Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][N:2]([CH2:6][CH2:7][O:8][C:9]1[CH:18]=[CH:17][CH:16]=[C:15]2[C:10]=1[C:11](=O)[NH:12][CH:13]=[N:14]2)[C:3](=[O:5])[CH3:4].C(N(C(C)C)CC)(C)C.P(Cl)(Cl)([Cl:31])=O.C(=O)([O-])O.[Na+]>C(Cl)Cl>[Cl:31][C:11]1[C:10]2[C:15](=[CH:16][CH:17]=[CH:18][C:9]=2[O:8][CH2:7][CH2:6][N:2]([CH3:1])[C:3](=[O:5])[CH3:4])[N:14]=[CH:13][N:12]=1
Reactant: CC(=O)N(C)CCOc1cccc2nc[nH]c(=O)c12
Reactant: O=P(Cl)(Cl)Cl
Agent: O=C([O-])O
Agent: [Na+]
Solvent: ClCCl
Solvent: CCN(C(C)C)C(C)C
Product: CC(=O)N(C)CCOc1cccc2ncnc(Cl)c12
Temperature: 0 °C
Reaction time: 2 h
Yield: 32.2 %

Procedure:
N-Methyl-N-{2-[(4-oxo-3,4-dihydroquinazolin-5-yl)oxy]ethyl}acetamide (261 mg, 1.00 mmol) and diiso-propylethylamine (522 μl, 3.00 mmol) were dissolved in DCM (25 ml), and the mixture cooled to 0° C. Phosphorus oxychloride (930 μl, 10 mmol) was added drop wise; the solution was warmed to ambient temperature and stirred for 2 hours. The mixture was cooled to 0° C., and saturated sodium hydrogen carbonate solution (30 ml) was added with vigorous stirring. The stirred mixture was allowed to warm to ambient temperature over 20 minutes. The DCM layer was separated, washed with saturated sodium hydrogen carbonate solution (30 ml), water (30 ml) and brine (30 ml), filtered through a silicone-treated filter paper, and evaporated to give N-{2-[(4-chloroquinazolin-5-yl)oxy]ethyl}-N-methylacetamide as an orange solid (90 mg, 32%); NMR Spectrum (DMSO-d6, 400 MHz, CDCl3) 2.05 (s, 3H), 3.17 (s, 3H), 3.85 (t, 2H), 4.28 (t, 2H), 6.99 (d, 1H), 7.58 (d, 1H), 7.76 (dd, 1H), 8.87 (s, 1H); Mass spectrum 276.4 MH+ (4-OMe derivative—product quenched with MeOH in instrument).
Reaction SMILES: [C:1]([C@@H:3]([NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[CH3:4])#[N:2].C(N(CC)CC)C.[NH2:20][OH:21]>C(O)C>[NH2:2]/[C:1](=[N:20]\[OH:21])/[C@@H:3]([NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[CH3:4]
Reactant: C[C@@H](C#N)NC(=O)OC(C)(C)C
Reactant: NO
Solvent: CCN(CC)CC
Solvent: CCO
Product: C[C@H](NC(=O)OC(C)(C)C)/C(N)=N/O
Temperature: 50 °C
Reaction time: 8 h
Yield: 98.4 %

Procedure:
To a mixture of tert-butyl [(1S)-1-cyanoethyl]carbamate (Step 2, 250 mg, 1.5 mmol) in ethanol (3 mL) were added triethylamine (0.41 mL, 2.9 mmol) and hydroxylamine (58 mg, 1.8 mmol). The mixture was stirred at 50° C. overnight. The reaction mixture was concentrated to afford the desired crude product (300 mg) which was directly used in the next step reaction without further purification. 1H-NMR (300 MHz, DMSO-d6): 8.94 (s, 1H), 6.80 (d, J=8.5 Hz, 1H), 5.24 (s, 2H), 4.01 (m, 1H), 1.36 (s, 9H), 1.15 (d, J=7.0 Hz, 3H).
Reaction SMILES: [H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl:7][C:8]1[CH:9]=[C:10]([C:20](OCC)=[O:21])[C:11](=[CH:18][CH:19]=1)[CH2:12][C:13](OCC)=[O:14].O>CCOCC>[Cl:7][C:8]1[CH:9]=[C:10]([CH2:20][OH:21])[C:11]([CH2:12][CH2:13][OH:14])=[CH:18][CH:19]=1
Reactant: CCOC(=O)Cc1ccc(Cl)cc1C(=O)OCC
Agent: [Al+3]
Agent: [H-]
Agent: [Li+]
Solvent: O
Solvent: CCOCC
Product: OCCc1ccc(Cl)cc1CO
Yield: 87 %

Procedure:
Lithium aluminium hydride (12 g) was suspended in dry ether (500 ml). A solution of diethyl 4-chlorohomophthalate (75 g) in ether (200 ml) was added dropwise to the above suspension over 30 minutes. The reaction mixture was heated at reflux for 2 hrs. Excess lithium aluminium hydride was decomposed carefully with water and the resulting mixture filtered through a pad of diatomaceous earth. The filtrate was partitioned between water (200 ml) and ether (800 ml). The organic layer was dried (magnesium sulphate) and evaporated in vacuo to a semi-solid which on trituation with petroleum ether (b.pt. 40°-60°) gave 2-(4-chloro-6-hydroxymethylphenyl)ethanol as a solid (45 g) m.pt. 75°-76°, characterised by its nmr spectrum.
Reaction SMILES: [NH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2.[C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[S:20](Cl)(=[O:22])=[O:21])#[N:13]>CN(C1C=CN=CC=1)C>[C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[S:20]([NH:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2)(=[O:22])=[O:21])#[N:13]
Reactant: N#Cc1ccccc1S(=O)(=O)Cl
Reactant: Nc1cccc2cccnc12
Agent: CN(C)c1ccncc1
Product: N#Cc1ccccc1S(=O)(=O)Nc1cccc2cccnc12
Yield: 46.9 %

Procedure:
In the similar fashion using route 14 general procedure 27, 8-aminoquinoline (100 mg, 0.69 mmol), 2-cyanobenzenesulfonyl chloride (140 mg, 0.69 mmol) and DMAP (cat.) gave the title compound (100 mg, 50%) after purification by column chromatography with DCM as the eluent.
Reaction SMILES: [Br:1][C:2]1[C:3]([O:14][CH3:15])=[C:4]([C:9]([CH2:12]Br)=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[CH:16]12[CH:22]([SH:23])[CH:19]([CH2:20][CH2:21]1)[CH2:18][CH2:17]2.C(=O)([O-])[O-].[K+].[K+]>C1COCC1>[CH:19]12[CH:22]([S:23][CH2:12][C:9]3[C:4]([C:5]([O:7][CH3:8])=[O:6])=[C:3]([O:14][CH3:15])[C:2]([Br:1])=[CH:11][CH:10]=3)[CH:16]([CH2:21][CH2:20]1)[CH2:17][CH2:18]2
Reactant: SC1C2CCC1CC2
Reactant: COC(=O)c1c(CBr)ccc(Br)c1OC
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: C1CCOC1
Product: COC(=O)c1c(CSC2C3CCC2CC3)ccc(Br)c1OC
Temperature: 60 °C
Yield: 63.3 %

Procedure:
A mixture of methyl 3-bromo-6-bromomethyl-2-methoxybenzoate (Intermediate 89, 0.338 g), bicyclo[2.2.1]heptane-7-thiol (Intermediate 183, 0.148 g) and potassium carbonate (0.345 g) in THF (5 ml) was stirred and heated at 60° C. for 3 days. After cooling, the mixture was partitioned between ethyl acetate and water and the organic layer was separated, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 0-10% to give methyl 6-(bicyclo[2.2.1]hept-7-ylthiomethyl)-3-bromo-2-methoxybenzoate (0.244 g).
Reaction SMILES: [C:1]([O:5][C:6]([NH:8][C:9]1[N:14]=[CH:13][C:12]([C:15]2[C:24]([N:25]([CH:27]([CH3:29])[CH3:28])[CH3:26])=[N:23][C:22]3[C:17](=[CH:18][CH:19]=[C:20]([C:30]([O:32]C)=[O:31])[CH:21]=3)[N:16]=2)=[CH:11][CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[OH-].[Na+].O>CO>[C:1]([O:5][C:6]([NH:8][C:9]1[N:14]=[CH:13][C:12]([C:15]2[C:24]([N:25]([CH:27]([CH3:28])[CH3:29])[CH3:26])=[N:23][C:22]3[C:17](=[CH:18][CH:19]=[C:20]([C:30]([OH:32])=[O:31])[CH:21]=3)[N:16]=2)=[CH:11][CH:10]=1)=[O:7])([CH3:2])([CH3:4])[CH3:3]
Reactant: COC(=O)c1ccc2nc(-c3ccc(NC(=O)OC(C)(C)C)nc3)c(N(C)C(C)C)nc2c1
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: CO
Product: CC(C)N(C)c1nc2cc(C(=O)O)ccc2nc1-c1ccc(NC(=O)OC(C)(C)C)nc1
Temperature: 25 °C
Reaction time: 8 h
Yield: 34.9 %

Procedure:
To a solution of methyl 2-(6-(tert-butoxycarbonylamino)pyridin-3-yl)-3-(isopropyl(methyl)amino)quinoxaline-6-carboxylate (160.0 mg, 0.35 mmol) in methanol (30 mL) was added sodium hydroxide (43.0 mg, 1.06 mmol) and water (1 mL). The reaction mixture was stirred overnight at room temperature and concentrated under vacuum. The residue was dissolved in water (30 mL) and adjusted to pH 6 with HCl (3N). The solids were collected, dried in an oven under reduced pressure to afford 2-(6-(tert-butoxycarbonylamino)pyridin-3-yl)-3-(isopropyl(methyl)amino)quinoxaline-6-carboxylic acid as a light yellow solid (53.5 mg, 33%).
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:6][C:7]=1I.C[Si](C)(C)[C:14]([F:17])([F:16])[F:15].[F-].[K+]>CN(C)C=O.C(OCC)C.[Cu]I>[Cl:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:6][C:7]=1[C:14]([F:17])([F:16])[F:15]
Reactant: O=[N+]([O-])c1ccc(I)c(Cl)c1
Reactant: C[Si](C)(C)C(F)(F)F
Agent: [Cu]I
Agent: [F-]
Agent: [K+]
Solvent: CCOCC
Solvent: CN(C)C=O
Product: O=[N+]([O-])c1ccc(C(F)(F)F)c(Cl)c1

Procedure:
A solution of 3-chloro-4-iodo-nitrobenzene (2.26 g), trimethyl(trifluoromethyl)silane (5.68 g), copper(I) iodide (2.28 g), and potassium fluoride (0.56 g) in N,N-dimethylformamide (8 mL) is heated in a sealed tube to 80° C. for 40 hours. The solution is then cooled, diluted with diethyl ether, filtered through diatomaceous earth, and the filtrate is washed successively with water, saturated aqueous sodium chloride, and then dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure and the residue is chromatographed over silica gel (1% diethyl ether in hexanes followed by 10% ethyl acetate in hexanes is used as the eluant) to provided the desired product as a colorless oil.
Reaction SMILES: [Na].[S:2](=[C:5]([C:7]1[CH:12]=[N:11][CH:10]=[CH:9][N:8]=1)[CH3:6])(=[O:4])=[O:3].[CH3:13]I>CO>[CH3:13][N:11]1[CH:10]=[CH:9][N:8]=[C:7]([C:5](=[S:2](=[O:4])=[O:3])[CH3:6])[CH2:12]1
Reactant: CI
Reactant: CC(c1cnccn1)=S(=O)=O
Agent: [Na]
Solvent: CO
Product: CC(C1=NC=CN(C)C1)=S(=O)=O

Procedure:
3.50 g of 2-(1-sulfonylethyl)pyrazine sodium salt (2300) was dissolved in 75 ml of methanol and 10 ml of methyl iodide added. The flask was then stoppered and stored in the dark at room temperature.
Reaction SMILES: [OH-].[K+].[C:3]1([C:9]2[NH:10][CH:11]=[C:12]([C:14]3[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=3)[N:13]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Br[CH2:23][CH2:24][CH2:25][CH3:26]>CS(C)=O>[CH2:23]([N:10]1[CH:11]=[C:12]([C:14]2[CH:15]=[CH:16][C:17]([O:20][CH3:21])=[CH:18][CH:19]=2)[N:13]=[C:9]1[C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1)[CH2:24][CH2:25][CH3:26]
Reactant: COc1ccc(-c2c[nH]c(-c3ccccc3)n2)cc1
Reactant: CCCCBr
Agent: [K+]
Agent: [OH-]
Solvent: CS(C)=O
Product: CCCCn1cc(-c2ccc(OC)cc2)nc1-c1ccccc1
Temperature: 0 °C

Procedure:
Potassium hydroxide (4.36, 76 mmol, 1.3 eq.) is suspended in 40 ml of anhydrous DMSO, to the suspension is added a solution 2-phenyl-4-(4-methoxyphenyl)imidazole (15.02, 60 mmol) and bromobutane (8.63 g, 63 mmol, 1.05 eq.) in 80 ml of DMSO at room temperature over 2h, the resulting mixture is stirred over 24h, and then poured into 400 ml of ice-water, extracted with ethyl acetate (100 ml×4), washed,with water and brine, dried over anhydrous sodium sulfate. The solvent is evaporated and the product is purified through flash chromatography to give 16.73 g of 4-({[3-Butyl-5-(4-methoxy-phenyl)-2-phenyl-3H-imidazole. MS (+VE) m/z 307 (M+1).
Reaction SMILES: [CH3:1][C:2]1[C:6]([C:7]2[CH:16]=[C:15]3[C:10]([C:11]([NH:18][CH2:19][CH:20]4[CH2:25][CH2:24][O:23][CH2:22][CH2:21]4)=[C:12]([NH2:17])[CH:13]=[N:14]3)=[CH:9][C:8]=2[O:26][CH3:27])=[C:5]([CH3:28])[O:4][N:3]=1.[Cl-].Cl[C:31](Cl)=[N+:32]([CH3:34])[CH3:33]>C(#N)C.CS(C)=O>[CH3:1][C:2]1[C:6]([C:7]2[C:8]([O:26][CH3:27])=[CH:9][C:10]3[C:11]4[N:18]([CH2:19][CH:20]5[CH2:21][CH2:22][O:23][CH2:24][CH2:25]5)[C:31]([N:32]([CH3:34])[CH3:33])=[N:17][C:12]=4[CH:13]=[N:14][C:15]=3[CH:16]=2)=[C:5]([CH3:28])[O:4][N:3]=1
Reactant: COc1cc2c(NCC3CCOCC3)c(N)cnc2cc1-c1c(C)noc1C
Reactant: C[N+](C)=C(Cl)Cl
Agent: [Cl-]
Solvent: CC#N
Solvent: CS(C)=O
Product: COc1cc2c(cc1-c1c(C)noc1C)ncc1nc(N(C)C)n(CC3CCOCC3)c12
Temperature: 120 °C
Yield: 77.1 %

Procedure:
7-(3,5-Dimethylisoxazol-4-yl)-6-methoxy-N4-((tetrahydro-2H-pyran-4-yl)methyl)quinoline-3,4-diamine (for preparation see intermediate 17) (50 mg, 0.131 mmol) and N-(dichloromethylene)-N-methylmethanaminium chloride (available from Aldrich) (42.5 mg, 0.261 mmol) were combined in anhydrous acetonitrile (0.5 ml) and heated at 120° C. for 10 min (microwave). The reaction mixture was reduced to dryness under a stream of nitrogen and the residue dissolved in DMSO (1 ml) and purified by MDAP (HpH). The solvent was evaporated under a stream of nitrogen to give 7-(3,5-dimethylisoxazol-4-yl)-8-methoxy-N,N-dimethyl-1-((tetrahydro-2H-pyran-4-yl)methyl)-1H-imidazo[4,5-c]quinolin-2-amine (44 mg, 0.101 mmol, 77% yield) as a yellow gum.
Reaction SMILES: [CH:1]([C:4]1[C:5](=[O:21])[NH:6][C:7](=[O:20])[NH:8][C:9]=1[C:10](=[O:19])[C:11]1[CH:16]=[C:15]([CH3:17])[CH:14]=[C:13]([CH3:18])[CH:12]=1)([CH3:3])[CH3:2].Cl[CH2:23][C:24](=[O:26])[CH3:25]>>[CH2:23]([N:8]1[C:9]([C:10](=[O:19])[C:11]2[CH:12]=[C:13]([CH3:18])[CH:14]=[C:15]([CH3:17])[CH:16]=2)=[C:4]([CH:1]([CH3:3])[CH3:2])[C:5](=[O:21])[NH:6][C:7]1=[O:20])[C:24]([CH3:25])=[O:26]
Reactant: CC(=O)CCl
Reactant: Cc1cc(C)cc(C(=O)c2[nH]c(=O)[nH]c(=O)c2C(C)C)c1
Product: CC(=O)Cn1c(C(=O)c2cc(C)cc(C)c2)c(C(C)C)c(=O)[nH]c1=O
Yield: 45 %

Procedure:
5-Isopropyl-6-(3,5-dimethylbenzoyl)-2,4-pyrimidinedione and chloroacetone were reacted by the same way with the example 1 to obtain the titled compound (155 mg, yield: 45%).
Reaction SMILES: [CH3:1][O:2][C:3](=[O:15])[C:4](=O)[CH:5]=[CH:6][C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=1.Cl.[Cl:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[NH:24][NH2:25]>C(O)(=O)C>[CH3:1][O:2][C:3]([C:4]1[CH2:5][CH:6]([C:7]2[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=2)[N:24]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=2[Cl:17])[N:25]=1)=[O:15]
Reactant: COC(=O)C(=O)C=Cc1ccc(Br)cc1
Reactant: NNc1ccccc1Cl
Agent: Cl
Solvent: CC(=O)O
Product: COC(=O)C1=NN(c2ccccc2Cl)C(c2ccc(Br)cc2)C1
Temperature: 125 °C
Reaction time: 4 h
Yield: 95.6 %

Procedure:
4-(4-Bromo-phenyl)-2-oxo-3-butenoic acid methyl ester (13.5 g, 50.2 mmol) prepared in Step 2 and 2-chlorophenylhydrazine hydrochloride (9.9 g, 55.2 mmol) were added to acetic acid (200.0 mL). The reaction mixture was stirred at 125° C. for 4 hours, concentrated under reduced pressure, and then ethyl acetate was added thereto. The reaction mixture was washed with a saturated solution of sodium hydrogen carbonate, dried on anhydrous magnesium sulfate, and then concentrated under reduced pressure to give a yellow liquid residue. The resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/5) to give 18.9 g of the titled compound as a brown liquid.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:22]=[CH:21][C:6]([CH2:7][O:8][C@H:9]([C@H:11]([OH:20])[C@H:12]([CH:18]=[CH2:19])[CH2:13][CH2:14][CH:15]([CH3:17])[CH3:16])[CH3:10])=[CH:5][CH:4]=1.[H-].[Na+].[CH3:25][C:26]1[CH:31]=CC(S(OCC(C)C)(=O)=O)=C[CH:27]=1>CN(C=O)C>[CH2:25]([O:20][C@H:11]([C@H:12]([CH:18]=[CH2:19])[CH2:13][CH2:14][CH:15]([CH3:16])[CH3:17])[C@@H:9]([O:8][CH2:7][C:6]1[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:22][CH:21]=1)[CH3:10])[CH:26]([CH3:31])[CH3:27]
Reactant: Cc1ccc(S(=O)(=O)OCC(C)C)cc1
Reactant: C=C[C@H](CCC(C)C)[C@@H](O)[C@H](C)OCc1ccc(OC)cc1
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: C=C[C@H](CCC(C)C)[C@@H](OCC(C)C)[C@H](C)OCc1ccc(OC)cc1
Temperature: 25 °C
Reaction time: 0.25 h
Yield: 86.6 %

Procedure:
A solution of (2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g, 6.53 mmol) in anhydrous DMF (15 mL) was added at room temperature to a solution of NaH (0.326 g, 8.16 mmol, 60% dispersion in mineral oil) in anhydrous DMF (6.0 mL). The reaction was stirred for 15 min at room temperature, then isobutyl 4-methylbenzenesulfonate (1.66 mL, 8.16 mmol) was added at room temperature and the reaction was heated at 50° C. and stirred for 1 h. The reaction was cooled down to room temperature and NaH (0.261 g, 6.53 mmol) followed by isobutyl 4-methylbenzenesulfonate (1.33 mL, 6.53 mmol) were added and heating continued for 2 h at 50° C., after which the reaction was again cooled down to room temperature and a third batch of NaH (0.131 g, 3.27 mmol) and isobutyl 4-methylbenzenesulfonate (0.67 mL, 3.27 mmol) were added and the reaction was heated at 50° C. for 7 h. The reaction mixture was quenched with saturated NH4Cl and the phases were separated. The aqueous phase was extracted with Et2O, and the combined organic phases were washed with brine, dried over MgSO4, concentrated, and purified by column chromatography on SiO2 (gradient, hexanes/ethyl acetate) to furnish the title product as a colorless oil (2.05 g, 87%): 1H NMR (400 MHz, CDCl3) δ 7.29-7.21 (m, 2H), 6.90-6.83 (m, 2H), 5.61-5.49 (m, 1H), 5.04-4.89 (m, 2H), 4.53-4.33 (m, 2H), 3.80 (s, 3H), 3.64-3.51 (m, 2H), 3.28-3.16 (m, 2H), 2.15-2.02 (m, 1H), 1.90-1.77 (m, 1H), 1.76-1.60 (m, 1H), 1.54-1.41 (m, 1H), 1.28-1.11 (m, 2H), 1.17 (d, J=6.3 Hz, 3H), 1.08-0.96 (m, 1H), 0.95-0.88 (m, 6H), 0.86 (d, J=6.4 Hz, 3H), 0.85 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 158.97, 140.43, 131.09, 129.06, 115.66, 113.67, 84.26, 79.58, 76.41, 70.05, 55.26, 47.38, 36.46, 29.13, 28.21, 27.85, 22.91, 22.47, 19.66, 19.55, 14.25; ESIMS m/z 385.4 ([M+Na]+).
Reaction SMILES: [C:1]12([CH2:11][OH:12])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.C1C=C[NH+]=CC=1.[O-][Cr](Cl)(=O)=O.O>C(Cl)Cl>[C:1]12([CH:11]=[O:12])[CH2:8][CH:7]3[CH2:6][CH:5]([CH2:4][CH:3]([CH2:9]3)[CH2:2]1)[CH2:10]2
Reactant: OCC12CC3CC(CC(C3)C1)C2
Agent: O=[Cr](=O)([O-])Cl
Agent: c1cc[nH+]cc1
Solvent: O
Solvent: ClCCl
Product: O=CC12CC3CC(CC(C3)C1)C2
Temperature: 25 °C
Reaction time: 0.17 h
Yield: 82.8 %

Procedure:
To a solution of 1-adamantanemethanol (1.66 g, 10 mmol) in CH2Cl2 was added PCC (4.3 g, 20 mmol) at 0° C. The resulting mixture was stirred at the same temperature for 10 mins before warming to ambient temperature. Stirring was continued for 1.5 hrs until the disappearance of starting material as checked by TLC. Water was added and extracted with CH2Cl2 for 3 times. The combined organic phase was dried over MgSO4, filtrated and concentrated in vacuo. The crude mixture was separated by flash chromatography (50%-100% CH2Cl2/Hexane) to give 49 as white solid (1.36 g, Yield: 83%). 1H-NMR (360 MHz, CDCl3) δ 9.32 (s, 1H), 2.07 (br s, 3H), 1.77 (br s, 6H), 1.72 (br s, 6H); 13C-NMR (90 MHz, CDCl3) δ 206.07, 45.03, 37.25, 36.10, 27.61; ESI-MS: Calculated for C11H16O (M+H)+ 165.2. Found: 165.5.
Reaction SMILES: [Cl:1][C:2]1[S:6][C:5]([S:7]([N:10]([C:19]2[C:27]3[C:22](=[CH:23][CH:24]=[CH:25][C:26]=3[O:28][CH3:29])[NH:21][N:20]=2)[CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])(=[O:9])=[O:8])=[CH:4][CH:3]=1.Cl[CH2:31][C:32]1[CH:44]=[CH:43][C:35]([C:36]([N:38]([CH2:41]C)[CH2:39]C)=[O:37])=[CH:34][CH:33]=1.[OH-].[K+]>>[Cl:1][C:2]1[S:6][C:5]([S:7]([N:10]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:16])[CH3:17])[C:19]2[C:27]3[C:22](=[CH:23][CH:24]=[CH:25][C:26]=3[O:28][CH3:29])[N:21]([CH2:31][C:32]3[CH:44]=[CH:43][C:35]([C:36]([N:38]([CH3:39])[CH3:41])=[O:37])=[CH:34][CH:33]=3)[N:20]=2)(=[O:9])=[O:8])=[CH:4][CH:3]=1
Reactant: COc1cccc2[nH]nc(N(COCC[Si](C)(C)C)S(=O)(=O)c3ccc(Cl)s3)c12
Reactant: CCN(CC)C(=O)c1ccc(CCl)cc1
Agent: [K+]
Agent: [OH-]
Product: COc1cccc2c1c(N(COCC[Si](C)(C)C)S(=O)(=O)c1ccc(Cl)s1)nn2Cc1ccc(C(=O)N(C)C)cc1
Temperature: 50 °C
Yield: 61.5 %

Procedure:
A solution of 5-chloro-N-[4-(methyloxy)-1H-indazol-3-yl]-N-({[2-(trimethylsilyl)ethyl]oxy}methyl)-2-thiophenesulfonamide (Intermediate 8) (150 mg, 0.32 mmol) was treated with 4-(chloromethyl)-N,N-diethylbenzamide (86 mg, 0.38 mmol) and potassium hydroxide (21.3 mg, 0.38 mmol), and the mixture was heated to 50° C. overnight. Reaction mixture was partitioned between DCM (3 mL) and water (3 mL). The organic phase was separated and the aqueous layer was further extracted with 2 mL of DCM. The combined organic solutions were dried (hydrophobic frit) and concentrated under a nitrogen stream in a blowdown unit. The residue was purified by chromatography using a Flash Master system (Solo machine), on a 50 g silica cartridge, eluting with 0 to 100% A in B, A being a 20% EtOAC in DCM solution and B being neat DCM over 60 min. Evaporation of the appropriate fractions gave the title compound (125 mg, 60%) LCMS (System A) RT=1.52 min, ES+ve m/z 680/682(M+NH4)+.
Reaction SMILES: [CH:1]([CH:13]1[CH2:18][C:17](=[O:19])[O:16][C:14]1=[O:15])=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].C([OH:23])C=C>>[CH2:1]([CH:13]([CH2:18][C:17]([OH:16])=[O:19])[C:14]([OH:23])=[O:15])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]
Reactant: C=CCO
Reactant: CCCCCCCCCCC=CC1CC(=O)OC1=O
Product: CCCCCCCCCCCCC(CC(=O)O)C(=O)O

Procedure:
In a 4-necked flask 1 mole of dodecenylsuccinic anhydride and 1 mole of allylalcohol were reacted together at 110°±5 ° C. for 2 hours to form a monoallyl ester of dodecylsuccinic acid. The product thus obtained was then converted to its triethanolamine salt whihc is a viscous yellowish brown liquid having a good self-emulsifiability in water.
Reaction SMILES: [C:1]([O:4][C:5](=[O:7])[CH3:6])(=O)[CH3:2].C(=O)([O-])[O-].[K+].[K+].[CH3:14][C:15](=[CH:17][CH2:18][CH2:19][CH:20](CC=O)[CH3:21])[CH3:16].C1(C)C=CC=CC=1>O>[C:5]([O:4][CH:1]=[CH:2][CH:20]([CH3:21])[CH2:19][CH2:18][CH:17]=[C:15]([CH3:16])[CH3:14])(=[O:7])[CH3:6]
Reactant: CC(=O)OC(C)=O
Reactant: CC(C)=CCCC(C)CC=O
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: Cc1ccccc1
Product: CC(=O)OC=CC(C)CCC=C(C)C

Procedure:
167 kg of acetic anhydride and 77 kg of potassium carbonate were heated to 80° in a reaction vessel equipped with an introduction pump and a condenser. 85 kg of (±)-citronellal were then added by means of the introduction pump during 40 min and the mixture was refluxed for 7 hours. After cooling, 100 kg of toluene and 500 l of water were added thereto and after separation of the organic phase the mixture was washed with 100 l of water to give a solution of 3,7-dimethyl-octa-1,6-dien-l-yl acetate in toluene accompanied by minor quantities of a diester of formula ##STR8##
Reaction SMILES: [C:1]1([N:7]2[CH:11]([C:12]3[CH:17]=[CH:16][C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:14][CH:13]=3)[CH:10]=[C:9]([C:22]3[CH:27]=[CH:26][C:25](I)=[CH:24][CH:23]=3)[NH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:29][Si:30]([C:33]#[CH:34])([CH3:32])[CH3:31].C(N(CC)CC)C>C1COCC1.[Cu](I)I>[C:1]1([N:7]2[CH:11]([C:12]3[CH:17]=[CH:16][C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:14][CH:13]=3)[CH:10]=[C:9]([C:22]3[CH:27]=[CH:26][C:25]([C:34]#[C:33][Si:30]([CH3:32])([CH3:31])[CH3:29])=[CH:24][CH:23]=3)[NH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: CC(C)(C)c1ccc(C2C=C(c3ccc(I)cc3)NN2c2ccccc2)cc1
Reactant: C#C[Si](C)(C)C
Agent: I[Cu]I
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CC(C)(C)c1ccc(C2C=C(c3ccc(C#C[Si](C)(C)C)cc3)NN2c2ccccc2)cc1
Temperature: 60 °C
Reaction time: 10 h

Procedure:
After charging 9.6 parts of 1-phenyl-3-(4-iodophenyl)-5-(4-t-butylphenyl)pyrazoline synthesized by a known method, 2.4 parts of trimethylsilylacetylene, 0.28 parts of bis(triphenylphosphine)palladium(II) dichloroide, 0.04 parts of copper iodide and 40 mL of triethylamine in 80 mL of THF, the mixture was stirred at 60° C. for 10 hours. The reaction mixture was filtered, the obtained filtrate was concentrated, and the precipitate was filtered, washed, recrystallized from methanol and dried at 60° C. to obtain 5.6 parts of 1-phenyl-3-(4-trimethylsilylethynylphenyl)-5-(4-t-butylphenyl)pyrazoline having a melting point of 160-162° C.
Reaction SMILES: I[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:5]([NH2:6])=[C:4]([CH3:12])[CH:3]=1.[CH2:13]([N:20]1[CH2:25][CH2:24][CH2:23][C:22]2([CH2:30][CH2:29][CH2:28][NH:27][CH2:26]2)[CH2:21]1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(O)CO.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C(O)(C)C.[Cu]I>[CH2:13]([N:20]1[CH2:25][CH2:24][CH2:23][C:22]2([CH2:26][N:27]([C:2]3[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:5]([NH2:6])=[C:4]([CH3:12])[CH:3]=3)[CH2:28][CH2:29][CH2:30]2)[CH2:21]1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1
Reactant: c1ccc(CN2CCCC3(CCCNC3)C2)cc1
Reactant: Cc1cc(I)cc([N+](=O)[O-])c1N
Agent: [Cu]I
Agent: O=P([O-])([O-])[O-]
Agent: [K+]
Solvent: OCCO
Solvent: CC(C)O
Product: Cc1cc(N2CCCC3(CCCN(Cc4ccccc4)C3)C2)cc([N+](=O)[O-])c1N
Temperature: 90 °C
Yield: 30.1 %

Procedure:
A suspension of 4-iodo-2-methyl-6-nitroaniline (1.39 g, 5 mmol), 2-benzyl-2,8-diaza-spiro[5.5]undecane (1.22 g, 5 mmol), CuI (190.5 mg, 1.0 mmol), ethylene glycol (931 mg, 15 mmol) and K3PO4 (3.2 g, 15 mmol) in isopropanol (40 mL) was sealed and heated at 90° C. for 19 h. After cooled down to room temperature, the reaction mixture was concentrated. The residue was purified by chromatography (99:1 CH2Cl2/MeOH) to afford the title compound (593 mg, 30%). 1H NMR (CDCl3) δ 1.24 (m, 2H), 1.48-1.68 (6H), 2.01-2.24 (m, 2H), 2.24 (s, 3H), 2.57 (m, 2H), 2.73 (d, J=12 Hz, 1H), 2.82 (m, 1H), 3.03 (m, 1H), 3.14 (d, J=12 Hz, 1H), 3.47 (d, J=9 Hz, 2H), 5.30 (br s, 2H NH), 7.11 (s, 1H), 7.19-7.33 (5H), 7.44 (s, 1H). ESI-MS m/z 395 (MH+).