Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: CS(C)=O.[F:5][C:6]1[CH:24]=[CH:23][C:9]([CH2:10][O:11][C:12]2[CH:17]=[CH:16][C:15](/[CH:18]=[CH:19]/[N+:20]([O-:22])=[O:21])=[CH:14][N:13]=2)=[CH:8][CH:7]=1.C(O)(=O)C.[BH4-].[Na+]>O>[F:5][C:6]1[CH:7]=[CH:8][C:9]([CH2:10][O:11][C:12]2[CH:17]=[CH:16][C:15]([CH2:18][CH2:19][N+:20]([O-:22])=[O:21])=[CH:14][N:13]=2)=[CH:23][CH:24]=1
Reactant: O=[N+]([O-])/C=C/c1ccc(OCc2ccc(F)cc2)nc1
Agent: [BH4-]
Agent: [Na+]
Solvent: O
Solvent: CC(=O)O
Solvent: CS(C)=O
Product: O=[N+]([O-])CCc1ccc(OCc2ccc(F)cc2)nc1
Reaction time: 0.33 h
Yield: 30 %

Procedure:
To a dimethyl sulfoxide (20.0 mL) solution of 2-(4-fluoro-benzyloxy)-5-((E)-2-nitro-vinyl)-pyridine (2.60 g, 9.48 mmol) described in Manufacturing Example 58-1-3 and acetic acid (3.00 mL) was added sodium borohydride (574 mg, 15.2 mmol) at room temperature while cooling appropriately under nitrogen atmosphere, which was stirred for 20 minutes. Water was then added dropwise at room temperature while cooling appropriately to quench sodium borohydride. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure, and the residue was purified by NH silica gel column chromatography (ethyl acetate:heptane=1:5) to obtain the title compound (785 mg, 30.0%).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10]2[C:5](=[CH:6][CH:7]=[C:8]([C:13]3[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=3)[CH:9]=2)[C:4]=1Br.[CH2:22]([Li])CCC.CN(CCN(C)C)C.IC>C1COCC1.O>[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10]2[C:5](=[CH:6][CH:7]=[C:8]([C:13]3[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=3)[CH:9]=2)[C:4]=1[CH3:22]
Reactant: [Li]CCCC
Reactant: COc1ccc(-c2ccc3c(Br)c(OC)ccc3c2)cc1
Agent: CN(C)CCN(C)C
Solvent: CI
Solvent: C1CCOC1
Solvent: O
Product: COc1ccc(-c2ccc3c(C)c(OC)ccc3c2)cc1
Temperature: 25 °C
Yield: 88 %

Procedure:
To a solution of 2-methoxy-6-(4-methoxyphenyl)-1-bromonaphthalene in THF (25 mL) at 0° C. was slowly added n-butyl lithium (2 mL of 2.5N) and TMEDA (0.60 g, 5.13 mmol, freshly distilled from KOH). After thirty minutes at 0° C. iodomethane (7.3 g, 51.3 mmol, passed through basic alumina) was added and the stirring solution was allowed to warm to room temperature overnight. The reaction was poured into water (100 mL) and extracted with ethyl acetate (3×200 mL). The combined organic layers were washed with water, dried over magnesium sulfate, filtered, evaporation of the solvent, and purification by silica column chromatography (5% THF-hexanes) yielded 0.63 g (88%) of a white solid: mp 136-138° C.; 1H NMR (CDCl3): δ 3.87 (3H, s), 3.96 (3H, s), 7.02 (2H, d, J=8.74 Hz), 7.29 (1H, d, J=9.01 Hz), 7.60-7.80 (4H, m), 7.95 (1H, d, J=1.76 Hz), 8.00 (1H, d, J=8.86 Hz); MS (ESI) m/z279 (M+H)+.
Reaction SMILES: [CH3:1][O:2][C:3](=[O:27])[C@H:4]([CH2:6][O:7][C:8]1([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:20]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[C:14]2[C:9]1=[CH:10][CH:11]=[CH:12][CH:13]=2)N.[CH2:28]=O.O.[C:31]([BH3-])#[N:32].[Na+]>CO.[Cl-].[Zn+2].[Cl-]>[CH3:1][O:2][C:3](=[O:27])[C@H:4]([CH2:6][O:7][C:8]1([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:20]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[C:14]2[C:9]1=[CH:10][CH:11]=[CH:12][CH:13]=2)[N:32]([CH3:31])[CH3:28]
Reactant: C=O
Reactant: COC(=O)[C@@H](N)COC1(c2ccccc2)c2ccccc2-c2ccccc21
Reactant: [BH3-]C#N
Agent: [Cl-]
Agent: [Na+]
Agent: [Zn+2]
Solvent: O
Solvent: CO
Product: COC(=O)[C@H](COC1(c2ccccc2)c2ccccc2-c2ccccc21)N(C)C
Temperature: 25 °C
Reaction time: 16 h
Yield: 80.7 %

Procedure:
To a stirred solution of 0.57 g (1.6 mmol) O-(9-phenyl-9H-fluoren-9-yl)-L-serine methyl ester (Example 4a, Step 2), 0.150 g (5 mmol) paraformaldehyde and water (0.4 mL) in methanol (5 mL) was added dropwise a solution of 0.11 g (0.8 mmol) zinc chloride and 0.1 g (1.6 mmol) sodium cyanoborohydride in methanol (5 mL) at room temperature. The mixture was stirred at room temperature for 16 h, the solvent was evaporated, water (50 mL) was added and the mixture extracted with dichloromethane (3×20 mL). The combined dichloromethane extracts were washed with brine, dried (MgSO4), the solvent evaporated and the residue chromatographed on silica gel with 30% ethyl acetate in hexanes to give 0.5 g (yield 81.6%) N,N-dimethyl--O--(9-phenyl-9H-fluoren-9-yl)-L-serine methyl ester as an oil. 1H NMR (CDCl3, 300 MHz) δ: 7.68 (d, 2H), 7.40-7.10 (m, 11H), 3.73 (s, 3H), 3.40-3.15 (m, 3H), 2.29 (s, 6H); 13C NMR (CDCl3, 75 MHz) 6: 171.3, 146.6, 146.5, 143.2, 140.7, 140.5, 129.1, 129.0, 128.2, 128.1, 128.0, 127.0, 125.5, 125.4, 125.3, 120.0, 119.9, 88.7, 67.7, 61.9, 51.4, 42.6, 14.2.
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:14](=[O:15])[CH2:13][C:12](=[O:16])[NH:11][C:10]3[C:17]4[C:22]([CH:23]=[CH:24][C:9]2=3)=[CH:21][CH:20]=[CH:19][CH:18]=4)=[CH:4][CH:3]=1.[N:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1[O:31][CH2:32][C:33](O)=[O:34].CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.C(N(CC)CC)C>O.CN(C)C=O>[N:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1[O:31][CH2:32][C:33]([NH:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:14](=[O:15])[CH2:13][C:12](=[O:16])[NH:11][C:10]3[C:17]4[C:22]([CH:23]=[CH:24][C:9]2=3)=[CH:21][CH:20]=[CH:19][CH:18]=4)=[CH:4][CH:3]=1)=[O:34]
Reactant: O=C(O)COc1ccccn1
Reactant: Nc1ccc(N2C(=O)CC(=O)Nc3c2ccc2ccccc32)cc1
Agent: CN(C)C(On1nnc2cccnc21)=[N+](C)C
Agent: F[P-](F)(F)(F)(F)F
Solvent: O
Solvent: CCN(CC)CC
Solvent: CN(C)C=O
Product: O=C(COc1ccccn1)Nc1ccc(N2C(=O)CC(=O)Nc3c2ccc2ccccc32)cc1
Temperature: 25 °C
Reaction time: 2 h
Yield: 48.6 %

Procedure:
5-(4-Aminophenyl)-1H-naphtho[1,2-b][1,4]diazepine-2,4(3H,5H)-dione (32 mg, 0.1 mmol) obtained in Example 1, (3), 2-(pyridin-2-yloxy)acetic acid (23 mg, 0.15 mmol), HATU (23 mg, 0.15 mmol), triethylamine (0.04 mL), and dry dimethylformamide (1 mL) were mixed, and the mixture was stirred at room temperature for 2 hours. This reaction mixture was added with water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (methanol/chloroform=1/50) to give the title compound (22 mg, yield 49%) as pale yellow crystals.
Reaction SMILES: [CH2:1]([O:8][C:9]1[CH:18]=[C:17]2[C:12]([C:13]([Cl:19])=[N:14][CH:15]=[N:16]2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:20][C:21]1[CH:22]=[N:23][N:24]([CH2:26][C:27]([NH:29][C:30]2[CH:35]=[CH:34][CH:33]=[C:32]([F:36])[CH:31]=2)=[O:28])[CH:25]=1>CC(N(C)C)=O.C(OCC)C>[ClH:19].[CH2:1]([O:8][C:9]1[CH:18]=[C:17]2[C:12]([C:13]([NH:20][C:21]3[CH:22]=[N:23][N:24]([CH2:26][C:27]([NH:29][C:30]4[CH:35]=[CH:34][CH:33]=[C:32]([F:36])[CH:31]=4)=[O:28])[CH:25]=3)=[N:14][CH:15]=[N:16]2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: Clc1ncnc2cc(OCc3ccccc3)ccc12
Reactant: Nc1cnn(CC(=O)Nc2cccc(F)c2)c1
Solvent: CCOCC
Solvent: CC(=O)N(C)C
Product: Cl
Product: O=C(Cn1cc(Nc2ncnc3cc(OCc4ccccc4)ccc23)cn1)Nc1cccc(F)c1
Temperature: 90 °C
Yield: 81.6 %

Procedure:
A mixture of 7-(benzyloxy)-4-chloroquinazoline (1.94 g, 7.17 mmol) and 2-(4-amino-1H-pyrazol-1-yl)-N-(3-fluorophenyl)acetamide (1.66 g, 7.09 mmol) in dimethylacetamide (25 ml) was heated at 90° C. for 1 hour. The mixture was cooled to room temperature and then diluted with diethyl ether (75 ml) and filtered. The solid was washed with diethyl ether and dried to yield 2-(4-{[7-(benzyloxy)quinazolin-4-yl]amino}-1H-pyrazol-1-yl)-N-(3-fluorophenyl)acetamide hydrochloride (2.92 g, 82% yield) as a yellow solid:
Reaction SMILES: [NH2:1][C:2]1[S:3][C:4]([S:7][C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)=[CH:5][N:6]=1.N1C=CC=CC=1.[F:20][C:21]1[CH:29]=[CH:28][C:24]([C:25](Cl)=[O:26])=[CH:23][CH:22]=1>CN(C)C=O>[F:20][C:21]1[CH:29]=[CH:28][C:24]([C:25]([NH:1][C:2]2[S:3][C:4]([S:7][C:8]3[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=3)=[CH:5][N:6]=2)=[O:26])=[CH:23][CH:22]=1
Reactant: Nc1ncc(Sc2ccncc2)s1
Reactant: O=C(Cl)c1ccc(F)cc1
Solvent: c1ccncc1
Solvent: CN(C)C=O
Product: O=C(Nc1ncc(Sc2ccncc2)s1)c1ccc(F)cc1
Yield: 63.2 %

Procedure:
To a mixture of 2-amino-5-(4-pyridylthio)thiazole (2.5 g) and pyridine (3 g) in N,N-dimethylformamide (25 ml) was added dropwise the 4-fluorobenzoyl chloride (2.7 g) at 5° C. under ice cooling with stirring. The mixture was stirred at 5° C. for 4 hours under ice cooling. The reaction mixture was concentrated under reduced pressure and the residue was triturated with water. The precipitates were collected by filtration, washed with water and dried in vacuo to give 2-(4-fluorobenzoylamino)-5-(4-pyridylthio)thiazole (2.5 g, yield: 63.1%). mp: 220°-225° C. (dec.)
Reaction SMILES: Br[C:2]1[CH:3]=[C:4]2[C@@:15]3([CH2:19][S:18][C:17]([NH2:20])=[N:16]3)[C:14]3[CH:13]=[C:12](Cl)[N:11]=[C:10]([F:22])[C:9]=3[O:8][C:5]2=[CH:6][CH:7]=1.[F:23][C:24]1[C:29](B(O)O)=[CH:28][CH:27]=[CH:26][N:25]=1.[CH3:33][C:34]1([CH3:49])[O:39][CH2:38][CH2:37][C:36](B2OC(C)(C)C(C)(C)O2)=[CH:35]1.CC1(C)CC(B2OC(C)(C)C(C)(C)O2)=CCO1>>[CH3:33][C:34]1([CH3:49])[O:39][CH2:38][CH2:37][C:36]([C:12]2[N:11]=[C:10]([F:22])[C:9]3[O:8][C:5]4[C:4]([C@@:15]5([CH2:19][S:18][C:17]([NH2:20])=[N:16]5)[C:14]=3[CH:13]=2)=[CH:3][C:2]([C:29]2[C:24]([F:23])=[N:25][CH:26]=[CH:27][CH:28]=2)=[CH:7][CH:6]=4)=[CH:35]1
Reactant: CC1(C)C=C(B2OC(C)(C)C(C)(C)O2)CCO1
Reactant: OB(O)c1cccnc1F
Reactant: NC1=N[C@@]2(CS1)c1cc(Br)ccc1Oc1c2cc(Cl)nc1F
Agent: CC1(C)CC(B2OC(C)(C)C(C)(C)O2)=CCO1
Product: CC1(C)C=C(c2cc3c(c(F)n2)Oc2ccc(-c4cccnc4F)cc2[C@@]32CSC(N)=N2)CCO1

Procedure:
The titled compound was synthesized by steps analogous to those described in method BB12 above, but using (S)-7-bromo-3-chloro-1-fluoro-5′H-spiro[chromeno[2,3-c]pyridine-5,4′-thiazol]-2′-amine (prepared as described in Method BB26 but using 7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-one), 2-fluoropyridin-3-ylboronic acid and a mixture of 2-(6,6-dimethyl-3,6-dihydro-2H-pyran-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 2-(2,2-dimethyl-3,6-dihydro-2H-pyran-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
Reaction SMILES: [CH2:1]([O:3][C:4]([C:6]1[NH:10][N:9]=[C:8]([C:11]2[CH:32]=[CH:31][C:30]([O:33][CH2:34][C:35]3[CH:39]=[CH:38][S:37][CH:36]=3)=[CH:29][C:12]=2[O:13][CH:14]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH3:28])[CH2:15][CH2:16][C:17]([O:19]CC)=[O:18])[CH:7]=1)=[O:5])[CH3:2].O>[OH-].[K+].CO>[OH2:3].[CH2:1]([O:3][C:4]([C:6]1[NH:10][N:9]=[C:8]([C:11]2[CH:32]=[CH:31][C:30]([O:33][CH2:34][C:35]3[CH:39]=[CH:38][S:37][CH:36]=3)=[CH:29][C:12]=2[O:13][CH:14]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH3:28])[CH2:15][CH2:16][C:17]([OH:19])=[O:18])[CH:7]=1)=[O:5])[CH3:2]
Reactant: CCOC(=O)CCC(Oc1cc(OCc2ccsc2)ccc1-c1cc(C(=O)OCC)[nH]n1)c1ccccc1C
Agent: [K+]
Agent: [OH-]
Solvent: CO
Solvent: O
Product: CCOC(=O)c1cc(-c2ccc(OCc3ccsc3)cc2OC(CCC(=O)O)c2ccccc2C)n[nH]1
Reaction time: 0.25 h
Yield: 96.8 %

Procedure:
To a stirred suspension of ethyl (RS)-4-[2-(5-ethoxycarbonylpyrazol-3-yl)-5-(3-thienylmethoxy)phenoxy]-4-(2-methylphenyl)butanoate (4 g) in 15% potassium hydroxide in methanol (100 mL, w/v) at room temperature is added water (10 mL). The solid slowly dissolves and after stirring for 15 minutes the reaction mixture is partitioned between ethyl acetate (200 mL) and 2 N hydrochloric acid (200 mL). The organic phase is washed with water (200 mL), dried over magnesium sulphate and evaporated. The residue is recrystallised from a mixture of ethyl acetate and cyclohexane to give (RS)-4-[2-(5-ethoxycarbonylpyrazol-3-yl)-5-(3-thienylmethoxy)phenoxy]-4-(2-methylphenyl)butanoic acid hydrate (1.9 g), m.p.167-168° C. [Elemental analysis:- C,63.9; H,5.39; N,5.22%. Calculated for C28H28N2O6S.0.5H2O:- C,63.5; H,5.48; N,5.29%].
Reaction SMILES: [NH:1]([C:3]1[N:8]=[C:7]([N:9]2[CH2:14][CH2:13][O:12][CH2:11][CH2:10]2)[N:6]=[C:5]([NH:15][C:16]2[CH:21]=[CH:20][C:19]([O:22][C:23]([F:26])([F:25])[F:24])=[CH:18][CH:17]=2)[N:4]=1)[NH2:2].[F:27][C:28]([F:41])([O:32][C:33]1[CH:40]=[CH:39][CH:38]=[CH:37][C:34]=1C=O)[CH:29]([F:31])[F:30].[CH2:42](O)C.O>CCOC(C)=O.C1CCCCC1>[N:9]1([C:7]2[N:8]=[C:3]([NH:1][N:2]=[CH:42][C:38]3[CH:37]=[CH:34][C:33]([O:32][C:28]([F:27])([F:41])[CH:29]([F:30])[F:31])=[CH:40][CH:39]=3)[N:4]=[C:5]([NH:15][C:16]3[CH:17]=[CH:18][C:19]([O:22][C:23]([F:26])([F:25])[F:24])=[CH:20][CH:21]=3)[N:6]=2)[CH2:14][CH2:13][O:12][CH2:11][CH2:10]1
Reactant: O=Cc1ccccc1OC(F)(F)C(F)F
Reactant: NNc1nc(Nc2ccc(OC(F)(F)F)cc2)nc(N2CCOCC2)n1
Reactant: CCO
Solvent: O
Solvent: CCOC(C)=O
Solvent: C1CCCCC1
Product: FC(F)C(F)(F)Oc1ccc(C=NNc2nc(Nc3ccc(OC(F)(F)F)cc3)nc(N3CCOCC3)n2)cc1
Yield: 68 %

Procedure:
A 10 mL flask was charged with (4-hydrazino-6-morpholin-4-yl-1,3,5-triazin-2-yl)-(4-trifluoromethoxyphenyl)amine (XV) (159 mg, 0.43 mmol), 4-(1,1,2,2-tetrafluoroethoxybenzaldehyde (142 μL, 0.86 mmol), and ethanol (5 mL) and the mixture was stirred at ambient temperature for 24 h. Water (5 mL) was added to the reaction mixture which was then extracted with EtOAc (3×5 mL). The combined organic extract was washed with brine (10 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. Flash chromatography (silica gel, 10% EtOAc/cyclohexane) afforded compound 1 (167 mg, 68% yield): m.p. 203-206° C.; 1H NMR (CDCl3) δ 8.65 (s, 1H), 7.79 (s, 1H), 7.66-7.55 (m, 4H), 7.20-7.12 (m, 4H), 6.10-5.73 (tt, J1=53.1 Hz, J2=2.56 Hz, 1H), 3.86-3.75 (m, 8H).
Reaction SMILES: [As].[Cu:2].[As:3](=[O:7])([OH:6])([OH:5])[OH:4]>>[As:3](=[O:4])([O-:7])([O-:6])[O-:5].[Cu+3:2].[As:3](=[O:4])([OH:7])([OH:6])[OH:5]
Reactant: [Cu]
Agent: O=[As](O)(O)O
Agent: [As]
Product: O=[As]([O-])([O-])[O-]
Product: [Cu+3]

Procedure:
The method of claims 1, 2 or 3 wherein the copper-arsenic precipitate is leached into a concentrated arsenic acid to produce copper arsenate and arsenic acid solution, so that by adding chromium acid to the copper arsenate and arsenic acid solution there is produced a wood anti-rot agent containing copper, chromium and arsenic.
Reaction SMILES: [Cl-].O[NH3+:3].[C:4](=[O:7])([O-])[OH:5].[Na+].CS(C)=O.[CH2:13]([C:17]1[N:18]([CH2:37][C:38]2[CH:43]=[CH:42][C:41]([C:44]3[C:45]([C:50]#[N:51])=[CH:46][CH:47]=[CH:48][CH:49]=3)=[CH:40][CH:39]=2)[C:19](=[O:36])[C:20]([C:26]2[CH:27]=[CH:28][C:29]3[O:33][CH:32]([CH3:34])[CH2:31][C:30]=3[CH:35]=2)=[C:21]([CH:23]2[CH2:25][CH2:24]2)[N:22]=1)[CH2:14][CH2:15][CH3:16]>O>[CH2:13]([C:17]1[N:18]([CH2:37][C:38]2[CH:39]=[CH:40][C:41]([C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][C:45]=3[C:50]3[NH:3][C:4](=[O:7])[O:5][N:51]=3)=[CH:42][CH:43]=2)[C:19](=[O:36])[C:20]([C:26]2[CH:27]=[CH:28][C:29]3[O:33][CH:32]([CH3:34])[CH2:31][C:30]=3[CH:35]=2)=[C:21]([CH:23]2[CH2:25][CH2:24]2)[N:22]=1)[CH2:14][CH2:15][CH3:16]
Reactant: O=C([O-])O
Reactant: [NH3+]O
Reactant: CCCCc1nc(C2CC2)c(-c2ccc3c(c2)CC(C)O3)c(=O)n1Cc1ccc(-c2ccccc2C#N)cc1
Agent: [Cl-]
Agent: [Na+]
Solvent: CS(C)=O
Solvent: O
Product: CCCCc1nc(C2CC2)c(-c2ccc3c(c2)CC(C)O3)c(=O)n1Cc1ccc(-c2ccccc2-c2noc(=O)[nH]2)cc1
Temperature: 40 °C
Reaction time: 0.5 h
Yield: 83.9 %

Procedure:
A mixture of hydroxylammonium chloride (0.54 g), sodium hydrogen carbonate (0.76 g) and dimethyl sulfoxide (10 mL) was stirred at 40° C. for 30 min, 4′-{[2-butyl-4-cyclopropyl-5-(2-methyl-2,3-dihydro-1-benzofuran-5-yl)-6-oxopyrimidin-1(6H)-yl]methyl}biphenyl-2-carbonitrile (0.46 g) was added, and the mixture was stirred at 90° C. for 16 hr. The mixture was allowed to cool to room temperature, water was added to the reaction mixture, and the precipitate was collected by filtration. The obtained solid was dissolved in ethyl acetate. The solution was washed with saturated brine and dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was dissolved in tetrahydrofuran (5 mL), N,N′-carbonyldiimidazole (0.22 g) and then 1,8-diazabicyclo[5.4.0]undec-7-ene (0.2 mL) were added, and the mixture was stirred at room temperature for 30 min. The reaction mixture was diluted with ethyl acetate, washed with 1 M hydrochloric acid and then with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give the title compound as colorless crystals (0.43 g, 82%).
Reaction SMILES: C(O[C:6]([N:8]1[CH2:12][C:11](=[N:13][O:14][CH3:15])[CH2:10][C@H:9]1[C:16]([OH:18])=O)=[O:7])(C)(C)C.[CH3:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1[C:26]1[CH:31]=[CH:30][C:29](C(O)=O)=[C:28]([CH3:35])[CH:27]=1.[NH2:36][C@H:37]([C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)[C@H:38]([C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)[OH:39]>>[CH3:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1[C:26]1[CH:31]=[CH:30][C:29]([C:6]([N:8]2[CH2:12][C:11](=[N:13][O:14][CH3:15])[CH2:10][C@H:9]2[C:16]([NH:36][C@H:37]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C@@H:38]([OH:39])[C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)=[O:18])=[O:7])=[C:28]([CH3:35])[CH:27]=1
Reactant: Cc1cc(-c2ccccc2C)ccc1C(=O)O
Reactant: CON=C1C[C@@H](C(=O)O)N(C(=O)OC(C)(C)C)C1
Reactant: N[C@H](c1ccccc1)[C@@H](O)c1ccccc1
Product: CON=C1C[C@@H](C(=O)N[C@H](c2ccccc2)[C@@H](O)c2ccccc2)N(C(=O)c2ccc(-c3ccccc3C)cc2C)C1

Procedure:
Following the general method as outlined in Example 22, starting from (2S,4EZ)-1-(tert-butoxycarbonyl)-4-(methoxyimino)-2-pyrrolidinecarboxylic acid, 2′,3-dimethyl[1,1-biphenyl]-4carboxylic acid, and (1S,2R)-2-amino-1,2-diphenylethanol, the title compound was obtained in 73% purity by HPLC. MS(ESI+): m/z=562.
Reaction SMILES: Br[C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].[CH:9]1[C:17]2[C:16]3[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=3[S:14][C:13]=2[C:12](B(O)O)=[CH:11][CH:10]=1.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1>[CH:9]1[C:17]2[C:16]3[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=3[S:14][C:13]=2[C:12]([C:2]2[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=2[NH2:4])=[CH:11][CH:10]=1
Reactant: OB(O)c1cccc2c1sc1ccccc12
Reactant: Nc1ccccc1Br
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: Cc1ccccc1
Product: Nc1ccccc1-c1cccc2c1sc1ccccc12
Yield: 78.9 %

Procedure:
The 300 ml round-bottom flask equipped with reflux condenser and magnetic stirrer was charged with 2-bromoaniline (8.00 g, 46.5 mmol), 4-dibenzothiopheneboronic acid (10.5 g, 46.5 mmol), potassium carbonate (20 g, saturated solution in water), tetrakis(triphenylphoshine)palladium (0) (500 mg) and 100 ml of toluene. The reaction mixture was refluxed overnight under nitrogen atmosphere, filtered through silica plug and evaporated. Product was purified by column chromatography on silica gel, eluent hexane/ethyl acetate 4/1 mixture, providing 2-(dibenzo[b,d]thiophen-4-yl)aniline (10.1 g) as yellow oil.
Reaction SMILES: [N-]=[C:2]=[O:3].[C:4]1(=[O:11])NCCC[CH2:6][CH2:5]1.[CH2:12]([OH:15])[CH2:13][OH:14]>>[C:2]1(=[O:3])[O:11][C:4](=[O:14])[CH:5]=[CH:6]1.[CH2:4]([OH:11])[CH2:5][CH2:13][CH2:12][OH:15]
Reactant: O=C1CCCCCN1
Reactant: OCCO
Reactant: [N-]=C=O
Product: O=C1C=CC(=O)O1
Product: OCCCCO

Procedure:
This Example demonstrates a new, interesting isocyanate polyaddition and vinyl copolymerization according to the invention using a multicomponent mixture of 1 mol of ε-caprolactam, 0.5 mol of ethylene glycol, and 1 mol of the semi-ester formed from 1 mol of maleic acid anhydride and 1 mol of 1,4-butane diol. The heat effect of the NCO-polyaddition reaction in the presence of radical formers is entirely adequate to initiate substantially quantitative vinyl polymerization or alternating copolymerization with the maleic acid semi-ester segments, incorporated through NCO-reactions, corresponding to the formula: ##STR54## in the presence of styrene.
Reaction SMILES: [CH3:1][N:2]([CH2:6][C:7]1[S:8][CH:9]=[CH:10][CH:11]=1)CCO.[C:12]([CH2:14][C:15]([OH:17])=[O:16])#[N:13].[CH2:18]1CCC(N=C=NC2CCCCC2)C[CH2:19]1>C1COCC1>[CH2:18]([O:16][C:15](=[O:17])[CH:14]([C:12]#[N:13])[N:2]([CH3:1])[CH2:6][C:7]1[S:8][CH:9]=[CH:10][CH:11]=1)[CH3:19]
Reactant: N#CCC(=O)O
Reactant: C(=NC1CCCCC1)=NC1CCCCC1
Reactant: CN(CCO)Cc1cccs1
Solvent: C1CCOC1
Product: CCOC(=O)C(C#N)N(C)Cc1cccs1
Reaction time: 3 h
Yield: 98.7 %

Procedure:
2-[Methyl(2-thienylmethyl)amino]ethanol (0.017 mol, 3 g) and cyanoacetic acid (0.017 mol, 1.5 g) were dissolved in 200 mL of THF and DCC (0.019 mol, 3.8 g) was added. After 3 h, the resulting solid was removed and the filtrate was concentrated. The residue was passed through a six-inch silica plug using ether as solvent to give 4.0 g of product. 1H NMR (300 MHz) CDCl3: 7.25 (d, 1H), 7.0-6.8 (m, 2H), 4.33 (t, 2H) 3.76 (s, 2H), 3.47 (s, 2H), 2.70 (t, 2H), 2.35 (s, 3H).
Reaction SMILES: [C:1]([O:5][C:6]([NH:8][C:9]1[S:13][N:12]=[C:11]([CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])[N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH:20](=[O:25])[CH2:21][CH2:22][CH2:23][CH3:24]>C(OCC)(=O)C>[C:1]([O:5][C:6]([NH:8][C:9]1[S:13][N:12]=[C:11]([CH:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH:20]([OH:25])[CH2:21][CH2:22][CH2:23][CH3:24])[N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]
Reactant: CCOC(=O)Cc1nsc(NC(=O)OC(C)(C)C)n1
Reactant: CCCCC=O
Solvent: CCOC(C)=O
Product: CCCCC(O)C(C(=O)OCC)c1nsc(NC(=O)OC(C)(C)C)n1

Procedure:
1.0 g (3.5 mMol) of product from Example 28 were reacted with 1.1 g (~10 mMol) of n-pentanal for 9 days in the manner described in Example 29 and, after aqueous work-up, the product was isolated from the ethyl acetate extract. A 1:1 mixture of the erythro and threo forms resulted.
Reaction SMILES: [CH:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:9]([C:11]([CH3:13])=[O:12])=[CH2:10].N(CCO)(CCO)CCO>CN(C)C=O>[C:2]1([C:1](=[O:8])[CH2:10][CH2:9][C:11](=[O:12])[CH3:13])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: C=CC(C)=O
Reactant: O=Cc1ccccc1
Solvent: OCCN(CCO)CCO
Solvent: CN(C)C=O
Product: CC(=O)CCC(=O)c1ccccc1
Reaction time: 15 h

Procedure:
Following the description in Example 1, 5.1 g (approx. 0.02 mol) of Cat. 3, 21.2 g (0.2 mol) of distilled benzaldehyde, 350 ml of dimethylformamide and 14 g (0.2 mol) of stabilized methyl vinyl ketone are introduced into a 500 ml three-necked flask. After displacing the air by pure nitrogen, the mixture is brought to a temperature of 80° C and 14.9 g (0.1 mol) of triethanolamine are added. The mixture is then stirred for 15 hours at the same temperature. Working up takes place as in Example 11 except that the mixture is filtered after having been taken up in chloroform. 1-Phenyl-pentane-1,4-dione is obtained.
Reaction SMILES: [CH3:1][C:2]1[N:7]=[C:6]([O:8][C:9]2[CH:10]=[C:11]([CH2:15]O)[CH:12]=[CH:13][CH:14]=2)[CH:5]=[CH:4][CH:3]=1.S(Cl)([Cl:19])=O.C(=O)(O)[O-].[Na+]>ClCCl>[Cl:19][CH2:15][C:11]1[CH:10]=[C:9]([CH:14]=[CH:13][CH:12]=1)[O:8][C:6]1[CH:5]=[CH:4][CH:3]=[C:2]([CH3:1])[N:7]=1
Reactant: O=S(Cl)Cl
Reactant: Cc1cccc(Oc2cccc(CO)c2)n1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: ClCCl
Product: Cc1cccc(Oc2cccc(CCl)c2)n1
Temperature: 25 °C
Reaction time: 3 h
Yield: 100.7 %

Procedure:
(3-(6-Methylpyridin-2-yloxy)phenyl)methanol from Step 1 (3.7 g, 17 mmol), in dichloromethane (50 mL), was cooled to 0° C., and treated dropwise with thionyl chloride (1.50 mL, 20.6 mmol). The reaction mixture was allowed to warm to ambient temperature and was stirred for 3 h. Saturated aqueous sodium bicarbonate (20 mL) was added and the mixture was stirred at RT for 5 min. The organic layer was separated, dried over sodium sulfate, filtered and concentrated by evaporation to afford the title compound (4.0 g, 99% yield) as an oil.