Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [O:1]=[C:2]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:3][NH:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8].[C:18]([O-])(O)=[O:19].[Na+].C=O.[Na+].[Cl-]>CCO>[OH:19][CH2:18][CH:3]([NH:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:8])[CH3:9])[C:2](=[O:1])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
Reactant: CC(C)(C)OC(=O)NCC(=O)c1ccccc1
Reactant: O=C([O-])O
Agent: C=O
Agent: [Cl-]
Agent: [Na+]
Solvent: CCO
Product: CC(C)(C)OC(=O)NC(CO)C(=O)c1ccccc1
Temperature: 25 °C
Reaction time: 144 h
Yield: 173.4 %

Procedure:
tert-butyl 1-oxo-1-phenylethan-2-ylcarbamate (18) (2.4 g, 10.0 mmol, 1.0 equiv.) was added to a 100 mL RBF followed by EtOH (41 mL, 200 proof). Next, a 0.5 M solution of NaHCO3 (420 mg, 5.0 mmol, 0.5 equiv.) was added followed by a 37% solution of formaldehyde (1.2 mL, 15.0 mmol, 1.5 equiv.). The solution was stirred at rt. for 6 days and transferred to a separatory funnel with a 1.0 M solution of NaCl (5.0 g, 85.5 mmol). The solution was extracted with CH2Cl2 (5×50 mL). The organic layer was dried over Na2SO4, concentrated on a rotary evaporator, and dried under vacuum to give a crude light yellow oil. The residue was purified by flash column chromatography (30% EtOAc/hexanes) to give 2.3 g (88%) of 19 as a colorless oil which crystallized to a white solid. (Note: It is essential to use a 100 mL RBF for full vortex stirring over the entire reaction period) Rf=0.16 (30% EtOAc/Hexanes); mp=69-71° C.; IR (film) 3420, 2976, 2931, 1683, 1503, 1366, 1165, 1061 cm−1; 1H NMR (500 MHz, CDCl3) δ 8.00 (d, J=7.0 Hz, 2H, Ph-H), 7.60 (t, J=7.0 Hz, 1H, Ph-H), 7.48 (t, J=7.0 Hz, 2H, Ph-H), 5.96 (d, J=6.0 Hz, 1H, carbamate-NH), 5.36 (br s, 1H, Boc-NH—CH), 4.00 (m, 1H, CH—CH2), 3.86 (m, 1H, CH—CH2), 3.29 (br s, 1H, CH2—OH), 1.45 (s, 9H, t-butyl-CH3); 13C (125 MHz, CDCl3) δ 197.4, 156.3, 134.6, 134.1, 129.0, 128.9, 80.5, 64.7, 58.1, 28.4; LRMS (ESI-MS m/z): Mass calcd for C14H19NNaO4 [M+Na]+, 288.29. Found 288. Anal. calcd for C14H19NO4: C, 63.38; H, 7.22; N, 5.28. Found: C, 63.22; H, 7.25; N, 5.28.
Reaction SMILES: [CH3:1][C:2](C)([O-:4])C.[K+].[Cl-].[CH3:8]OC[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:30][C:31]1[CH:32]=[C:33]([C:48]2[S:52][C:51](C=O)=[N:50][CH:49]=2)[CH:34]=[C:35]([NH:37][C:38]2[N:43]=[C:42]([C:44]([F:47])([F:46])[F:45])[CH:41]=[CH:40][N:39]=2)[CH:36]=1>O1CCCC1>[CH3:8][O:4]/[CH:2]=[CH:1]/[C:51]1[S:52][C:48]([C:33]2[CH:34]=[C:35]([NH:37][C:38]3[N:43]=[C:42]([C:44]([F:46])([F:45])[F:47])[CH:41]=[CH:40][N:39]=3)[CH:36]=[C:31]([CH3:30])[CH:32]=2)=[CH:49][N:50]=1
Reactant: Cc1cc(Nc2nccc(C(F)(F)F)n2)cc(-c2cnc(C=O)s2)c1
Reactant: CC(C)(C)[O-]
Reactant: COC[P+](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: [Cl-]
Agent: [K+]
Solvent: C1CCOC1
Product: CO/C=C/c1ncc(-c2cc(C)cc(Nc3nccc(C(F)(F)F)n3)c2)s1
Temperature: 0 °C
Reaction time: 0.33 h
Yield: 19.7 %

Procedure:
A solution of potassium tert-butoxide (429 mg, 3.82 mmol) in tetrahydrofuran (2 ml) was added dropwise to a cooled −78° C. solution of (methoxymethyl)triphenylphosphonium chloride (1.31 g, 3.82 mmol) in tetrahydrofuran (6 ml). The mixture was warmed to 0° C. and stirred for 20 minutes. A solution of the product of Step 1 (464 mg, 1.27 mmol) in THF (4 ml) was then added, and the resulting mixture was stirred at 0° C. for 1 hour and then warmed to room temperature and stirred overnight. The mixture was then partitioned between saturated aqueous ammonium chloride and ethyl acetate. The layers were separated and the aqueous layer was extracted once more with ethyl acetate. The combined organics were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Purification via silica gel chromatography (ethyl acetate/hexanes) afforded N-(3-{2-[(E)-2-methoxyethenyl]-1,3-thiazol-5-yl}-5-methylphenyl)-4-(trifluoromethyl)pyrimidin-2-amine (98 mg, 0.25 mmol, 19% yield) as a yellow solid. MS ESI: [M+H]+ m/z 393.1. 1H NMR (500 MHz, DMSO-d6) δ 10.23 (s, 1H), 8.80 (d, J=4.0 Hz, 1H), 7.91 (s, 1H), 7.90 (s, 1H), 7.56 (d, J=10.5 Hz, 1H), 7.41 (s, 1H), 7.26 (d, J=4.0 Hz, 1H), 7.11 (s, 1H), 6.14 (d, J=10.5 Hz, 1H), 3.69 (s, 3H), 2.28 (s, 3H). rhSYK activity=+++
Reaction SMILES: [N:1]1([C:7]2[CH:8]=[C:9]3[C:14](=[CH:15][CH:16]=2)[NH:13][C:12](=[O:17])[CH2:11][CH2:10]3)[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.CN(C=O)C.C(=O)([O-])[O-].[K+].[K+].[CH2:29](Br)[CH:30]=[CH2:31]>O>[CH2:31]([N:4]1[CH2:5][CH2:6][N:1]([C:7]2[CH:8]=[C:9]3[C:14](=[CH:15][CH:16]=2)[NH:13][C:12](=[O:17])[CH2:11][CH2:10]3)[CH2:2][CH2:3]1)[CH:30]=[CH2:29]
Reactant: C=CCBr
Reactant: O=C1CCc2cc(N3CCNCC3)ccc2N1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CN(C)C=O
Product: C=CCN1CCN(c2ccc3c(c2)CCC(=O)N3)CC1
Temperature: 25 °C
Reaction time: 2 h
Yield: 38.3 %

Procedure:
To a mixture of 1 g of 6-(1-piperazinyl)-3,4-dihydrocarbostyril, 15 ml of DMF and 1.82 g of potassium carbonate was added 500 mg of allyl bromide and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into a large amount of water and extracted with chloroform. After washing with water, the extract was dried over anhydrous sodium sulfate. Then, chloroform was distilled off and the residue was purified through silica gel column chromatography and recrystallized from chloroform-ether to give 0.43 g of 6-(4-allyl-1-piperazinyl)-3,4-dihydrocarbostyril, m.p. 175°-176° C., colorless scales.
Reaction SMILES: [CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7]([NH2:10])=[CH:6][CH:5]=1.N1C=CC=CC=1.[Br:18][CH:19]([CH3:23])[C:20](Br)=[O:21]>C1(C)C=CC=CC=1.O>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:20](=[O:21])[CH:19]([Br:18])[CH3:23])=[CH:6][CH:5]=1
Reactant: CC(Br)C(=O)Br
Reactant: COC(=O)c1ccc(N)cc1
Solvent: c1ccncc1
Solvent: Cc1ccccc1
Solvent: O
Product: COC(=O)c1ccc(NC(=O)C(C)Br)cc1

Procedure:
To a solution of 1.1 g of 4-Amino-benzoic acid methyl ester in 17 ml of toluene were added 2.2 ml of pyridine and 1.5 g of 2-Bromo-propionyl bromide at room temperature. After 16 h the reaction mixture was diluted with water and filtered through a chem Elut® cartridge by eluting with ethyl acetate. The solvents were removed under reduced pressure and the crude product was purified by chromatography on silica gel eluting with a gradient of n-heptane/ethyl acetate. The fractions containing the product were combined and the solvent evaporated under reduced pressure. Yield: 2 g.
Reaction SMILES: [CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C@H:8]1[C@@H:12]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[CH3:19])[NH:11][C:10](=[S:20])[NH:9]1.[CH3:21][I:22]>CCO>[IH:22].[CH3:19][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=1[C@H:12]1[C@@H:8]([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[CH3:1])[NH:9][C:10]([S:20][CH3:21])=[N:11]1
Reactant: Cc1ccccc1[C@H]1NC(=S)N[C@H]1c1ccccc1C
Reactant: CI
Solvent: CCO
Product: CSC1=N[C@@H](c2ccccc2C)[C@@H](c2ccccc2C)N1
Product: I
Temperature: 25 °C
Yield: 96.3 %

Procedure:
A mixture of cis-4,5-bis-(2-methylphenyl)imidazolidine-2-thione (29) (6.08 g, 0.0215 mol) and methyl iodide (2.01 mL, 0.0323 mol) in abs. EtOH (50 mL) is heated at 85° C. overnight. The reaction mixture is cooled to rt, concentrated in vacuo, and the residue suspended in Et2O. The insoluble material is filtered to give 8.79 g of the product 46. 1H NMR (DMSO-d6) δ 10.67 (s, 2H), 7.10-6.90 (m, 8H), 6.02 (s, 2H), 2.79 (s, 3H), 2.16 (s, 6H); MS: m/z 297 (M++1).
Reaction SMILES: Cl[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[N:5]=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].[CH2:15]([O:17][CH:18]([O:21][CH2:22][CH3:23])[CH2:19][NH2:20])[CH3:16].C(N(CC)CC)C>ClCCl>[CH2:15]([O:17][CH:18]([O:21][CH2:22][CH3:23])[CH2:19][NH:20][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[N:5]=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13])[CH3:16]
Reactant: CCOC(CN)OCC
Reactant: O=[N+]([O-])c1cnc2ccccc2c1Cl
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: CCOC(CNc1c([N+](=O)[O-])cnc2ccccc12)OCC
Yield: 97.3 %

Procedure:
The general method described in Step 1 of Example 1 was used to react 4-chloro-3-nitroquinoline (20.9 g, 100 mmol), aminoacetaldehyde diethyl acetal (14.4 g, 110 mmol), and triethylamine (12.6 g, 125 mmol) in dichloromethane for 15 hours to provide (2,2-diethoxyethyl)-(3-nitroquinolin-4-yl)amine (29.7 g) as a yellow solid.
Reaction SMILES: [N:1]1[CH:6]=[CH:5][C:4]([CH2:7][C:8]([CH2:19][C:20]2[CH:25]=[CH:24][N:23]=[CH:22][CH:21]=2)([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[O:17][CH3:18])[C:9]#N)=[CH:3][CH:2]=1.[OH-:26].[K+].[Cl-].C(O)C[OH:31]>O>[N:1]1[CH:2]=[CH:3][C:4]([CH2:7][C:8]([CH2:19][C:20]2[CH:21]=[CH:22][N:23]=[CH:24][CH:25]=2)([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[O:17][CH3:18])[C:9]([OH:31])=[O:26])=[CH:5][CH:6]=1
Reactant: [OH-]
Reactant: OCCO
Reactant: COc1ccccc1C(C#N)(Cc1ccncc1)Cc1ccncc1
Agent: [Cl-]
Agent: [K+]
Solvent: O
Product: COc1ccccc1C(Cc1ccncc1)(Cc1ccncc1)C(=O)O
Temperature: 25 °C
Yield: 50 %

Procedure:
To a solution of α,α-Bis(4-pyridinylmethyl)- 2-methoxybenzeneacetonitrile (14.36 g, 43.6 nmol) in ethylene glycol (100 ml), was added KOH (40 ml of a saturated solution) and the mixture was heated at 120°-130° under nitrogen for 20 h. The solution was cooled to room temperature, diluted with 200 ml water, and neutralized with aqueous anmonium chloride to about pH 7. The mixture was extracted with chloroform: isopropanol (4:1) until complete by TLC. The ccrbined extraRs were washed with brine, dried over sodium sulfate, and evaporated (rotary evaporator). The solid was dried in a vacuum oven at 50° and 5 torr to give 7.7 g, 22 mmol, 50% yield of α,α-bis(4-pyridinylmethyl)-2-methoxybenzeneacetic acid as a white powder.
Reaction SMILES: C([Li])CCC.[Br-].[CH3:7][N:8]([CH3:30])[CH2:9][CH2:10][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[O:31]([CH2:38][CH2:39][N:40]1[CH2:45][CH2:44][C:43](=O)[CH2:42][CH2:41]1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[ClH:47]>C1COCC1.CCOCC>[ClH:47].[ClH:47].[CH3:7][N:8]([CH3:30])[CH2:9][CH:10]=[C:43]1[CH2:44][CH2:45][N:40]([CH2:39][CH2:38][O:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH2:41][CH2:42]1
Reactant: CN(C)CC[P+](c1ccccc1)(c1ccccc1)c1ccccc1
Reactant: O=C1CCN(CCOc2ccccc2)CC1
Agent: Cl
Agent: [Br-]
Agent: [Li]CCCC
Solvent: CCOCC
Solvent: C1CCOC1
Product: CN(C)CC=C1CCN(CCOc2ccccc2)CC1
Temperature: 0 °C
Reaction time: 0.5 h

Procedure:
n-Butyllithium (9.13 ml, 2.5M solution in hexanes) was added to a suspension of (2-dimethylaminoethyl)triphenylphosphonium bromide (9.46 g) in dry THF (60 ml) under nitrogen at 0° C. over 5 minutes. The mixture was stirred at 0° C. for 30 minutes and then 1-(2-phenoxyethyl)-4-piperidone (5.0 g) in THF (15 ml) was added dropwise over 5 minutes. The mixture was warmed to ambient temperature and then heated at 60° C. for 5 hours. The mixture was left at ambient temperature for 18 hours and then quenched with water and diluted with ethyl acetate. 2M Hydrochloric acid was added and the mixture was separated. The organic layer was extracted with 2M hydrochloric acid and the combined acidic layers were basified and extracted with dichloromethane to give an oil. The oil was purified by flash column chromatography on silica using dichloromethane and then dichloromethane/methanol (1:1) as the mobile phase. The oil obtained after chromatography was dissolved in ether and treated with ethereal hydrogen chloride. The ether was decanted off and the residual semi-solid was triturated with acetone/ether (1:1) and filtered to give a solid which was recrystallised from IMS to give 4-(2-dimethylaminoethylidene)-1-(2-phenoxyethyl)piperidine dihydrochloride, m.p. 234°-235° C.
Reaction SMILES: [H-].[Na+].[Br:3][C:4]1[CH:16]=[CH:15][C:7]([CH2:8][N:9]2[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]2)=[C:6](F)[CH:5]=1.C(NC([O:23][CH2:24][CH3:25])=O)C>O1CCOCC1.O>[Br:3][C:4]1[CH:16]=[CH:15][C:7]([CH2:8][N:9]2[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]2)=[C:6]([O:23][CH2:24][CH3:25])[CH:5]=1
Reactant: Fc1cc(Br)ccc1CN1CCCCC1
Reactant: CCNC(=O)OCC
Agent: [H-]
Agent: [Na+]
Solvent: O
Solvent: C1COCCO1
Product: CCOc1cc(Br)ccc1CN1CCCCC1
Temperature: 140 °C
Yield: 73.4 %

Procedure:
Sodium hydride (306 mg, 60%, 7.6 mmol) was added in portions to a solution of 1-(4-bromo-2-fluorobenzyl)-piperidine (520 mg, 1.9 mmol) and ethyl urethane (0.91 mL, 7.6 mmol) in dioxane (10 mL) under an atmosphere of nitrogen. The reaction mixture was then sonicated for 30 minutes until gas evolution ceased then heated at 140° C. overnight in a sealed tube. The reaction mixture was diluted with water and extracted with DCM (3×30 mL). The combined organic layer was dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to afford a colourless oil that was then purified by flash chromatography (silica, 12 g column, ISCO, 0-10% methanol in DCM) to afford the title compound as a white solid (416 mg, 74%). 1H NMR (CDCl3, 400 MHz): 7.23 (d, J=8.1 Hz, 1H), 7.03 (dd, J=8.1, 1.9 Hz, 1H), 6.95 (d, J=1.9 Hz, 1H), 3.99 (q, J=7.0 Hz, 2H), 3.47 (s, 2H), 2.46-2.35 (m, 4H), 1.61-1.53 (m, 4H), 1.45-1.36 (m, 5H).
Reaction SMILES: [SH:1][C:2]1[N:7]2[N:8]=[C:9]([CH2:11][O:12][CH3:13])[N:10]=[C:6]2[N:5]=[C:4]([CH3:14])[CH:3]=1.CC(O[CH2:19][C:20]1[CH2:29][S:28][C@@H:23]2[C@H:24]([NH2:27])[C:25](=[O:26])[N:22]2[C:21]=1[C:30]([OH:32])=[O:31])=O.O.N>C(#N)C>[NH2:27][CH:24]1[C:25](=[O:26])[N:22]2[C:21]([C:30]([OH:32])=[O:31])=[C:20]([CH2:19][S:1][C:2]3[N:7]4[N:8]=[C:9]([CH2:11][O:12][CH3:13])[N:10]=[C:6]4[N:5]=[C:4]([CH3:14])[CH:3]=3)[CH2:29][S:28][C@H:23]12
Reactant: CC(=O)OCC1=C(C(=O)O)N2C(=O)[C@@H](N)[C@H]2SC1
Reactant: COCc1nc2nc(C)cc(S)n2n1
Agent: N
Solvent: O
Solvent: CC#N
Product: COCc1nc2nc(C)cc(SCC3=C(C(=O)O)N4C(=O)C(N)[C@H]4SC3)n2n1
Temperature: 25 °C
Reaction time: 6 h
Yield: 49.7 %

Procedure:
In 600 ml of acetonitrile were suspended 30.1 g of 7-mercapto-2-methoxymethyl-5-methyl-s-triazolo[1,5-a]pyrimidine and 38.9 g of 7-aminocephalosporanic acid and 68.7 ml of boron trifluoride - ethyl ether complex was added thereto, and the mixture was stirred at room temperature for 6 hours. One liter of water was added to the reaction mixture and the mixture was adjusted to pH 2 with addition of a conc. aqueous ammonia. The precipitated crystals were collected by filtration, washed with water and with acetone, and then dried to obtain 30 g of the title compound.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:12]2[CH2:13][CH2:14][NH:15][CH2:16][CH:17]=2)[CH:6]=[CH:7][C:8]=1[N+:9]([O-:11])=[O:10].Cl.[C:19]([O:23][C:24]([N:26]1[CH2:31][CH2:30][N:29]([C:32](=[O:35])[CH2:33]Br)[CH2:28][CH2:27]1)=[O:25])([CH3:22])([CH3:21])[CH3:20].C(=O)([O-])[O-].[Cs+].[Cs+].C(#N)C>O>[C:19]([O:23][C:24]([N:26]1[CH2:27][CH2:28][N:29]([C:32](=[O:35])[CH2:33][N:15]2[CH2:14][CH:13]=[C:12]([C:5]3[CH:6]=[CH:7][C:8]([N+:9]([O-:11])=[O:10])=[C:3]([O:2][CH3:1])[CH:4]=3)[CH2:17][CH2:16]2)[CH2:30][CH2:31]1)=[O:25])([CH3:22])([CH3:20])[CH3:21]
Reactant: CC(C)(C)OC(=O)N1CCN(C(=O)CBr)CC1
Reactant: COc1cc(C2=CCNCC2)ccc1[N+](=O)[O-]
Agent: Cl
Agent: O=C([O-])[O-]
Agent: [Cs+]
Solvent: CC#N
Solvent: O
Product: COc1cc(C2=CCN(CC(=O)N3CCN(C(=O)OC(C)(C)C)CC3)CC2)ccc1[N+](=O)[O-]
Temperature: 25 °C
Reaction time: 8 h

Procedure:
Into a 1-Neck round-bottom flask was added 4-(3-Methoxy-4-nitro-phenyl)-1,2,3,6-tetrahydro-pyridine; hydrochloride (364 mg, 1.34 mmol) (generated by 4N HCl treatment of the 450 mg of BOC precursor for 1 h), 4-(2-Bromo-acetyl)-piperazine-1-carboxylic acid tert-butyl ester (413.0 mg, 1.345 mmol) and cesium carbonate (1095 mg, 3.362 mmol) in acetonitrile (10 mL, 200 mmol). The reaction was stirred overnight at reflux. The reaction mixture was cooled to RT, diluted with water and was extracted (twice) from EtOAc. Combined organic was washed with brine and was dried over MgSO4. After solvent evaporation and flash chromatography (ISCO, EtOAC: MeOH 98:2), the product, 4-{2-[4-(3-Methoxy-4-nitro-phenyl)-3,6-dihydro-2H-pyridin-1-yl]-acetyl}-piperazine-1-carboxylic acid tert-butyl ester, was isolated as a gum/solid (301 mg, 49%). NMR 1H (DMSO-d6)-7.86 (d, 1H, J=8.54 Hz), 7.29 (s, 1H), 7.17 (d, 1H, J=8.58 Hz), 6.44 (s, 1H), 3.96 (s, 3H), 3.52 (br s, 2H), 3.44 (br s, 2H), 3.32 m with the water peak, 8H), 3.30 (m, 2H).
Reaction SMILES: [CH3:1][O:2][C:3]1[C:7](=[CH:8][C:9]2[NH:10][C:11]([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])=[CH:12][CH:13]=2)[NH:6][C:5](=[O:25])[CH:4]=1.CS(O)(=O)=O.O>C(O)CCCC.O1CCOCC1>[CH2:1]([O:2][C:3]1[C:7](=[CH:8][C:9]2[NH:10][C:11]([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])=[CH:12][CH:13]=2)[NH:6][C:5](=[O:25])[CH:4]=1)[CH2:7][CH2:3][CH2:4][CH3:5]
Reactant: CCCCCCCCCCCc1ccc(C=C2NC(=O)C=C2OC)[nH]1
Agent: CS(=O)(=O)O
Solvent: O
Solvent: C1COCCO1
Solvent: CCCCCO
Product: CCCCCCCCCCCc1ccc(C=C2NC(=O)C=C2OCCCCC)[nH]1
Temperature: 25 °C
Reaction time: 6 h
Yield: 90 %

Procedure:
A solution of 4-methoxy-5-(5-undecyl-1H-pyrrol-2-yl-methylene)-1,5-dihydro-pyrrol-2-one (190 mg; 1 mmol) in amyl alcohol (4.75 ml) and dioxane (4.75 ml) is treated with 0.25 N methansulphonic acid in dioxane (1 ml) and stirred at room temperature under nitrogen atmosphere for 6 hours. The mixture is then poured into water (50 ml) and extracted with ethyl acetate (3×30 ml). The organic phase is shaken with brine, dried over sodium sulphate and evaporated to dryness. The crude material is purified on silica gel eluting with ethyl acetate/methanol 98/2 to give 4-amyloxy-5-(5-undecyl-1H-pyrrol-2-yl-methylene)-1,5-dihydro-pyrrol-2-one (110 mg; 0.45 mmols). Yield: 45%.
Reaction SMILES: C(O[C:6](=O)[N:7]([CH2:9][C:10]1[CH:14]=[C:13]([S:15][C:16]2[CH:17]=[N:18][C:19]([Cl:22])=[CH:20][CH:21]=2)[N:12]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[Cl:29])[N:11]=1)C)(C)(C)C.C(OCC)(=O)C.Cl>C(OCC)(=O)C.CO>[ClH:22].[Cl:29][C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=1[N:12]1[C:13]([S:15][C:16]2[CH:17]=[N:18][C:19]([Cl:22])=[CH:20][CH:21]=2)=[CH:14][C:10]([CH2:9][NH:7][CH3:6])=[N:11]1
Reactant: CN(Cc1cc(Sc2ccc(Cl)nc2)n(-c2ccccc2Cl)n1)C(=O)OC(C)(C)C
Agent: Cl
Solvent: CO
Solvent: CCOC(C)=O
Product: CNCc1cc(Sc2ccc(Cl)nc2)n(-c2ccccc2Cl)n1
Temperature: 25 °C
Reaction time: 3 h
Yield: 166.8 %

Procedure:
tert-Butyl({1-(2-chlorophenyl)-5-[(6-chloropyridin-3-yl)thio]-1H-pyrazol-3-yl}methyl)methylcarbamate (350 mg) was dissolved in ethyl acetate (3 mL) and methanol (2 mL), 4 mol/L hydrogen chloride-ethyl acetate solution (5 mL) was added and the mixture was stirred at room temperature for 3 hr. The reaction mixture was concentrated under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane, and recrystallized from a mixed solvent of ethyl acetate and ethanol to give the title compound as colorless crystals (yield 252 mg, 83%).
Reaction SMILES: Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH:8]=[CH2:9].[OH:10][C:11]1[CH:20]=[CH:19][C:14]([C:15]([O:17][CH3:18])=[O:16])=[CH:13][CH:12]=1.C(=O)([O-])[O-].[K+].[K+]>CC(=O)CC>[CH2:2]([O:10][C:11]1[CH:12]=[CH:13][C:14]([C:15]([O:17][CH3:18])=[O:16])=[CH:19][CH:20]=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH:8]=[CH2:9]
Reactant: C=CCCCCCCBr
Reactant: COC(=O)c1ccc(O)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CCC(C)=O
Product: C=CCCCCCCOc1ccc(C(=O)OC)cc1
Yield: 68.6 %

Procedure:
5.2 g of 8-bromooctene, 5.0 g of methyl 4-hydroxybenzoate and 14 g of potassium carbonate were added to 70 ml of 2-butanone, and the mixture was refluxed for 7 hours in an atmosphere of argon. After the solid matters formed therein were filtered off, the solvent was distilled off under reduced pressure. The residue was purified by a silica gel column chromatography, to obtain 4.9 g of compound (8) (Yield: 68%)
Reaction SMILES: [Si:1]([Cl:5])(Cl)([Cl:3])[Cl:2].[CH3:6][Si:7]([CH3:14])([CH3:13])[NH:8][Si](C)(C)C>>[Cl:2][Si:1]([Cl:5])([Cl:3])[NH:8][Si:7]([CH3:14])([CH3:13])[CH3:6]
Reactant: C[Si](C)(C)N[Si](C)(C)C
Reactant: Cl[Si](Cl)(Cl)Cl
Product: C[Si](C)(C)N[Si](Cl)(Cl)Cl
Temperature: 25 °C
Reaction time: 20 h
Yield: 91 %

Procedure:
70 g of silicon tetrachloride (0.41 mol) and 12.5 g of hexamethyldisilazane (0.08 mol) were brought together in a 250 ml three-necked flask and stirred at room temperature for 20 hours. Subsequent fractional distillation in a short Vigreux column yielded 16.2 g (92%) of 1,1,1-trichloro-3,3,3-trimethyldisilazane as a colourless liquid.
Reaction SMILES: [CH3:1][N:2]([C:19]([F:35])([F:34])[C:20]1[CH:25]=[CH:24][C:23]([C:26]2[CH:31]=[CH:30][C:29]([CH2:32]Cl)=[CH:28][CH:27]=2)=[CH:22][CH:21]=1)[S:3]([C:6]([F:18])([F:17])[C:7]([F:16])([F:15])[C:8]([F:14])([F:13])[C:9]([F:12])([F:11])[F:10])(=[O:5])=[O:4].NC(N)=[S:38].[OH-].[Na+].Cl>C(C(C)=O)C.C(Cl)Cl.O>[CH3:1][N:2]([C:19]([F:35])([F:34])[C:20]1[CH:25]=[CH:24][C:23]([C:26]2[CH:31]=[CH:30][C:29]([CH2:32][SH:38])=[CH:28][CH:27]=2)=[CH:22][CH:21]=1)[S:3]([C:6]([F:18])([F:17])[C:7]([F:16])([F:15])[C:8]([F:14])([F:13])[C:9]([F:12])([F:11])[F:10])(=[O:5])=[O:4]
Reactant: CN(C(F)(F)c1ccc(-c2ccc(CCl)cc2)cc1)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
Reactant: NC(N)=S
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: ClCCl
Solvent: CCC(C)=O
Product: CN(C(F)(F)c1ccc(-c2ccc(CS)cc2)cc1)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F

Procedure:
A mixture of 10.5 g (0.02 mol) of 4-(N-methylperfluorobutanesulfonamidomethyl)-4′-chloromethylbiphenyl, and 1.90 g (0.024 mol) thiourea in 100 mL methyl ethyl ketone was stirred and heated at reflux. The initial solution became cloudy and by 1 hr a white precipitate formed. The mixture was heated for 17 hr, cooled, and filtered. The product (8.2 g) was heated in 150 mL boiling ethanol under N2 and treated with 8 g (0.1 mol) 50% NaOH and heated for 20 hr. The resulting hazy solution was cooled, treated with 20 mL 10% HCl, and poured into 200 mL water to give a white solid. This was taken up in methylene chloride, dried over MgSO4, and stripped to 7.0 g of the desired product.
Reaction SMILES: [CH2:1]1[O:3][C@@H:2]1[CH2:4][OH:5].C(N(CC)CC)C.[Si:13](Cl)([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]>ClCCl.CN(C1C=CN=CC=1)C>[CH2:4]([O:5][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14])[C@H:2]1[O:3][CH2:1]1
Reactant: CC(C)(C)[Si](C)(C)Cl
Reactant: OC[C@@H]1CO1
Agent: CN(C)c1ccncc1
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: CC(C)(C)[Si](C)(C)OC[C@@H]1CO1
Temperature: 0 °C
Reaction time: 5 h
Yield: 81 %

Procedure:
To a solution of (R)-glycidol (5 g, 67.5 mmol) in dry dichloromethane containing triethylamine (10.3 ml, 74 mmol) cooled down to 0° C., was added a solution of tert-butyldimethylsilyl chloride (11.2 g, 74 mmol) in dry dichloromethane (30 ml). Then DMAP (0.33 g, 2.7 mmol) was added. The mixture was allowed to warm up to room temperature and stirred for 5 hours. The triethylammonium chloride crystals were filtered out and washed with dichloromethane (2×10 ml). The organic solution was washed with brine (2×50 ml) and dried over anhydrous sodium sulfate. The solution was concentrated and passed though a short silica gel column to remove polar impurities, and eluted with hexane/ethyl acetate (3:2). After removing the solvent, a colourless oil was collected and dried in vacuo to provide pure (S)-glycidyl-tert-butyldimethylsilyl ether (10.3 g, 81.2%).
Reaction SMILES: [C:1]1([C:7]2[N:8]=[N:9][NH:10][C:11]=2[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][OH:28].C(=O)([O-])[O-].[K+].[K+]>CC(=O)CC>[OH:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][N:9]1[N:8]=[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:11]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[N:10]1
Reactant: OCCCCCCCCCBr
Reactant: c1ccc(-c2nn[nH]c2-c2ccccc2)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CCC(C)=O
Product: OCCCCCCCCCn1nc(-c2ccccc2)c(-c2ccccc2)n1

Procedure:
4,5-Diphenyl-1,2,3-triazole was treated with 9-bromononan-1-ol and potassium carbonate in butanone to give after chromatography the title compound as a light brown oil. Found: C, 76.0; H, 8.2; N, 11.2% C23H29N30 requires: C, 76.0; H, 8.0; N, 11.6%.