Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [IH:1].N[C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:8])=[CH:5][CH:4]=1.C([O-])([O-])=O.[K+].[K+]>CS(C)=O.CCOCC>[I:1][C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:8])=[CH:5][CH:4]=1
Reactant: Nc1ccc(C(=O)c2ccccc2)cc1
Reactant: I
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CS(C)=O
Solvent: CCOCC
Product: O=C(c1ccccc1)c1ccc(I)cc1
Temperature: 35 °C
Reaction time: 0.17 h

Procedure:
A solution of 57% aqueous HI (3.29 ml, 25 mmol) dissolved in DMSO (25 ml) was added dropwise to a solution of 4-aminobenzophenone (0.986 g, 5 mmol) in a mixture of 25 ml of DMSO and KNO2 (0.851 g, 10 mmol) at 35° C. with agitation. The added mixture was stirred at 35° C. for 10 minutes and then was transferred to a solution containing K2CO3 (5 g) in 100 ml ice-water. The reaction mixture was then taken up in ether, and then the ethereal extracts were washed with water and dried over anhydrous magnesium sulfate. Removal of the solvent under reduced pressure gave the crude 4-iodobenzophenone. The crude product was further purified by column chromatography to obtain 4-iodobenzophenone. The yield determined by gas chromatography was 88% (based on decane as an internal standard).
Reaction SMILES: [S-2:1].[Na+].[Na+].[Cl:4][C:5]1[CH:12]=[CH:11][CH:10]=[C:9]([Cl:13])[C:6]=1[CH2:7]Cl>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O>[Cl:4][C:5]1[CH:12]=[CH:11][CH:10]=[C:9]([Cl:13])[C:6]=1[CH2:7][S:1][CH2:7][C:6]1[C:5]([Cl:4])=[CH:12][CH:11]=[CH:10][C:9]=1[Cl:13]
Reactant: ClCc1c(Cl)cccc1Cl
Reactant: [S-2]
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: O=S(=O)([O-])O
Agent: [Na+]
Solvent: O
Product: Clc1cccc(Cl)c1CSCc1c(Cl)cccc1Cl
Yield: 80.4 %

Procedure:
A mixture of 98.8 g (0.411 mol) of sodium sulfide, 5.0 g of tetrabutylammonium hydrogen sulfate and 110 ml of water are stirred in a reaction vessel equipped with a stirrer, thermometer and heatable dropping funnel, until a solution is obtained. 107.2 g of melted 2,6-dichlorobenzyl chloride are added with vigorous stirring over a period of 25 minutes at such a rate that the inside temperature does not exceed 55° C. The reaction mixture is worked up as in Example 9(a) to give 77.6 g (80% of theory) of bis(2,6-dichlorobenzyl) sulfide in the form of white crystals of melting point 128°-130° C.
Reaction SMILES: [CH2:1]([CH2:10][CH2:11][NH:12][C:13]1[C:21]2[C:16](=[CH:17][C:18]([Cl:23])=[CH:19][C:20]=2[Cl:22])[N:15](C(OC(C)(C)C)=O)[C:14]=1[C:31]([O:33][CH2:34][CH3:35])=[O:32])[C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[O:3].FC(F)(F)C(O)=O.C(=O)([O-])O.[Na+]>C(Cl)Cl>[CH2:1]([CH2:10][CH2:11][NH:12][C:13]1[C:21]2[C:16](=[CH:17][C:18]([Cl:23])=[CH:19][C:20]=2[Cl:22])[NH:15][C:14]=1[C:31]([O:33][CH2:34][CH3:35])=[O:32])[C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[O:3]
Reactant: CCOC(=O)c1c(NCCCC(=O)c2ccccc2)c2c(Cl)cc(Cl)cc2n1C(=O)OC(C)(C)C
Agent: O=C([O-])O
Agent: [Na+]
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: CCOC(=O)c1[nH]c2cc(Cl)cc(Cl)c2c1NCCCC(=O)c1ccccc1
Reaction time: 4 h
Yield: 34.9 %

Procedure:
Dissolve 3-[(phenacyl)ethylamino]-2-carbethoxy-4,6-dichloro-1-tert-butyloxycarbonyl-indole (0.79 g, 1.57 mmol) in methylene chloride (5 mL) and add, by dropwise addition, trifluoroacetic acid (5 mL). Stir for 4 hours and pour carefully into saturated sodium hydrogen carbonate (100 mL). Extract into ethyl acetate, dry (MgSO4) and evaporate the solvent in vacuo to give as yellow oil. Recrystallize (ethyl acetate/hexane) to give the title compound (0.23 g, 36%); mp 203°-5° C.
Reaction SMILES: [N:1]1[CH:6]=[CH:5][C:4]([C:7]2[C:15]3[C:10](=[CH:11][CH:12]=[C:13]([NH2:16])[CH:14]=3)[N:9]([C:17]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[N:8]=2)=[CH:3][CH:2]=1.OS(O)(=O)=O.N([O-])=O.[Na+].[N-:45]=[N+:46]=[N-].[Na+]>O>[N:16]([C:13]1[CH:14]=[C:15]2[C:10](=[CH:11][CH:12]=1)[N:9]([C:17]([C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1)([C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[N:8]=[C:7]2[C:4]1[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=1)=[N+:45]=[N-:46]
Reactant: Nc1ccc2c(c1)c(-c1ccncc1)nn2C(c1ccccc1)(c1ccccc1)c1ccccc1
Reactant: [N-]=[N+]=[N-]
Agent: O=N[O-]
Agent: O=S(=O)(O)O
Agent: [Na+]
Solvent: O
Product: [N-]=[N+]=Nc1ccc2c(c1)c(-c1ccncc1)nn2C(c1ccccc1)(c1ccccc1)c1ccccc1
Temperature: 0 °C
Reaction time: 0.5 h
Yield: 91.9 %

Procedure:
To a 1 L round bottom flask equipped with a magnetic stir bar was suspended 3-(pyridin-4-yl)-1-trityl-1H-indazol-5-amine (13.00 g, 28.7 mmol) in 400.00 ml of water and cooled to 0° C. 80 ml of cone. H2SO4 was added slowly over a period of 15 min at 0° C. A solution of NaNO2(2.48 g, 35.9 mmol) in 15 ml of water was added to the mixture and allowed to stir at 0° C. for 30 min. A solution of NaN3 (3.36 g, 51.7 mmol) in water was then added dropwise over a period of 15 min. The mixture was slowly warmed to room temperature and stirred overnight. Upon completion, the precipitate was filtered, washed with water and dried to give 5-azido-3-(pyridin-4-yl)-1-trityl-1H-indazole (12.62 g) as a yellow solid.
Reaction SMILES: C([BH3-])#N.[Na+].[C:5]([O:9][C:10]([N:12]1[CH2:17][CH2:16][CH:15]([CH2:18][NH2:19])[CH2:14][CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6].[C:20]([O:24][C:25]([N:27]1[CH2:32][CH2:31][CH:30]([CH:33]=O)[CH2:29][CH2:28]1)=[O:26])([CH3:23])([CH3:22])[CH3:21].C(O)(=O)C>CO>[C:5]([O:9][C:10]([N:12]1[CH2:17][CH2:16][CH:15]([CH2:18][NH:19][CH2:33][CH:30]2[CH2:31][CH2:32][N:27]([C:25]([O:24][C:20]([CH3:21])([CH3:23])[CH3:22])=[O:26])[CH2:28][CH2:29]2)[CH2:14][CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]
Reactant: CC(C)(C)OC(=O)N1CCC(CN)CC1
Reactant: CC(C)(C)OC(=O)N1CCC(C=O)CC1
Agent: [BH3-]C#N
Agent: [Na+]
Solvent: CC(=O)O
Solvent: CO
Product: CC(C)(C)OC(=O)N1CCC(CNCC2CCN(C(=O)OC(C)(C)C)CC2)CC1
Reaction time: 0.25 h
Yield: 63.5 %

Procedure:
Sodium cyanoborohydride (440 mg; 7.0 mmol) was added to a solution of [(1-tert-butoxycarbonyl-4-piperidinyl)-methyl]amine (1.5 g; 7.0 mmol) in methanol (30 ml) under ice cooling, and the mixture was stirred for 15 minutes. A solution of 1-tert-butoxycarbonyl-4-piperidine-carbaldehyde (1.4 g; 9.1 mmol) in methanol (5 ml) and acetic acid (0.40 ml; 7.0 mmol) were added to the resultant solution, and the mixture was stirred for 4 hours. After the ice bath was removed, the mixture was stirred at room temperature for 48 hours. The reaction mixture was concentrated under reduced pressure and the resultant concentrated residue was added to a saturated aqueous solution of sodium hydrogencarbonate to conduct extraction with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resultant crude oil was purified by column chromatography on silica gel, thereby obtaining 1.83 g (yield: 63%) of N,N-bis[(1-tert-butoxycarbonyl-4-piperidinyl)methyl]amine as a colorless oil.
Reaction SMILES: [C:1](#N)C.C1OCCOCCOCCOCCOCCOC1.CI.[OH:24][C:25]1[CH:34]=[C:33]([O:35][CH:36]([CH2:38][CH3:39])[CH3:37])[CH:32]=[C:31]2[C:26]=1[C:27](=[O:42])[CH2:28][C:29]([CH3:41])([CH3:40])[O:30]2>[Na]>[CH3:1][O:24][C:25]1[CH:34]=[C:33]([O:35][CH:36]([CH2:38][CH3:39])[CH3:37])[CH:32]=[C:31]2[C:26]=1[C:27](=[O:42])[CH2:28][C:29]([CH3:40])([CH3:41])[O:30]2
Reactant: CC#N
Reactant: CCC(C)Oc1cc(O)c2c(c1)OC(C)(C)CC2=O
Agent: C1COCCOCCOCCOCCOCCO1
Agent: [Na]
Solvent: CI
Product: CCC(C)Oc1cc(OC)c2c(c1)OC(C)(C)CC2=O
Reaction time: 3 h
Yield: 92 %

Procedure:
In 100 ml of acetonitrile 5.6 g (20 millimoles) of the sodium salt of 5-hydroxy-7-sec. butoxy-2,2-dimethyl-4-chromanone are dissolved and stirred in the presence of 0.5 g (2 millimoles) of 18-Crown-6 for 30 minutes. Thereafter 4.25 g (1.9 ml, 30 millimoles) of methyl iodide are added and the reaction mixture is stirred for a further 3 hours. The inorganic salt is filtered off, the solvent removed and the residue suspended in carbon tetrachloride, extracted twice with 30 ml of water each, the organic phase is dried over sodium sulfate and evaporated. Thus 5.1 g of the desired compound are obtained in the form of a light yellow oil, yield 92%.
Reaction SMILES: [Cl:1][C:2]1[CH:11]=[N:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([O:12][CH3:13])[CH:8]=2)[N:3]=1.[NH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>C(Cl)Cl>[ClH:1].[NH:14]([C:2]1[CH:11]=[N:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([O:12][CH3:13])[CH:8]=2)[N:3]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: Nc1ccccc1
Reactant: COc1ccc2nc(Cl)cnc2c1
Solvent: ClCCl
Product: COc1ccc2nc(Nc3ccccc3)cnc2c1
Product: Cl
Temperature: 120 °C
Reaction time: 1.5 h

Procedure:
To 2-chloro-6-methoxy-quinoxaline (0.93 g, 4.8 mmol) under argon is added aniline (1.3 mL, 14.3 mmol). The reaction mixture is heated at 120° C. for 2 hours, then at 150° C. for 1.5 hours. The mixture is cooled and CH2Cl2 is added. The resulting suspension is stirred and the orange solid is filtered off, washed with CH2Cl2/Et2O, then stirred vigorously in H2O for 40 minutes, filtered, and washed with Et2O to provide a bright-yellow solid.
Reaction SMILES: [CH2:1]([N:5]1[C:10](=[O:11])[C:9]2[CH:12]=[C:13]([CH2:15][CH3:16])[S:14][C:8]=2[NH:7][C:6]1=[O:17])[CH2:2][CH2:3][CH3:4].Br[CH2:19][C:20]1[CH:25]=[CH:24][C:23]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=2[C:32]2[N:36]=[C:35](C(Cl)(Cl)Cl)[O:34][N:33]=2)=[CH:22][CH:21]=1.CN(C)C=[O:44].[H-].[Na+]>C(OCC)(=O)C>[CH2:1]([N:5]1[C:10](=[O:11])[C:9]2[CH:12]=[C:13]([CH2:15][CH3:16])[S:14][C:8]=2[N:7]([CH2:19][C:20]2[CH:25]=[CH:24][C:23]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=3[C:32]3[NH:36][C:35](=[O:44])[O:34][N:33]=3)=[CH:22][CH:21]=2)[C:6]1=[O:17])[CH2:2][CH2:3][CH3:4]
Reactant: ClC(Cl)(Cl)c1nc(-c2ccccc2-c2ccc(CBr)cc2)no1
Reactant: CCCCn1c(=O)[nH]c2sc(CC)cc2c1=O
Reactant: CN(C)C=O
Agent: [H-]
Agent: [Na+]
Solvent: CCOC(C)=O
Product: CCCCn1c(=O)c2cc(CC)sc2n(Cc2ccc(-c3ccccc3-c3noc(=O)[nH]3)cc2)c1=O
Temperature: 50 °C
Reaction time: 1 h
Yield: 58 %

Procedure:
To a mixture of 3-butyl-6-ethylthieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (1 g), 3-[4′-(bromomethyl)biphenyl-2-yl]-5-(trichloromethyl)-1,2,4-oxadiazole (1.89 g) and N,N-dimethylformamide (50 mL) was added sodium hydride (0.17 g), and the mixture was stirred at 50° C. for 1 hr. The reaction mixture was diluted with ethyl acetate, washed successively with 5% aqueous potassium hydrogensulfate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. To the obtained residue was added 1N aqueous sodium hydroxide solution (50 mL), and the mixture was stirred at 60° C. for 1 hr. The reaction mixture was adjusted to pH 4 with 1N hydrochloric acid, extracted with ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography, and the obtained solid was recrystallized from tetrahydrofuran-diisopropylether to give the title compound as colorless crystals (1.13 g, 58%).
Reaction SMILES: [Br:1][C:2]([Br:5])(Br)Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Si:25]([O:42][C@@H:43]1[CH2:60][CH2:59][C@@:58]2([CH3:61])[C@@H:45]([CH2:46][CH2:47][C@@H:48]3[C@@H:57]2[CH2:56][CH2:55][C@@:53]2([CH3:54])[C@H:49]3[CH2:50][CH2:51][C@@H:52]2[CH:62]=O)[CH2:44]1)([C:38]([CH3:41])([CH3:40])[CH3:39])([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>C(Cl)Cl.C(OCC)(=O)C>[Br:1][C:2]([Br:5])=[CH:62][C@H:52]1[CH2:51][CH2:50][C@H:49]2[C@H:48]3[C@H:57]([CH2:56][CH2:55][C@:53]12[CH3:54])[C@:58]1([CH3:61])[C@H:45]([CH2:44][C@H:43]([O:42][Si:25]([C:38]([CH3:39])([CH3:41])[CH3:40])([C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:60][CH2:59]1)[CH2:46][CH2:47]3
Reactant: BrC(Br)(Br)Br
Reactant: CC(C)(C)[Si](O[C@@H]1CC[C@@]2(C)[C@@H](CC[C@@H]3[C@@H]2CC[C@]2(C)[C@@H](C=O)CC[C@@H]32)C1)(c1ccccc1)c1ccccc1
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: ClCCl
Solvent: CCOC(C)=O
Product: CC(C)(C)[Si](O[C@@H]1CC[C@@]2(C)[C@@H](CC[C@@H]3[C@@H]2CC[C@]2(C)[C@@H](C=C(Br)Br)CC[C@@H]32)C1)(c1ccccc1)c1ccccc1
Temperature: 0 °C
Reaction time: 0.17 h

Procedure:
To a solution of tetrabromomethane (1.99 g, 6 mmol) in anhydrous methylene chloride (31 mL) was added at 0° C., triphenylphosphine (3.14 g, 6 mmol) and the resulting mixture is stirred for 10 min. Subsequently, a solution of 3α-(t-butyidiphenylsilyloxy)-5α-androstan-17β-carboxaldehyde (540 mg, 1 mmol) in methylene chloride (6 mL) was added and the mixture was stirred at 0° C. for an additional 10 min. The reaction mixture was diluted with ethyl acetate and the organic layer is washed with water, saturated aqueous NaCl solution and was dried with anhydrous Na2SO4. The solvent was evaporated in vacuo and the residue was purified with flash column chromatography using petroleum ether/ether 95/5 as eluent afforded the desired compound named.
Reaction SMILES: [Cl:1][C:2]1[CH:26]=[CH:25][C:24](I)=[CH:23][C:3]=1[N:4]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=1)[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][CH:7]=1.C([Mg]Cl)(C)C.CON(C)[C:36]([C:38]1([CH3:41])[CH2:40][CH2:39]1)=[O:37]>C1COCC1.C(OCC)C>[CH3:13][O:12][C:9]1[CH:10]=[CH:11][C:6]([CH2:5][N:4]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=2)[C:3]2[CH:23]=[C:24]([C:36]([C:38]3([CH3:41])[CH2:40][CH2:39]3)=[O:37])[CH:25]=[CH:26][C:2]=2[Cl:1])=[CH:7][CH:8]=1
Reactant: CON(C)C(=O)C1(C)CC1
Reactant: COc1ccc(CN(Cc2ccc(OC)cc2)c2cc(I)ccc2Cl)cc1
Agent: CC(C)[Mg]Cl
Solvent: CCOCC
Solvent: C1CCOC1
Product: COc1ccc(CN(Cc2ccc(OC)cc2)c2cc(C(=O)C3(C)CC3)ccc2Cl)cc1
Temperature: -78 °C
Reaction time: 0.5 h

Procedure:
Under argon, 7.587 g (15.37 mmol) of 2-chloro-5-iodo-N,N-bis(4-methoxybenzyl)aniline were dissolved in 100 ml of THF and cooled to −78° C. 7.65 ml (15.27 mmol) of a 2 M solution of isopropylmagnesium chloride in diethyl ether were then slowly added dropwise. The reaction solution was then slowly warmed to −40° C. and stirred at this temperature for 30 min. 2 g (13.97 mmol) of N-methoxy-N,1-dimethylcyclopropanecarboxamide [R. Shintani et al., Chem. Eur. J., 15 (35), 8692-8694 (2009)], dissolved in 20 ml of THF, were then slowly added dropwise to the reaction solution. The reaction mixture obtained was then slowly warmed to room temperature and stirred at this temperature overnight. 50 ml of an ice-cold saturated aqueous ammonium chloride solution were then added to the reaction mixture. After separation of the phases, the aqueous phase was extracted three more times with ethyl acetate, and the combined organic phases were dried over magnesium sulphate, filtered and evaporated to dryness. The crude product obtained was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 10:1). This gave 3.977 g (63% of theory) of the title compound.
Reaction SMILES: C(OC([N:8]1[CH2:12][CH2:11][C@H:10]([NH:13][C:14](=[O:33])[CH2:15][NH:16][C:17]([NH:19][C:20]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=2)=[O:21])=[NH:18])[CH2:9]1)=O)(C)(C)C.[S:34](=[O:38])(=[O:37])([OH:36])[OH:35].C(OC(C)C)(C)C>CO>[S:34]([O:36][S:34]([OH:37])(=[O:36])=[O:35])([OH:35])(=[O:38])=[O:37].[N+:30]([C:27]1[CH:28]=[CH:29][C:24]([CH2:23][O:22][C:20]([NH:19][C:17](=[NH:18])[NH:16][CH2:15][C:14]([NH:13][C@H:10]2[CH2:11][CH2:12][NH:8][CH2:9]2)=[O:33])=[O:21])=[CH:25][CH:26]=1)([O-:32])=[O:31]
Reactant: CC(C)(C)OC(=O)N1CC[C@H](NC(=O)CNC(=N)NC(=O)OCc2ccc([N+](=O)[O-])cc2)C1
Reactant: O=S(=O)(O)O
Solvent: CC(C)OC(C)C
Solvent: CO
Product: N=C(NCC(=O)N[C@H]1CCNC1)NC(=O)OCc1ccc([N+](=O)[O-])cc1
Product: O=S(=O)(O)OS(=O)(=O)O
Temperature: 42.5 °C
Reaction time: 2.5 h
Yield: 80.2 %

Procedure:
(S)-1-(t-butyloxycarbonyl)-3-[2-[3-(4-nitrobenzyloxycarbonyl)guanidino]acetylamino]pyrrolidine ½ sulfate (350 g, purity 86%) was added to a solution of concentrated sulfuric acid (234 g) and methanol (2.45 L) and the mixture was stirred at from 40 to 45° C. for 2.5 hours. The reaction mixture was cooled to from 20 to 30° C., and then was stirred at the same temperature for 0.5 hours. Diisopropyl ether (3.5 L) was added to the mixture, which was stirred at the same temperature for 1 hour. The crystals which precipitated were collected by filtration to give the title compound (328 g, purity 95.8%, yield 95.4%)
Reaction SMILES: [N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][S:13][C:14]1[NH:15][C:16]2[CH:22]=[CH:21][CH:20]=[CH:19][C:17]=2[N:18]=1.[C:23](=O)([O-])[O-].[K+].[K+].CI.O>CN(C=O)C>[CH3:23][N:18]1[C:17]2[CH:19]=[CH:20][CH:21]=[CH:22][C:16]=2[N:15]=[C:14]1[S:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][O:7][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][N:1]=1
Reactant: O=C([O-])[O-]
Reactant: c1ccc(OCCCCCSc2nc3ccccc3[nH]2)nc1
Agent: [K+]
Solvent: CI
Solvent: CN(C)C=O
Solvent: O
Product: Cn1c(SCCCCCOc2ccccn2)nc2ccccc21
Temperature: 50 °C
Reaction time: 1.5 h
Yield: 72 %

Procedure:
0.2 g of (Compound 1) was dissolved in 1.2 ml of DMF, added with 0.27 g of potassium carbonate and 0.12 g of methyl iodide and the mixture was stirred at 50° C. for 1.5 hours. The reaction mixture was added with water and extracted with ethyl acetate. The organic layer was washed with water and dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (ethyl acetate:methylene chloride=1:6) to obtain 0.15 g of the title compound (yield: 72%).
Reaction SMILES: [CH3:1][C:2]1([C:9]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[CH:12]=[CH:11][CH:10]=2)[NH:6][C:5](=[O:7])[NH:4][C:3]1=[O:8].[C:19]1([C:25]([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[N:26]2[CH:30]=[C:29]([CH2:31][CH2:32][CH2:33]O)[N:28]=[CH:27]2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1>[C:41]1([C:25]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)([C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[N:26]2[CH:30]=[C:29]([CH2:31][CH2:32][CH2:33][N:4]3[C:3](=[O:8])[C:2]([CH3:1])([C:9]4[C:18]5[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=5)[CH:12]=[CH:11][CH:10]=4)[NH:6][C:5]3=[O:7])[N:28]=[CH:27]2)[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1
Reactant: OCCCc1cn(C(c2ccccc2)(c2ccccc2)c2ccccc2)cn1
Reactant: CC1(c2cccc3ccccc23)NC(=O)NC1=O
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: C1CCOC1
Product: CC1(c2cccc3ccccc23)NC(=O)N(CCCc2cn(C(c3ccccc3)(c3ccccc3)c3ccccc3)cn2)C1=O
Reaction time: 24 h
Yield: 79.2 %

Procedure:
0.60 g(2.5 mmol) of 5-methyl-5-naphthalen-1-yl-imidazolidin-2,4-dione prepared in Preparation 1, 1.02 g(2.76 mmol) of 3-(1-triphenylmethyl-imidazol-4-yl)-propanol and 0.87 g(3.3 mmol) of triphenylphosphine (Ph3P) were dissolved in 50 ml of tetrahydrofuran. 0.52 ml(3.3 mmol) of diethylazodicarboxylate[DEAD] was added thereto and the resulting solution was stirred for 24 hours. Tetrahydrofuran was removed under reduced pressure and the residue was subjected to chromatography using ethyl acetate the eluent to obtain 1.17 g(Yield: 80%) of the title compound.
Reaction SMILES: [CH2:1]([Li])CCC.C(NC(C)C)(C)C.[C:13](#[N:17])[CH:14]([CH3:16])[CH3:15].Br[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35]C.[Cl-].[NH4+]>O1CCCC1.C(OCC)C>[C:13]([C:14]([CH3:1])([CH2:16][CH2:35][CH2:34][CH2:33][CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH3:19])[CH3:15])#[N:17]
Reactant: CC(C)C#N
Reactant: [Li]CCCC
Reactant: CCCCCCCCCCCCCCCCCCBr
Agent: [Cl-]
Agent: [NH4+]
Solvent: CC(C)NC(C)C
Solvent: C1CCOC1
Solvent: CCOCC
Product: CCCCCCCCCCCCCCCCCCC(C)(C)C#N
Reaction time: 0.25 h

Procedure:
To a solution of 24 mL of a 2.5M n-butyllithium solution in hexanes and 60 mL of tetrahydrofuran at -78° C. is added dropwise 6.07 g of diisopropylamine. After the reaction mixture is stirred at this temperature for 15 minutes, a solution of 5.5 mL of isobutyronitrile in 60 mL of tetrahydrofuran is added dropwise and the resultant reaction mixture is stirred for 2 hours at -78° C. To the reaction mixture at room temperature is added a solution of 20 g of 1-bromooctadecane in 50 mL of tetrahydrofuran. The reaction mixture is stirred for 18 hours at room temperature and then 100 mL of saturated ammonium chloride is added. To the reaction mixture is added 100 mL of diethyl ether and the organic phase is separated. The organic phase is dried over anhydrous magnesium sulfate and the solvent is removed in vacuo to give 18.2 g of the title compound as a white solid. The 1H NMR spectrum is consistent with the desired product.
Reaction SMILES: [NH:1]=[C:2]=N.[Cl:4][C:5]1[C:10]([F:11])=[CH:9][CH:8]=[CH:7][C:6]=1[NH:12][C:13]([NH:15][C:16]1[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([S:23]([N:26]([CH3:28])[CH3:27])(=[O:25])=[O:24])[C:17]=1[O:29][Si](C(C)(C)C)(C)C)=S.CS(Cl)(=O)=O.C([N:44](CC)CC)C>>[Cl:22][C:19]1[CH:20]=[CH:21][C:16]([N:15]([C:2]#[N:1])[C:13]([NH:12][C:6]2[CH:7]=[CH:8][CH:9]=[C:10]([F:11])[C:5]=2[Cl:4])=[NH:44])=[C:17]([OH:29])[C:18]=1[S:23]([N:26]([CH3:28])[CH3:27])(=[O:24])=[O:25]
Reactant: CN(C)S(=O)(=O)c1c(Cl)ccc(NC(=S)Nc2cccc(F)c2Cl)c1O[Si](C)(C)C(C)(C)C
Reactant: N=C=N
Reactant: CCN(CC)CC
Agent: CS(=O)(=O)Cl
Product: CN(C)S(=O)(=O)c1c(Cl)ccc(N(C#N)C(=N)Nc2cccc(F)c2Cl)c1O

Procedure:
Following the general procedure for carbodiimide formation outlined in example 12, N-(2-chloro-3-fluorophenyl)-N′-[4-chloro-2-tert-butyldimethylsilyloxy-3-(N″,N″-dimethylaminosulfonyl)phenyl]thiourea (367 mg, 0.67 mmol), methanesulfonyl chloride (0.12 mL, 1.38 mmol) and triethylamine (0.2 mL, 1.04 mmol) were reacted to form the desired product (360 mg, crude). 1H NMR (CDCl3) δ 0.36 (s, 6H), 1.03 (s, 9H), 1.2.87 (s, 6H), 7.01 (m, 2H), 7.09 (d, 1H), 7.21 (m, 1H), 7.34 (d, 1H).
Reaction SMILES: [C:1]([C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].ClC(Cl)C.[Pb](=O)=[O:17]>[Ti].[Ni].S(=O)(=O)(O)O>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([CH:11]=[O:17])=[CH:9][CH:10]=1)([CH3:4])([CH3:3])[CH3:2]
Reactant: Cc1ccc(C(C)(C)C)cc1
Reactant: O=[Pb]=O
Agent: [Ni]
Agent: [Ti]
Agent: O=S(=O)(O)O
Solvent: CC(Cl)Cl
Product: CC(C)(C)c1ccc(C=O)cc1

Procedure:
2.5 ml of p-tert.butyltoluene, 10 ml of dichloroethane and 110 ml of 10N sulphuric acid are emulsified while stirring magnetically in a glass vessel provided with a cover. Expanded titanium metal (5×5 cm) coated with lead dioxide [lead dioxide-titanium composite electrode described in "Zeitschrift fur Naturforschung" 31 b, 39-50 (1976)] is used as the anode and the cathode is a nickel wire at a distance of 3 cm from the anode. A voltage of 3.4 volt is applied between the electrodes, whereupon a current of 50 mA is set. The temperature is held at 25° C. by external cooling. After the throughput of 1.55 aH, corresponding to 100% of the theoretically required current, the electrolysis is discontinued. The solution is extracted three times with 60 ml of chloroform each time and the combined extracts are analysed quantitatively by gas chromatography. With a conversion of 83% there is obtained a yield of p-tert.butylbenzaldehyde which amounts to 77% of theory.