Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [F:1][C:2]1[CH:13]=[CH:12][C:5]([O:6][CH2:7][CH2:8][CH:9]([OH:11])[CH3:10])=[CH:4][CH:3]=1.[CH3:14][S:15](Cl)(=[O:17])=[O:16]>N1C=CC=CC=1>[CH3:14][S:15]([O:11][CH:9]([CH2:8][CH2:7][O:6][C:5]1[CH:12]=[CH:13][C:2]([F:1])=[CH:3][CH:4]=1)[CH3:10])(=[O:17])=[O:16]
Reactant: CC(O)CCOc1ccc(F)cc1
Reactant: CS(=O)(=O)Cl
Solvent: c1ccncc1
Product: CC(CCOc1ccc(F)cc1)OS(C)(=O)=O
Reaction time: 1 h
Yield: 64 %

Procedure:
To a stirred and cooled mixture of 10 parts of 4-(4-fluorophenoxy)-2-butanol and 30 parts of pyridine were added portionwise 7.4 parts of methanesulfonyl chloride at a temperature below 10° C. Upon completion, stirring was continued for 1 hour at room temperature. The reaction mixture was allowed to stand overnight in an ice-box. Then it was poured onto water and the product was extracted with dichloromethane. The extract was washed with a cold hydrochloric acid solution 20% and with water, dried, filtered and evaporated. The oily residue was purified by column-chromatography over silica gel using a mixture of trichloromethane and methanol (95:5 by volume) as eluent. The pure fractions were collected and the eluent was evaporated, yielding 10 parts (64%) of 4-(4-fluorophenoxy)-2-butanol methanesulfonate (ester) as an oily residue (intermediate 28).
Reaction SMILES: FC(F)(F)C(O)=O.[Cl:8][C:9]1[CH:14]=[C:13]2[NH:15][C:16](=[O:38])[C:17]3([CH:21]([C:22]4[CH:27]=[CH:26][CH:25]=[C:24]([Cl:28])[C:23]=4[F:29])[CH:20]([C:30](O)=[O:31])[NH:19][CH:18]3[CH2:33][C:34]([CH3:37])([CH3:36])[CH3:35])[C:12]2=[CH:11][CH:10]=1.C(N(C(C)C)CC)(C)C.C1(P(Cl)(C2C=CC=CC=2)=O)C=CC=CC=1.[C:63]([O:67][C:68]([C:70]1[N:71]([CH3:76])[C:72]([NH2:75])=[CH:73][CH:74]=1)=[O:69])([CH3:66])([CH3:65])[CH3:64]>>[C:63]([O:67][C:68]([C:70]1[N:71]([CH3:76])[C:72]([NH:75][C:30]([C@@H:20]2[NH:19][C@@H:18]([CH2:33][C:34]([CH3:37])([CH3:36])[CH3:35])[C@:17]3([C:12]4[C:13](=[CH:14][C:9]([Cl:8])=[CH:10][CH:11]=4)[NH:15][C:16]3=[O:38])[C@H:21]2[C:22]2[CH:27]=[CH:26][CH:25]=[C:24]([Cl:28])[C:23]=2[F:29])=[O:31])=[CH:73][CH:74]=1)=[O:69])([CH3:66])([CH3:65])[CH3:64]
Reactant: Cn1c(N)ccc1C(=O)OC(C)(C)C
Reactant: CC(C)(C)CC1NC(C(=O)O)C(c2cccc(Cl)c2F)C12C(=O)Nc1cc(Cl)ccc12
Agent: O=P(Cl)(c1ccccc1)c1ccccc1
Solvent: O=C(O)C(F)(F)F
Solvent: CCN(C(C)C)C(C)C
Product: Cn1c(NC(=O)[C@@H]2N[C@@H](CC(C)(C)C)[C@@]3(C(=O)Nc4cc(Cl)ccc43)[C@H]2c2cccc(Cl)c2F)ccc1C(=O)OC(C)(C)C
Yield: 35.9 %

Procedure:
In a manner similar to the method described in Example 5, rac-(2′S,3′R,4′S,5′R)-6-chloro-4′-(3-chloro-2-fluoro-phenyl)-2′-(2,2-dimethyl-propyl)-2-oxo-1,2-dihydro-spiro[indole-3,3′-pyrrolidine]-5′-carboxylic acid trifluoroacetic acid prepared in Example 4 (0.3 g, 0.52 mmol), was reacted with diisopropylethylamine (0.34 g, 2.6 mmol), diphenylphosphinic chloride (0.25 g, 1 mmol), then reacted with 5-amino-1-methyl-1H-pyrrole-2-carboxylic acid tert-butyl ester prepared in Example 193 (0.15 g, 0.78 mmol) to give rac-5-{[(2′S,3′R,4′S,5′R)-6-chloro-4′-(3-chloro-2-fluoro-phenyl)-2′-(2,2-dimethyl-propyl)-2-oxo-1,2-dihydro-spiro[indole-3,3′-pyrrolidine]-5′-carbonyl]amino}-1-methyl-1H-pyrrole-2-carboxylic acid tert-butyl ester as a yellow solid (Yield 0.12 g, 36%).
Reaction SMILES: ClC1C=CC=C(C(OO)=[O:9])C=1.[Br:12][C:13]1[CH:18]=[CH:17][C:16]([CH:19]2[C:24](=[O:25])[C:23]([CH3:27])([CH3:26])[S:22][C:21]([CH3:29])([CH3:28])[C:20]2=[O:30])=[C:15]([CH2:31][CH3:32])[CH:14]=1>ClCCl.O>[Br:12][C:13]1[CH:18]=[CH:17][C:16]([CH:19]2[C:24](=[O:25])[C:23]([CH3:26])([CH3:27])[S:22](=[O:9])[C:21]([CH3:29])([CH3:28])[C:20]2=[O:30])=[C:15]([CH2:31][CH3:32])[CH:14]=1
Reactant: CCc1cc(Br)ccc1C1C(=O)C(C)(C)SC(C)(C)C1=O
Reactant: O=C(OO)c1cccc(Cl)c1
Solvent: O
Solvent: ClCCl
Product: CCc1cc(Br)ccc1C1C(=O)C(C)(C)S(=O)C(C)(C)C1=O
Temperature: 0 °C
Reaction time: 1 h
Yield: 54.6 %

Procedure:
A solution of 3-chloroperbenzoic acid (2.45 g, 0.0142 mol) in dichloromethane (40 ml) is added to a pre-cooled solution (0° C.) of 4-(4-bromo-2-ethylphenyl)-2,2,6,6-tetramethyl-thiopyran-3,5-dione (3.5 g, 0.0095 mol) in dichloromethane (100 ml). The reaction mixture is stirred at 0° C. for one hour and then allowed to come to room temperature. The reaction mixture is stirred at room temperature for one hour, diluted with water (100 ml) and separated. The organic phase is collected, and the aqueous layer is extracted with dichloromethane (2×50 ml). The organic phases are combined, washed with water, and dried over anhydrous sodium sulfate. The mixture is filtered, and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give 4-(4-bromo-2-ethylphenyl)-2,2,6,6-tetramethyl-1-oxo-dihydrothiopyran-3,5-dione as a white solid (2.0 g).
Reaction SMILES: C(OC([N:8]1[CH2:13][CH2:12][O:11][CH2:10][C@@H:9]1[CH2:14][O:15][C:16]([N:18]1[CH2:23][CH2:22][N:21]([C:24]2[CH:29]=[CH:28][C:27]([F:30])=[CH:26][CH:25]=2)[CH2:20][CH2:19]1)=[O:17])=O)(C)(C)C.Cl>O1CCOCC1>[F:30][C:27]1[CH:28]=[CH:29][C:24]([N:21]2[CH2:20][CH2:19][N:18]([C:16]([O:15][CH2:14][C@H:9]3[CH2:10][O:11][CH2:12][CH2:13][NH:8]3)=[O:17])[CH2:23][CH2:22]2)=[CH:25][CH:26]=1
Reactant: CC(C)(C)OC(=O)N1CCOC[C@@H]1COC(=O)N1CCN(c2ccc(F)cc2)CC1
Agent: Cl
Solvent: C1COCCO1
Product: O=C(OC[C@H]1COCCN1)N1CCN(c2ccc(F)cc2)CC1
Temperature: 25 °C
Reaction time: 24 h
Yield: 99.7 %

Procedure:
(3R)-3-[4-(4-Fluorophenyl)-piperazine-1-carbonyloxymethyl]-morpholine-4-carboxylic acid tert-butyl ester (5.07 g, 12.0 mmol) was stirred in dry dioxane (35 mL) at room temperature and HCl in dioxane (4M; 15 mL, 60 mmol) was added dropwise. The reaction mixture was stirred for 24 h at room temperature. A further portion of HCl in dioxane (4M; 10 mL, 40 mmol) was added and stirred overnight. The dioxane was decanted and the residual gum was washed with dioxane (×3) and Et2O (×2). The residue was partitioned between DCM (300 mL) and 1.2M aqueous NaHCO3. The aqueous layer was extracted with DCM (2×200 mL). The combined DCM extracts were dried (Na2SO4) and the solvent removed in vacuo. The residue was dissolved in DCM and dried in vacuo to give (3R)-morpholin-3-ylmethyl 4-(4-fluorophenyl)piperazine-1-carboxylate (3.87 g, quant.) as an off white solid.
Reaction SMILES: [NH2:1][C:2]1[N:6](C)[N:5]=[C:4](C)[CH:3]=1.F[C:10]1[CH:27]=CC(C=C(C(=O)C(C)C)C(OCC)=O)=C[CH:11]=1>>[NH:6]1[C:2]2=[N:1][CH:11]=[CH:10][CH:27]=[C:3]2[CH2:4][NH:5]1
Reactant: CCOC(=O)C(=Cc1ccc(F)cc1)C(=O)C(C)C
Reactant: Cc1cc(N)n(C)n1
Product: c1cnc2c(c1)CNN2
Temperature: 130 °C

Procedure:
2.22 g (0.02 mol) of 5-amino-1,3-dimethylpyrazole and 5.3 g (0.02 mol) of ethyl 2-(4'-fluorobenzylidene)-4-methyl-3-oxo-pentanoate were mixed and heated at about 130° C. for one hour. Substances having a low boiling point were distilled off under reduced pressure by a rotary evaporator. Then, the reaction mixture was dissolved in chloroform, washed with a sodium carbonate aqueous solution and with water and dried over anhydrous magnesium sulfate. Chloroform was evaporated, and the residual oil was purified by silica gel column chromatography to obtain dihydropyrazolo[3,4-b]pyridine (XI 1).
Reaction SMILES: [NH:1]1[C:5]2[CH:6]=[C:7]([C:10]3[O:14][C:13]([SH:15])=[N:12][N:11]=3)[CH:8]=[CH:9][C:4]=2[N:3]=[CH:2]1.Cl.[N:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[CH2:23]Cl>CCO>[N:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[CH2:23][S:15][C:13]1[O:14][C:10]([C:7]2[CH:8]=[CH:9][C:4]3[NH:3][CH:2]=[N:1][C:5]=3[CH:6]=2)=[N:11][N:12]=1
Reactant: ClCc1ccccn1
Reactant: Sc1nnc(-c2ccc3nc[nH]c3c2)o1
Agent: Cl
Solvent: CCO
Product: c1ccc(CSc2nnc(-c3ccc4[nH]cnc4c3)o2)nc1

Procedure:
1 (0.33 g, 1.5 mmol), TEA (0.418 mL, 3.0 mmol) and (pyridin-2-yl)methylchloride hydrochloride (0.246 g, 1.5 mmol) were dissolved in 10 mL of EtOH and kept under reflux overnight. The solvent was removed and the remaining oil was purified by flash-chromatography on silica gel, applying a CHCl3/MeOH gradient.
Reaction SMILES: [CH2:1]([O:3][C:4]1[CH:5]=[C:6]([CH:10]=[C:11]([O:13][CH2:14][CH3:15])[CH:12]=1)[C:7]([OH:9])=O)[CH3:2].[NH2:16][C:17]1[S:18][CH:19]=[C:20]([CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[N:21]=1>>[CH2:26]([O:25][C:23](=[O:24])[CH2:22][C:20]1[N:21]=[C:17]([NH:16][C:7](=[O:9])[C:6]2[CH:10]=[C:11]([O:13][CH2:14][CH3:15])[CH:12]=[C:4]([O:3][CH2:1][CH3:2])[CH:5]=2)[S:18][CH:19]=1)[CH3:27]
Reactant: CCOC(=O)Cc1csc(N)n1
Reactant: CCOc1cc(OCC)cc(C(=O)O)c1
Product: CCOC(=O)Cc1csc(NC(=O)c2cc(OCC)cc(OCC)c2)n1
Yield: 84.6 %

Procedure:
[2-(3,5-Diethoxy-benzoylamino)-thiazol-4-yl]-acetic acid ethyl ester (80 mg, 86%) was prepared from 3,5-diethoxybenzoic acid (52 mg, 0.25 mmol) and ethyl 2-aminothiazol-4-ylacetate (93 mg) following synthetic description A.
Reaction SMILES: [CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([OH:11])=[CH:7][CH:6]=1.C(=O)([O-])[O-].[K+].[K+].[CH2:19](Br)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CC(C)=O>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([O:11][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[CH:7][CH:6]=1
Reactant: BrCc1ccccc1
Reactant: COC(=O)Cc1ccc(O)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC(C)=O
Product: COC(=O)Cc1ccc(OCc2ccccc2)cc1
Temperature: 90 °C
Yield: 92.3 %

Procedure:
A mixture of (4-hydroxy-phenyl)-acetic acid methyl ester (5.0 g, 30.0 mmol) and potassium carbonate (5.0 g, 36.1 mmol) in acetone (10 mL) was treated with benzyl bromide (4.29 mL, 36.1 mmol). The reaction mixture was then heated at 90° C. for 6 h. At this time, the potassium carbonate was removed by filtration. The filtrate was concentrated in vacuo. Flash chromatography (Merck Silica gel 60, 230-400 mesh, 95/5 hexanes/ethyl acetate) afforded (4-benzyloxy-phenyl)-acetic acid methyl ester (7.1 g, 92.1%) as a clear oil: EI-HRMS m/e calcd for C16H16O3 (M+) 256.1099 found 256.1103.
Reaction SMILES: CN1CCCCC1.[CH3:8][C:9]1[CH:26]=[CH:25][C:12]([CH2:13][O:14][C:15]([NH:17][C@H:18]([C:22]([OH:24])=O)[CH:19]([CH3:21])[CH3:20])=[O:16])=[CH:11][CH:10]=1.ClC(OCC(C)C)=O.[C:35]([C:37]1[CH:47]=[CH:46][C:40]([O:41][CH2:42][CH:43]([NH2:45])[CH3:44])=[CH:39][CH:38]=1)#[N:36]>C(Cl)Cl.O>[C:35]([C:37]1[CH:47]=[CH:46][C:40]([O:41][CH2:42][CH:43]([NH:45][C:22](=[O:24])[C@H:18]([CH:19]([CH3:20])[CH3:21])[NH:17][C:15]([O:14][CH2:13][C:12]2[CH:11]=[CH:10][C:9]([CH3:8])=[CH:26][CH:25]=2)=[O:16])[CH3:44])=[CH:39][CH:38]=1)#[N:36]
Reactant: Cc1ccc(COC(=O)N[C@H](C(=O)O)C(C)C)cc1
Reactant: CC(N)COc1ccc(C#N)cc1
Agent: CC(C)COC(=O)Cl
Solvent: ClCCl
Solvent: O
Solvent: CN1CCCCC1
Product: Cc1ccc(COC(=O)N[C@H](C(=O)NC(C)COc2ccc(C#N)cc2)C(C)C)cc1
Temperature: -20 °C
Reaction time: 1 h
Yield: 25.1 %

Procedure:
0.6 g of N-methylpiperidine was added to a solution containing 1.5 g of N-(4-methylbenzyloxycarbonyl)-L-valine dissolved in 100 ml of methylene chloride, at -20° C. After the mixture was stirred for 10 minutes at the same temperature, 0.8 g of isobutyl chloroformate was added to the mixture, and stirred for 1 hour at -20° C. 1.0 g of 2-(4-cyanophenoxy)-1-methylethylamine was added to this mixture at -60° C., and then the reaction mixture was allowed to sit and warm naturally to room temperature while being stirred, and was stirred for 20 hours at room temperature. Water was subsequently added to the reaction mixture. After the methylene chloride layer was washed successively with a 5% aqueous solution of sodium bicarbonate and water, the organic layer was dried over anhydrous magnesium sulfate and the methylene chloride was removed under reduced pressure. The residue, which was a crude crystal, was purified by column chromatography on silica gel, thus obtaining 0.6 g of the desired product in the form of light white powder (yield: 28%).
Reaction SMILES: Cl.N1C=CC=CC=1.[Cl:8][C:9]1[C:14]([Cl:15])=[C:13]([C:16](=[O:23])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:12]=[CH:11][C:10]=1[O:24]C>>[Cl:8][C:9]1[C:14]([Cl:15])=[C:13]([C:16](=[O:23])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:12]=[CH:11][C:10]=1[OH:24]
Reactant: COc1ccc(C(=O)c2ccccc2)c(Cl)c1Cl
Agent: Cl
Solvent: c1ccncc1
Product: O=C(c1ccccc1)c1ccc(O)c(Cl)c1Cl
Temperature: 180 °C
Reaction time: 2 h

Procedure:
4.3 g of pyridinehydrochloride salt was added to 500 mg of the obtained anisole compound. The mixture was stirred for two hours at 180° C., and poured into ice-water and extracted with ether.
Reaction SMILES: [OH-].[K+].[Br:3][C:4]1[CH:5]=[C:6]([O:12]C(=O)C)[CH:7]=[CH:8][C:9]=1[O:10][CH3:11]>O.CO>[Br:3][C:4]1[CH:5]=[C:6]([OH:12])[CH:7]=[CH:8][C:9]=1[O:10][CH3:11]
Reactant: COc1ccc(OC(C)=O)cc1Br
Agent: [K+]
Agent: [OH-]
Solvent: CO
Solvent: O
Product: COc1ccc(O)cc1Br
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 98.1 %

Procedure:
A solution of potassium hydroxide (290 mg, 5.19 mmol) in water (2.5 mL) was added to a solution of acetic acid 3-bromo-4-methoxy-phenyl ester (1.2 g, 4.9 mmol) in methanol (18.5 mL). Mixture was stirred at ambient temperature for 30 min, then solvents were removed in vacuo and water (40 mL) added. The mixture was made acidic by drop-wise addition of 1.2 M aq HCl solution (4.3 mL) and the mixture extracted with dichloromethane (2×40 mL). Combined organics were dried over sodium sulphate, filtered and filtrate solvents evaporated in vacuo to give the title compound (976 mg, 98%) as a pale yellow solid.
Reaction SMILES: [OH:1][CH:2]([C:7]1[CH:19]=[C:18]2[C:10]([CH:11]=[CH:12][C:13]3[O:14][C:15](=[O:22])[C:16]([CH3:21])([CH3:20])[C:17]=32)=[CH:9][CH:8]=1)[C:3]([F:6])([F:5])[F:4].N1C=CC=CC=1.[S:29](Cl)([C:32]1[CH:38]=[CH:37][C:35]([CH3:36])=[CH:34][CH:33]=1)(=[O:31])=[O:30].Cl>O>[CH3:21][C:16]1([CH3:20])[C:15](=[O:22])[O:14][C:13]2[CH:12]=[CH:11][C:10]3[C:18]([C:17]1=2)=[CH:19][C:7]([CH:2]([O:1][S:29]([C:32]1[CH:38]=[CH:37][C:35]([CH3:36])=[CH:34][CH:33]=1)(=[O:31])=[O:30])[C:3]([F:4])([F:6])[F:5])=[CH:8][CH:9]=3
Reactant: Cc1ccc(S(=O)(=O)Cl)cc1
Reactant: CC1(C)C(=O)Oc2ccc3ccc(C(O)C(F)(F)F)cc3c21
Agent: Cl
Solvent: O
Solvent: c1ccncc1
Product: Cc1ccc(S(=O)(=O)OC(c2ccc3ccc4c(c3c2)C(C)(C)C(=O)O4)C(F)(F)F)cc1
Temperature: 25 °C
Reaction time: 18 h

Procedure:
A mixture of 8-(1-hydroxy-2,2,2-trifluoroethyl)-1,1-dimethyl-2(1H)-naphtho[2,1-b]furanone (0.04 g), pyridine (0.5 ml) and tosyl chloride (0.04 g) was stirred at room temperature for 18 h and then heated at 50° for 6 h. The mixture was cooled to room temperature, treated with water (10 ml) and the mixture was stirred at room temperature for 5 minutes and acidified with 2N aqueous hydrochloric acid. The mixture was extracted with ethyl acetate and the extract was dried and evaporated to dryness under reduced pressure to give the required starting material, 1,1-dimethyl-8-(2,2,2-trifluoro-1-tosyloxyethyl)-2(1H)-naphtho[2,1-b]furanone, which was used without further purification. ##STR3##
Reaction SMILES: [C:1]1([C:7]2[N:8]([C:12]3[CH:17]=[CH:16][C:15]([C:18](=O)[CH2:19][CH2:20][C:21](O)=[O:22])=[CH:14][CH:13]=3)[CH:9]=[CH:10][N:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O.[NH2:26][NH2:27]>>[C:1]1([C:7]2[N:8]([C:12]3[CH:17]=[CH:16][C:15]([C:18]4[CH2:19][CH2:20][C:21](=[O:22])[NH:26][N:27]=4)=[CH:14][CH:13]=3)[CH:9]=[CH:10][N:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: NN
Reactant: O=C(O)CCC(=O)c1ccc(-n2ccnc2-c2ccccc2)cc1
Solvent: O
Product: O=C1CCC(c2ccc(-n3ccnc3-c3ccccc3)cc2)=NN1

Procedure:
Similarly, reaction of 4-(2-phenyl-1H-imidazol-1-yl)-γ-oxobenzenebutanoic acid with hydrazine hydrate according to the procedure of this Example gives 4,5-dihydro-6-[4-(2-phenyl-1H-imidazol-1-yl)phenyl]-3(2H)-pyridazinone.
Reaction SMILES: [S:1]1[CH:5]=[N:4][N:3]=[C:2]1[NH2:6].N1C=CC=CC=1.Cl[C:14]([O:16][CH2:17][C:18]([Cl:21])([Cl:20])[Cl:19])=[O:15].O>O1CCCC1>[S:1]1[CH:5]=[N:4][N:3]=[C:2]1[NH:6][C:14](=[O:15])[O:16][CH2:17][C:18]([Cl:21])([Cl:20])[Cl:19]
Reactant: O=C(Cl)OCC(Cl)(Cl)Cl
Reactant: Nc1nncs1
Solvent: C1CCOC1
Solvent: O
Solvent: c1ccncc1
Product: O=C(Nc1nncs1)OCC(Cl)(Cl)Cl
Temperature: 25 °C
Reaction time: 1 h
Yield: 79 %

Procedure:
To a solution of 1,3,4-thiadiazole-2-amine (1.00 g, 9.89 mmol) and pyridine (0.968 ml, 11.9 mmol) in tetrahydrofuran (33 ml) was added 2,2,2-trichloroethyl chloroformate (1.64 ml, 11.9 mmol) with ice-cooling and the mixture was stirred at room temperature for 1 hour. Water was poured into the reaction mixture and the mixture was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. Hexane was poured to the residue and a solid was collected by filtration to obtain the desired product (2.16 g, 79.1%).
Reaction SMILES: [N+:1]([C:4]1[CH:13]=[CH:12][CH:11]=[C:10]2[C:5]=1[C:6](=[O:15])[CH:7]=[CH:8][C:9]2=[O:14])([O-:3])=[O:2].[N+]([C:19]1[CH:20]=C2C(=[CH:27][CH:28]=1)C(=O)C=CC2=O)([O-])=O>O>[N+:1]([C:4]1[CH:13]=[CH:12][CH:11]=[C:10]2[C:5]=1[C:6](=[O:15])[C:7]1[CH2:20][CH2:19][CH2:28][CH2:27][C:8]=1[C:9]2=[O:14])([O-:3])=[O:2]
Reactant: O=C1C=CC(=O)c2c1cccc2[N+](=O)[O-]
Reactant: O=C1C=CC(=O)c2cc([N+](=O)[O-])ccc21
Solvent: O
Product: O=C1C2=C(CCCC2)C(=O)c2c1cccc2[N+](=O)[O-]
Yield: 87 %

Procedure:
49.6 g of a crude 5-nitronaphthoquinone cake (which had a water content of 50 wt% and a dry weight of 24.8 g, and comprised of 82 wt% of 5-nitronaphthoquinone and 10 wt% of 6-nitronaphthoquinone when determined under dried condition by a gas chromatography), 12.1 g of 1,3-butadiene and 49.6 g of benzene were introduced into an autoclave, which was then hermetically sealed for reaction at 80°C for 2.5 hours. The resultant reaction solution was cooled to 25°-30°C to crystalize 5-nitrotetrahydroanthraquinone, subjected to filtration, washed with 40 g of methanol, and dried to obtain 22.4 g of 5-nitrotetrahydroanthraquinone. The yield was 87.0% of the theoretical (based on the 5-nitronaphthoquinone contained in the crude starting material).
Reaction SMILES: [Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:12](=[O:13])[C:11]3[CH2:14][CH2:15][CH2:16][CH2:17][C:10]=3[C:9]2=[O:18])=[CH:4][C:3]=1[O:19][CH:20]([CH2:24][CH2:25][CH3:26])[C:21](=[O:23])[CH3:22].[CH2:27](O)[CH2:28][OH:29].C1(C)C=CC(S(O)(=O)=O)=CC=1.C1C=CC=CC=1>C(N(CC)CC)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:12](=[O:13])[C:11]3[CH2:14][CH2:15][CH2:16][CH2:17][C:10]=3[C:9]2=[O:18])=[CH:4][C:3]=1[O:19][CH:20]([CH2:24][CH2:25][CH3:26])[C:21]1([O:29][CH2:28][CH2:27][O:23]1)[CH3:22]
Reactant: CCCC(Oc1cc(N2C(=O)C3=C(CCCC3)C2=O)ccc1Br)C(C)=O
Reactant: OCCO
Agent: Cc1ccc(S(=O)(=O)O)cc1
Solvent: c1ccccc1
Solvent: CCN(CC)CC
Product: CCCC(Oc1cc(N2C(=O)C3=C(CCCC3)C2=O)ccc1Br)C1(C)OCCO1
Temperature: 25 °C
Reaction time: 5.5 h

Procedure:
A mixture of 1.5 g. of N-[4-bromo-3(1-propyl-2-oxopropoxy)phenyl]-3,4,5,6-tetrahydrophthalimide, 0.7 g. of ethyleneglycol, 0.1 g. of p-toluenesulfonic acid and 30 ml. of benzene was refluxed with stirring under removing water for 5.5 hours and the reaction mixture was cooled to room temperature and 0.4 ml. of triethylamine was added. The solvent was distilled off under a reduced pressure. The residue was purified by a chromatography on a column of silica gel (developing solvent: ethyl acetate:n-hexane:triethylamine of 30:80:1) to obtain 1.2 g. of Compound No. 49 shown in Table 1.
Reaction SMILES: [Al+3].[Cl-].[Cl-].[Cl-].[CH2:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH2:7][CH2:6]1.[C:14]1(=O)O[C:17](=[O:18])[CH2:16][CH2:15]1.Cl.S(=O)(=O)(O)O.[OH-].[Na+].P(Cl)(Cl)Cl.Cl[Sn](Cl)(Cl)Cl>ClCCl.[N+](C)([O-])=O.O1CCOCC1.C(O)C.CO.C(Cl)Cl.[Pd]>[CH2:5]1[C:13]2=[CH:12][C:11]3[CH2:14][CH2:15][CH2:16][C:17](=[O:18])[C:10]=3[CH:9]=[C:8]2[CH2:7][CH2:6]1
Reactant: O=C1CCC(=O)O1
Reactant: c1ccc2c(c1)CCC2
Agent: [Pd]
Agent: Cl
Agent: Cl[Sn](Cl)(Cl)Cl
Solvent: C[N+](=O)[O-]
Solvent: C1COCCO1
Solvent: ClCCl
Product: O=C1CCCc2cc3c(cc21)CCC3
Temperature: 2.5 °C
Reaction time: 1 h
Yield: 17.2 %

Procedure:
A suspension of 61 g (0.457 mol) of anhydrous AlCl3 in 188 ml of a dichloromethane/nitromethane=8/1 mixture is cooled to 0-5° C. and 22.15 g of indan and, in portions, 22.5 g (0.225 mol) of succinic anhydride are added thereto. After one hour at 0° C., the medium is poured into a water/ice mixture, hydrochloric acid at 37% is added until a clear solution is obtained. The medium is extracted with ethyl acetate, washed with water, the organic phase is dried and the solvent is evaporated off under reduced pressure. A white solid is obtained which is dissolved in 500 ml of dioxane. 4.6 ml of sulfuric acid at 98% in 50 ml of ethanol and 3.6 g of 10% Pd/C are added thereto. After 5 hours under a hydrogen atmosphere, the catalyst is filtered off, the solvent is evaporated off, the residue is taken up in water and the medium is extracted with ethyl acetate. The product obtained is dissolved in 20 ml of methanol and 8 ml of a 1 N aqueous sodium hydroxide solution are added thereto and the medium is stirred at room temperature for 2 hours. The solvent is evaporated off, water is added, the medium is brought to an acidic pH, it is extracted and a white solid is isolated. 38.7 g of this product are dissolved in 1000 ml of anhydrous methylene chloride under a nitrogen atmosphere; the medium is cooled to 0° C. and 47 g (0.225 mol) of PCl3 are carefully added thereto, the medium is stirred at 0° C. for two hours and 121.8 g (0.467 mol) of SnCl4 are slowly added thereto and, after 10 minutes, the medium is allowed to heat up to room temperature. After two hours at room temperature, the medium is poured into a water/ice mixture, extracted with methylene chloride and an oil is isolated which is then purified by chromatography on a silica gel column, eluting with a cyclohexane/ethyl acetate=8/2 mixture. 6.0 g of the title compound are obtained.
Reaction SMILES: [CH3:1][N:2]([CH3:17])[C:3](=[O:16])[C@@H:4]([NH:8]C(OC(C)(C)C)=O)[CH:5]([CH3:7])[CH3:6].[ClH:18]>O1CCOCC1>[ClH:18].[CH3:1][N:2]([CH3:17])[C:3](=[O:16])[C@@H:4]([NH2:8])[CH:5]([CH3:7])[CH3:6]
Reactant: CC(C)[C@H](NC(=O)OC(C)(C)C)C(=O)N(C)C
Agent: Cl
Solvent: C1COCCO1
Product: CC(C)[C@H](N)C(=O)N(C)C
Temperature: 0 °C
Reaction time: 7 h

Procedure:
0.85 g of 2(S)-tert-butoxycarbonylamino-3-methylbutanoic acid (N,N-dimethyl)amide is dissolved in 10 ml of 4N hydrochloric acid in dioxane at 0° C. and stirred for 7 hours at 0° C. The reaction mixture is lyophilised and the title compound is obtained: Rf (ethyl acetate/methanol/conc. ammonia=80:15:5)=0.23.
Reaction SMILES: [CH2:1]([NH:3][CH2:4][CH3:5])[CH3:2].[C:6]([B-:8]([C:13]#[N:14])([C:11]#[N:12])[C:9]#[N:10])#[N:7].[CH3:15][N:16]([C+:18]([N:20]([CH3:22])[CH3:21])Cl)[CH3:17]>O>[C:6]([B-:8]([C:13]#[N:14])([C:11]#[N:12])[C:9]#[N:10])#[N:7].[CH3:15][N:16]([CH3:17])[C:18]([N:20]([CH3:22])[CH3:21])=[N+:3]([CH2:4][CH3:5])[CH2:1][CH3:2]
Reactant: CCNCC
Reactant: CN(C)[C+](Cl)N(C)C
Agent: N#C[B-](C#N)(C#N)C#N
Solvent: O
Product: CC[N+](CC)=C(N(C)C)N(C)C
Yield: 97.4 %

Procedure:
10.5 g (143.6 mmol) of diethylamine are added with stirring and cooling to 12.0 g (47.9 mmol) of bis(dimethylamino)chlorocarbenium tetracyanoborate. The reaction mixture is stirred for 3 hours at room temperature, and 30 ml of water are then added. The lower phase is separated off and diluted with 30 ml of dichloromethane. The organic phases are subsequently washed a number of times with 30 ml of water and dried using MgSO4. The solvent is then distilled off, and the residue is dried for 3 hours under reduced pressure at 7 Pa and 60° C., giving 13.4 g of N,N,N′,N′-tetramethyl-N″,N″-diethylguanidinium tetracyanoborate as a liquid, corresponding to a yield of 97.4%.