product: C=CC(=O)Cc1ccccc1C
Temperature: 0 °C
Reaction time: 0.5 h
Yield: 83.1 %

Procedure:
To a solution of vinylmagnesium bromide (220 mL, 1.0 M, 220 mmol) in 100 mL THF, was added dropwise under nitrogen atmosphere at 0° C. a solution of 2-(2-methylphenyl)-N-methoxy-N-methylacetamide (Step A, 21 g, 106.6 mmol) in ˜150 mL dry ether. The reaction mixture was stirred at 0° C. for 0.5 hr then poured slowly into an ice/2N aq HCl (300 mL) mixture. The resulting mixture was diluted with ether, transferred to a separation funnel. The organic layer was separated, washed with brine, dried over MgSO4, filtered and the solvent evaporated under vacuum to give 14.2 g of the crude title compound which was used without further purification. 1H-NMR (CDCl3): δ: 7.15-7.25 (4H, m), 6.47 (1H, dd, J1=14.2 Hz, J2=11 Hz), 6.35 (1H, d, J=14.2 Hz), 5.86 (1H, d, J=11 Hz), 3.83 (2H, s), 2.28 (3H, s).
Reaction SMILES: [Cl:1][C:2]1[CH:32]=[CH:31][C:5]([CH2:6][NH:7][C:8]([C:10]2[C:19](=[O:20])[C:18]3[C:13](=[CH:14][CH:15]=[C:16]([CH2:21][N:22]4[CH2:27][CH2:26][O:25][CH2:24][CH2:23]4)[CH:17]=3)[N:12]([CH2:28][S:29][CH3:30])[CH:11]=2)=[O:9])=[CH:4][CH:3]=1.O.C1(C)C=CC(S(O)(=O)=[O:41])=CC=1.ClC1C=C(C=CC=1)C(OO)=O>ClCCl>[Cl:1][C:2]1[CH:32]=[CH:31][C:5]([CH2:6][NH:7][C:8]([C:10]2[C:19](=[O:20])[C:18]3[C:13](=[CH:14][CH:15]=[C:16]([CH2:21][N:22]4[CH2:27][CH2:26][O:25][CH2:24][CH2:23]4)[CH:17]=3)[N:12]([CH2:28][S:29]([CH3:30])=[O:41])[CH:11]=2)=[O:9])=[CH:4][CH:3]=1
Reactant: Cc1ccc(S(=O)(=O)O)cc1
Reactant: CSCn1cc(C(=O)NCc2ccc(Cl)cc2)c(=O)c2cc(CN3CCOCC3)ccc21
Agent: O=C(OO)c1cccc(Cl)c1
Solvent: O
Solvent: ClCCl
Product: CS(=O)Cn1cc(C(=O)NCc2ccc(Cl)cc2)c(=O)c2cc(CN3CCOCC3)ccc21
Reaction time: 1 h
Yield: 76 %

Procedure:
A solution of N-(4-chlorobenzyl)-1-[(methylsulfanyl)methyl]-6-(4-morpholinylmethyl)-4-oxo-1,4-dihydro-3-quinolinecarboxamide (0.14 gm) from Example No. 73 in dichloromethane (4 mL) at 0° C. is added p-toluenesulfonic acid hydrate (0.06 gm) followed by m-chloroperoxybenzoic acid (˜85%) (0.06 gm). The mixture is stirred for 1 hr. The reaction mixture is diluted with dichloromethane, washed with saturated aqueous sodium sulfite, saturated aqueous sodium bicarbonate, brine, dried (Na2SO4) and concentrated under reduced pressure. The crude product is purified by recrystallization from methanol-acetonitrile to afford 0.11 gm of the title compound as a white solid.
Reaction SMILES: [C:1]([O:5][C:6](=[O:16])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([OH:15])=[O:14])([CH3:4])([CH3:3])[CH3:2].[B-](F)(F)(F)F.CN(C(O[N:30]1[C:35](=[O:36])[CH2:34][CH2:33][C:31]1=[O:32])=[N+](C)C)C.CCN(C(C)C)C(C)C>C1COCC1>[O:32]=[C:31]1[CH2:33][CH2:34][C:35](=[O:36])[N:30]1[O:14][C:13](=[O:15])[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:16]
Reactant: CC(C)(C)OC(=O)CCCCCCC(=O)O
Reactant: CN(C)C(ON1C(=O)CCC1=O)=[N+](C)C
Agent: F[B-](F)(F)F
Solvent: C1CCOC1
Solvent: CCN(C(C)C)C(C)C
Product: CC(C)(C)OC(=O)CCCCCCC(=O)ON1C(=O)CCC1=O

Procedure:
Octanedioic acid mono-tert-butyl ester (3.14 g, 13.63 mmol) was dissolved in THF (100 mL). TSTU (4.9 g, 16.3 mmol) was added and pH was adjusted to 8.5 with DIPEA (2.85 mL).
Reaction SMILES: [CH3:1][C:2]1[O:6][C:5]([CH2:7][NH:8][C:9]2[CH:18]=[CH:17][C:16]3[C:15]([CH:19]=[O:20])=[CH:14][CH:13]=[CH:12][C:11]=3[N:10]=2)=[CH:4][CH:3]=1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)CCl>[CH3:1][C:2]1[O:6][C:5]([CH2:7][NH:8][C:9]2[CH:18]=[CH:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][C:15]=3[CH2:19][OH:20])[N:10]=2)=[CH:4][CH:3]=1
Reactant: Cc1ccc(CNc2ccc3c(C=O)cccc3n2)o1
Agent: CC(=O)O[BH-](OC(C)=O)OC(C)=O
Agent: [Na+]
Solvent: ClCCCl
Solvent: CC(=O)O
Product: Cc1ccc(CNc2ccc3c(CO)cccc3n2)o1
Temperature: 25 °C
Reaction time: 1 h

Procedure:
2-[(5-Methyl-furan-2-ylmethyl)-amino]-quinoline-5-carbaldehyde (example 21, step A+B, 150 mg, 0.564 mmol) was dissolved in 5 mL ethylendichloride and acetic acid (136 mg, 2.27 mmol) was added. The reaction mixture was stirred at room temperature for 1 h. Sodium triacetoxy borohydride (258 mg, 1.22 mmol) was added and stirring was continued overnight. The reaction mixture was quenched by addition of 50 mL water. The mixture was extracted three times with dichloromethane (50 mL each). The organic phases ware pooled, dried with sodium sulfate, filtered and evaporated. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 100:0->50:50 gradient). {2-[(5-Methyl-furan-2-ylmethyl)-amino]-quinolin-5-yl}-methanol was obtained as a light brown solid (105 mg, 69%), MS: m/e=269.5 (M+H+).
Reaction SMILES: [C:1]([N:8]([CH2:20][C:21]([CH3:25])([CH3:24])[CH2:22][OH:23])[C:9](=[O:19])[C@H:10]([CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[NH2:11])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].C1([CH:32]([S:39]([O:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)(=[O:41])=[O:40])[CH2:33][CH2:34][S:35](Cl)(=[O:37])=[O:36])C=CC=CC=1>N1C=CC=CC=1.ClCCl.ClCCl>[C:1]([N:8]([CH2:20][C:21]([CH3:25])([CH3:24])[CH2:22][O:23][S:35]([CH2:34][CH2:33][CH2:32][S:39]([O:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)(=[O:41])=[O:40])(=[O:36])=[O:37])[C:9](=[O:19])[C@H:10]([CH2:12][C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[NH2:11])([O:3][C:4]([CH3:5])([CH3:7])[CH3:6])=[O:2]
Reactant: O=S(=O)(Cl)CCC(c1ccccc1)S(=O)(=O)Oc1ccccc1
Reactant: CC(C)(CO)CN(C(=O)OC(C)(C)C)C(=O)[C@@H](N)Cc1ccccc1
Solvent: ClCCl
Solvent: c1ccncc1
Product: CC(C)(COS(=O)(=O)CCCS(=O)(=O)Oc1ccccc1)CN(C(=O)OC(C)(C)C)C(=O)[C@@H](N)Cc1ccccc1
Temperature: 25 °C
Reaction time: 15 h

Procedure:
To a stirred solution of 3-(N-Boc-L-phenylalaninamido)-2,2-dimethylpropanol from Step 1 (2 mmol) in a mixture of pyridine/dichloromethane (5 mL:10 mL) was added a solution of phenyl 3-phenoxysulfonyl-1-propanesulfonyl chloride (Example 1 (b)) (2.2 mmol) in dichloromethane (5 mL). The reaction mixture was stirred at room temperature for 15 h, then concentrated and rediluted with ethyl acetate and aqueous hydrochloric acid (1 N). The organic phase was isolated, washed with aqueous hydrochloric acid (1 N) and concentrated. The residual material was purified by silica gel chromatography using hexanes/ethyl acetate (70:30 to 50:50) as eluent to afford 3-phenoxysulfonyl-1-propanesulfonic acid 3-(N-Boc-L-phenylalaninamido)-2,2-dimethylpropyl ester.
Reaction SMILES: O[C:2]1[N:3]=[N:4][CH:5]=[C:6]([O:8][CH3:9])[CH:7]=1.P(Cl)(Cl)([Cl:12])=O>>[Cl:12][C:2]1[N:3]=[N:4][CH:5]=[C:6]([O:8][CH3:9])[CH:7]=1
Reactant: O=P(Cl)(Cl)Cl
Reactant: COc1cnnc(O)c1
Product: COc1cnnc(Cl)c1
Temperature: 75 °C
Reaction time: 0.03 h
Yield: 78.2 %

Procedure:
Anal. Calc. for C5H6N2O2:C, 47.62; H, 4.80;N, 22.21 Found: C, 47.60; H, 4.83;N, 22.18 E. 3-Hydroxy-5-methoxypyridazine (629.6 g, 4.99 moles) and phosphorus oxychloride (2.5 L, 27 moles) were added to a 5 L round bottomed flask equipped with a heating mantle and a mechanical stirrer. The resulting stirred slurry was rapidly heated (<30 min) to 75° C. At this temperature the heating mantle was removed. The reaction mixture continued to exotherm to a final temperature of 82.3° C. After the solids had dissolved in the darkening reaction mixture, stirring was continued an additional 2 minutes. The homogeneous reaction mixture was then rapidly cooled to room temperature with an ice/water bath. The reaction mixture was concentrated via rotary evaporator using pump vacuum and a water bath temperature of 45° C. The residue was taken up in 2 L of CH2Cl2 and slowly poured into a stirring mixture of 2 L CH2Cl2 and 6 L of H2O chilled to 10° C. The layers were separated and enough 50% NaOH was added to the aqueous phase to give a pH of 2-4. The aqueous phase was extracted with additional CH2Cl2 (2×2 L). The combined organic layers were washed with 4 L of H2O and dried (MgSO4). The solution was vacuum filtered through 1 kg of silica gel. The silica gel was washed with 4 L of ethyl acetate/hexanes (1:1). The filtrate was concentrated in-vacuo to afford 564 g (78% yield) of 3-chloro-5-methoxypyridazine as a pale yellow solid. The product was stored in a freezer to minimize decomposition. The product was recrystallized from ethyl acetate/cyclohexane to give a white solid, mp=98° C.-100° C.
Reaction SMILES: [F:1][C:2]([F:13])([F:12])[C:3]1[CH:4]=[C:5]([N:9]=[C:10]=[O:11])[CH:6]=[CH:7][CH:8]=1.[C:14]1([CH:20]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH2:21][CH2:22][NH:23][CH:24]2[CH2:29][CH2:28][N:27]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:26][CH2:25]2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>ClCCl>[C:33]([O:32][C:30]([N:27]1[CH2:26][CH2:25][CH:24]([N:23]([CH2:22][CH2:21][CH:20]([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C:10]([NH:9][C:5]2[CH:6]=[CH:7][CH:8]=[C:3]([C:2]([F:12])([F:13])[F:1])[CH:4]=2)=[O:11])[CH2:29][CH2:28]1)=[O:31])([CH3:36])([CH3:34])[CH3:35]
Reactant: O=C=Nc1cccc(C(F)(F)F)c1
Reactant: CC(C)(C)OC(=O)N1CCC(NCCC(c2ccccc2)c2ccccc2)CC1
Solvent: ClCCl
Product: CC(C)(C)OC(=O)N1CCC(N(CCC(c2ccccc2)c2ccccc2)C(=O)Nc2cccc(C(F)(F)F)c2)CC1
Reaction time: 0.75 h
Yield: 87.4 %

Procedure:
246 mg (1.32 mmol) of 3-(trifluoromethyl)phenyl isocyanate is added to a solution of tert-butyl 4-[(3,3-diphenylpropyl)amino]-1-piperidine carboxylate (470 mg, 1.2 mmol) in 5 ml of dichloromethane. The solution is agitated for 45 minutes, and the aminomethyl resin (180 mg, 0.36 mmol) is added and the reaction medium is again placed on an orbital shaker for 45 minutes. The resin is filtered and washed with dichloromethane. The filtrate is concentrated in vacuo in order to produce 610 mg (yield=87%) of a white foam.
Reaction SMILES: [Cl:1][CH2:2][C:3](Cl)=[O:4].[NH2:6][C:7]1[C:8]([I:21])=[C:9]([C:18]([Cl:20])=[O:19])[C:10]([I:17])=[C:11]([C:15]=1[I:16])[C:12]([Cl:14])=[O:13].O>CC(N(C)C)=O>[Cl:1][CH2:2][C:3]([NH:6][C:7]1[C:15]([I:16])=[C:11]([C:12]([Cl:14])=[O:13])[C:10]([I:17])=[C:9]([C:8]=1[I:21])[C:18]([Cl:20])=[O:19])=[O:4]
Reactant: O=C(Cl)CCl
Reactant: Nc1c(I)c(C(=O)Cl)c(I)c(C(=O)Cl)c1I
Solvent: O
Solvent: CC(=O)N(C)C
Product: O=C(CCl)Nc1c(I)c(C(=O)Cl)c(I)c(C(=O)Cl)c1I
Reaction time: 1 h
Yield: 75 %

Procedure:
At maximally 10° C., 67.7 g (0.6 mol) of chloroacetyl chloride is added dropwise under agitation within 20 minutes to a solution of 119.1 g (0.2 mol) of 5-amino-2,4,6-triiodoisophthalic acid dichloride in 400 ml of dimethylacetamide; the mixture is further stirred for 1 hour under ice cooling and then overnight at room temperature. The reaction mixture is then treated with 6 l of water, the thus-produced precipitate is vacuum-filtered and dissolved in 3.5 l of ethyl acetate. The ethyl acetate solution is washed neutral with 400 ml of saturated NaHCO3 solution and twice with water, dried with Na2SO4, and concentrated under vacuum. The residue is treated with 800 ml of ether and dried under vacuum at 50° C., thus obtaining 100.8 g (75% of theory) of 5-chloroacetamido-2,4,6-triiodoisophthalic acid dichloride, m.p. 254°-256° C. (decomposition).
Reaction SMILES: [C:1]([O:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])(=[O:4])[CH:2]=[CH2:3].[CH3:18][N:19]1[CH2:24][CH2:23][NH:22][CH2:21][CH2:20]1>>[CH3:18][N:19]1[CH2:24][CH2:23][N:22]([CH2:3][CH2:2][C:1]([O:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])=[O:4])[CH2:21][CH2:20]1
Reactant: C=CC(=O)OCCCCCCCCCCCC
Reactant: CN1CCNCC1
Product: CCCCCCCCCCCCOC(=O)CCN1CCN(C)CC1
Temperature: 85 °C

Procedure:
In a 40-mL scintillation vial, 12.0 g (0.05 moles) of lauryl acrylate are charged followed by the slow addition of 5.0 g (0.05 moles) of 1-methyl piperazine. The mixture is agitated using a magnetic stirrer bar and heated to 85° C. for at least 16 hours using a heating block. The final product is a light brown liquid at ambient temperature. Complete conversion is apparent from the lack of olefin protons in the 1H-NMR spectra. 1H-NMR (300 MHz, CDCl3): δ 3.83 (t, 6.6 Hz, 2H), 2.45 (t, 7.3 Hz, 2H), 2.24 (m, 10H), 2.02 (s, 3H), 1.38 (t, 6.8 Hz, 2H), 1.03 (m, 18H), 0.65 (t, 7.1 Hz, 3H). 13C-NMR (75 MHz, CDCl3): δ 171.78, 63.92, 54.64, 53.12, 52.39, 45.53, 31.93, 31.45, 29.19, 21.17, 29.12, 29.08, 28.89, 28.80, 28.20, 25.47, 22.20, 13.63.
Reaction SMILES: [I-].[CH2:2]([N+:6]1[C:10]([CH3:11])=[CH:9][S:8][C:7]=1[CH3:12])[CH2:3][CH2:4][CH3:5].[Cl:13][C:14]1[C:15]2[CH:25]=[CH:24][CH:23]=[CH:22][C:16]=2[S:17][C:18]=1[C:19](Cl)=[O:20]>C(Cl)Cl.CN(C1C=CN=CC=1)C.CS(C)=O.CO>[CH2:2]([N:6]1[C:10]([CH3:11])=[CH:9][S:8]/[C:7]/1=[CH:12]\[C:19]([C:18]1[S:17][C:16]2[CH:22]=[CH:23][CH:24]=[CH:25][C:15]=2[C:14]=1[Cl:13])=[O:20])[CH2:3][CH2:4][CH3:5]
Reactant: CCCC[n+]1c(C)csc1C
Reactant: O=C(Cl)c1sc2ccccc2c1Cl
Agent: CN(C)c1ccncc1
Agent: [I-]
Solvent: ClCCl
Solvent: CO
Solvent: CS(C)=O
Product: CCCCN1C(C)=CS/C1=C\C(=O)c1sc2ccccc2c1Cl
Temperature: 25 °C
Reaction time: 8 h

Procedure:
In a 20 mL vial a solution of 3-butyl-2,4-dimethylthiazol-3-ium iodide (47.92 mg, 0.16 mmol) dissolved in CH2Cl2 (0.5 mL) was added, followed by the addition of DMAP (49.24 mg, 0.40 mmol) dissolved in CH2Cl2 (0.8 mL). Then, to the solution was added 3-chlorobenzo[b]thiophene-2-carbonyl chloride (37.0 mg, 0.16 mmol) dissolved in CH2Cl2 (0.5 mL). The vial was capped and shaken overnight at room temperature. The residue was dissolved in 1:1 DMSO/MeOH and purified by reverse phase HPLC using a method analogous to that described in Example 53 to provide the title compound. 1H NMR (500 MHz, DMSO-d6/D2O) δ ppm 0.98 (t, 3 H) 1.39-1.48 (m, 2 H) 1.70-1.80 (m, 2 H) 2.31-2.37 (m, 3 H) 4.00-4.09 (m, 2 H) 6.67-6.70 (m, 1 H) 6.85-6.89 (m, 1 H) 7.49-7.56 (m, 2 H) 7.85-7.92 (m, 1 H) 8.01-8.07 (m, 1 H); MS (ESI) positive ion 364 (M+H).
Reaction SMILES: [I:1][C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][C:9]=2[N+:11]([O-:13])=[O:12])[NH:4][N:3]=1.C([O-])([O-])=O.[K+].[K+].Br[CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([O:28][CH3:29])[N:23]=1>CN(C=O)C>[I:1][C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][C:9]=2[N+:11]([O-:13])=[O:12])[N:4]([CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[C:24]([O:28][CH3:29])[N:23]=2)[N:3]=1
Reactant: COc1cccc(CBr)n1
Reactant: O=[N+]([O-])c1cccc2[nH]nc(I)c12
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CN(C)C=O
Product: COc1cccc(Cn2nc(I)c3c([N+](=O)[O-])cccc32)n1
Reaction time: 4 h
Yield: 80 %

Procedure:
To 3-iodo-4-nitro-1H-indazole (5.01 g, 17.3 mmol) in DMF (40 mL) was added K2CO3 (4.79 g, 34.7 mmol) and 2-(bromomethyl)-6-methoxypyridine (4.20 g, 20.8 mmol). The reaction mixture was stirred for 4 hours. The reaction mixture was concentrated to remove DMF, diluted with EtOAc and washed with H2O and brine. The organic phase was dried (Na2SO4) and concentrated. Silica gel chromatography (EtOAc/Hexane 1:5) gave the desired product (5.68 g).
Reaction SMILES: [Fe:1].[S:2](=[O:6])(=[O:5])([OH:4])[OH:3]>O>[OH2:3].[OH2:3].[OH2:3].[OH2:3].[OH2:3].[OH2:3].[OH2:3].[S:2]([O-:6])([O-:5])(=[O:4])=[O:3].[Fe+2:1]
Reactant: O=S(=O)(O)O
Reactant: [Fe]
Solvent: O
Product: O=S(=O)([O-])[O-]
Product: [Fe+2]
Reaction time: 8 h

Procedure:
Initially, iron sulfate heptahydrate was prepared from iron powder and sulfuric acid. 100 g of iron powder was added to 7.6 liters of deionized water in a 22 liter round bottomed flask. Separately, 86 ml of concentrated H2SO4 was mixed with 500 ml of deionized water to prepare a sulfuric acid solution. The sulfuric acid solution was added dropwise over a period of 2 hours to the iron powder slurry while mixing the slurry. The slurry was stirred overnight after completion of addition of the sulfuric acid solution to the slurry to form a solution of iron sulfate heptahydrate. After stirring, the solution was heated between 30-45° C. for 3 hours and gas evolution was observed. The warm iron sulfate solution was then added over a period of 1 hour to a stirred solution, under nitrogen, containing 398 g of (NH4)2MoS4 in 7.6 liters of deionized water. The iron sulfate solution was added to the (NH4)2MoS4 solution by pumping the iron sulfate solution through a 2.75″×0.020″ outer diameter injector nozzle immersed in the (NH4)2MoS4 solution. After addition of the iron sulfate solution to the (NH4)2MoS4 solution was completed, the mixture was stirred under nitrogen at ambient temperature (28° C.) for a period of 2 hours. The mixture was then allowed to settle overnight. The solids were then separated from the mixture using a continuous centrifuge. The separated solids were washed with deionized water, then dried by azeotropic distillation. 526 grams of solid catalyst was recovered. Semi-quantitative fluorometry (XRF) indicated that the catalyst contained, on a mass % basis, 17.6% Fe, 37.8% Mo, 44.5% S, and 0.04% Ni. The catalyst material was particulate and had a particle size distribution with a mean particle size of 213 μm as determined by laser diffractometry using a Mastersizer S made by Malvern Instruments. The BET surface area of the catalyst was measured and found to be 301 m2/g. The pore volume of the catalyst was found to be 0.311 cm3/g and the mean pore diameter was found to be from 20 to 150 angstroms. X-ray diffraction and Raman IR spectroscopy confirmed that at least a portion of the catalyst had a iron tetrathiomolybdate structure in which iron, sulfur, and molybdenum were arranged as shown in Formula (IX) above.