Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [F:1][C:2]([F:46])([F:45])[C:3]1[CH:4]=[C:5]([C@H:13]2[O:17][C:16](=[O:18])[N:15]([CH2:19][C:20]3[C:25]([C:26]4[S:30][C:29]([C:31]5[CH:39]=[CH:38][C:34]([C:35]([OH:37])=[O:36])=[CH:33][C:32]=5[CH3:40])=[N:28][C:27]=4[CH3:41])=[CH:24][N:23]=[C:22](SC)[N:21]=3)[C@H:14]2[CH3:44])[CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1.[S:47]([O-:52])(O[O-])(=O)=[O:48].[K+].[K+].[CH3:55]OC(C)(C)C>C1COCC1.O>[F:46][C:2]([F:1])([F:45])[C:3]1[CH:4]=[C:5]([C@H:13]2[O:17][C:16](=[O:18])[N:15]([CH2:19][C:20]3[C:25]([C:26]4[S:30][C:29]([C:31]5[CH:39]=[CH:38][C:34]([C:35]([OH:37])=[O:36])=[CH:33][C:32]=5[CH3:40])=[N:28][C:27]=4[CH3:41])=[CH:24][N:23]=[C:22]([S:47]([CH3:55])(=[O:52])=[O:48])[N:21]=3)[C@H:14]2[CH3:44])[CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1
Reactant: COC(C)(C)C
Reactant: O=S(=O)([O-])O[O-]
Reactant: CSc1ncc(-c2sc(-c3ccc(C(=O)O)cc3C)nc2C)c(CN2C(=O)O[C@H](c3cc(C(F)(F)F)cc(C(F)(F)F)c3)[C@@H]2C)n1
Agent: [K+]
Solvent: O
Solvent: C1CCOC1
Product: Cc1cc(C(=O)O)ccc1-c1nc(C)c(-c2cnc(S(C)(=O)=O)nc2CN2C(=O)O[C@H](c3cc(C(F)(F)F)cc(C(F)(F)F)c3)[C@@H]2C)s1
Temperature: 60 °C
Reaction time: 2 h

Procedure:
4-{5-[4-({(4S,5R)-5-[3,5-Bis(trifluoromethyl)phenyl]-4-methyl-2-oxo-1,3-oxazolidin-3-yl}methyl)-2-(methylthio)pyrimidin-5-yl]-4-methyl-1,3-thiazol-2-yl}-3-methylbenzoic acid (INTERMEDIATE 53, 2.2 g, 3.22 mmol), was dissolved in 10 mL of THF and 10 mL of water. Potassium peroxymonosulfate (5.11 g, 8.31 mmol) was added, and it was stirred at 60° C. for 2 hours. Then, it was worked up with water (100 mL) and t-butyl methyl ether (200 mL). The organic layer was concentrated and purified on a silica gel column, eluting with 60% ethyl acetate in hexanes to give the title compound as a slightly yellow solid. LCMS (M+1): 715.0 1H NMR (CDCl3, 500 MHz): δ 8.93 (s, 1H), 8.93 (s, 1H), 8.10 (s, 1H), 8.03 (d, 8.5 Hz, 1H), 7.93 (m, 2H), 7.82 (s, 2H), 6.00 (d, 8.5 Hz, 1H), 5.08 (d, 16.5 Hz, 1H), 4.67 (m, 1H), 4.31 (d, 16.6 Hz, 1H), 3.46 (s, 3H), 2.75 (s, 3H), 2.50 (s, 3H), 0.86 (d, 6.5 Hz, 3H).
Reaction SMILES: C(OC([N:11]1[CH2:15][CH:14]([F:16])[C@@:13]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])([CH3:17])[CH2:12]1)=O)C1C=CC=CC=1>C(O)C.[C].[Pd].[H][H]>[C:22]([O:21][C:19]([NH:18][C@@:13]1([CH3:17])[CH:14]([F:16])[CH2:15][NH:11][CH2:12]1)=[O:20])([CH3:25])([CH3:23])[CH3:24]
Reactant: [H][H]
Reactant: CC(C)(C)OC(=O)N[C@]1(C)CN(C(=O)OCc2ccccc2)CC1F
Agent: [Pd]
Solvent: CCO
Product: CC(C)(C)OC(=O)N[C@]1(C)CNCC1F

Procedure:
To a solution of (3R)-1-benzyloxycarbonyl-3-(tert-butoxycarbonylamino)-4-fluoro-3-methylpyrrolidine (isomer A) (271 mg, 0.769 mmol) in ethanol (10 mL) was added 10% palladium-carbon catalyst (containing 52.8% water, 27.0 mg), and the suspension was stirred for 2 hours in hydrogen gas atmosphere. After removing the catalyst by filtration, the filtrate was concentrated under reduced pressure to obtain 156 mg (93%) of the crude target compound (isomer A) as a colorless transparent syrup substance.
Reaction SMILES: [NH2:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[CH:7][C:3]=1[C:4]([OH:6])=O.C(O[C:15]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)(OCC)[CH2:16][CH3:17])C>C1C=CC(C2C=CC=CC=2)=CC=1.C1C=CC(OC2C=CC=CC=2)=CC=1>[Cl:11][C:8]1[CH:7]=[C:3]2[C:2](=[CH:10][CH:9]=1)[NH:1][C:15]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[C:16]([CH3:17])[C:4]2=[O:6]
Reactant: Nc1ccc(Cl)cc1C(=O)O
Reactant: CCOC(CC)(OCC)c1ccccc1
Solvent: c1ccc(Oc2ccccc2)cc1
Solvent: c1ccc(-c2ccccc2)cc1
Product: Cc1c(-c2ccccc2)[nH]c2ccc(Cl)cc2c1=O
Temperature: 25 °C
Yield: 44.8 %

Procedure:
To a mixture of 2-amino-5-chloro-benzoic acid (0.82 g, 4.80 mmol) in Dowtherm A (20 mL), was added the compound of Step A (1.0 g, 4.80 mmol). The mixture was warmed to reflux for 15 hours, then cooled to room temperature. Upon cooling, a white precipitate formed which was collected by filtration. The solid was triturated with diisopropyl ether followed by methylene chloride to give the title compound (0.58 g, 45%), m.p. 296-302° C. Anal. calcd. for C16H12CINO: C, 71.25; H, 4.48; N, 5.19. Found: C, 70.92; H, 4.44; N, 5.04.
Reaction SMILES: [I:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[N:14]=[CH:13][CH:12]=[CH:11][N:10]=2)=[CH:4][CH:3]=1.[H-].[Na+].[C:17]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH2:25]Cl)=[CH:23][CH:22]=1)(=[O:19])[CH3:18]>CN(C=O)C.[Cl-].[Na+].O>[C:17]([O:20][C:21]1[CH:28]=[CH:27][C:24]([CH2:25][N:8]([C:5]2[CH:4]=[CH:3][C:2]([I:1])=[CH:7][CH:6]=2)[C:9]2[N:10]=[CH:11][CH:12]=[CH:13][N:14]=2)=[CH:23][CH:22]=1)(=[O:19])[CH3:18]
Reactant: Ic1ccc(Nc2ncccn2)cc1
Reactant: CC(=O)Oc1ccc(CCl)cc1
Agent: [Cl-]
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Solvent: O
Product: CC(=O)Oc1ccc(CN(c2ccc(I)cc2)c2ncccn2)cc1
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
Under an argon atmosphere, a solution of N-(4-iodophenyl)pyrimidin-2-amine (68 mg) in anhydrous DMF (1.0 ml) was added dropwise to a solution of sodium hydride (16 mg) in anhydrous DMF (1.0 ml), and the resulting mixture was stirred at room temperature for 30 minutes. To the reaction solution, a solution of 4-acetoxybenzyl chloride (0.04 ml) in anhydrous DMF (0.5 ml) was added, and the resulting mixture was stirred at room temperature overnight. Saturated brine was added to the reaction solution and the resulting mixture was extracted with chloroform. Organic layer was dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was purified by column chromatography (silica gel, eluent: hexane/ethyl acetate=6/1) to obtain (4-acetoxybenzyl)-(4-iodophenyl)pyrimidin-2-ylamine (67 mg). NMR (HL, CDCl3): δ 2.28 (3H, s), 5.22 (2H, s), 6.63 (1H, t, J=4.6 Hz), 6.98-7.02 (4H, m), 7.26 (2H, d, J=8.1 Hz), 7.64-7.67 (2H, m), 8.34 (2H, d, J=4.6 Hz)
Reaction SMILES: [C:1]1([C:13](Cl)=[O:14])[CH:6]=[C:5]([C:7](Cl)=[O:8])[CH:4]=[C:3](C(Cl)=O)[CH:2]=1.C1(N)C=CC=C(N)C=1.NC1C=CC=CC=1.C[CH:32]([OH:35])CN>CN1C(=O)CCC1.O>[C:13](=[C:1]1[CH2:2][CH:3]=[CH:4][C:5](=[C:7]=[O:8])[C:6]1=[C:32]=[O:35])=[O:14]
Reactant: O=C(Cl)c1cc(C(=O)Cl)cc(C(=O)Cl)c1
Reactant: CC(O)CN
Agent: Nc1cccc(N)c1
Solvent: Nc1ccccc1
Solvent: CN1CCCC1=O
Solvent: O
Product: O=C=C1C=CCC(=C=O)C1=C=O
Temperature: 70 °C
Reaction time: 0.5 h

Procedure:
In a nitrogen atmosphere, a 300 mL four-neck flask was charged with 30 g (0.113 mol) of 1,3,5-benzenetricarbonyl trichloride (Tokyo Chemical Industry) and 133.3 g of N-methyl-2-pyrrolidone (abbreviated below as “NMP”; Junsei Chemical Co., Ltd.), following which a solution of 9.16 g (84.8 mmol) of 1,3-phenylenediamine (DuPont K.K.) and 7.89 g (84.8 mmol) of aniline (Junsei Chemical Co., Ltd.) dissolved in 133.3 g of NMP (Junsei Chemical Co., Ltd.) was added dropwise over a period of 30 minutes at an internal temperature of 0 to 5° C. Following the completion of dropwise addition, the flask contents were stirred for 30 minutes at a temperature of 10° C. or below. A solution of 12.73 g (169.5 mmol) of DL-1-amino-2-propanol (Tokyo Chemical Industry) dissolved in 90 g of NMP (Junsei Chemical Co., Ltd.) was added dropwise to this at an internal temperature of from −3 to −1° C. over a period of 30 minutes, following which the temperature was raised to 70° C. and stirring was carried out for 2 hours. The reaction mixture was added to 3,000 g of pure water to effect re-precipitation and the resulting precipitate was collected by filtration, then dried at 150° C. for 3 hours in a vacuum desiccator. The resulting moist product was again dissolved in 180 g of N,N-dimethylacetamide (abbreviated below as “DMAc”) and stirred at 55° C. for 1 hour. Next, the DMAc solution was allowed to cool to 30° C., then added to 600 g of pure water heated to 50° C. and re-precipitated, followed by stirring at 50° C. for 1 hour. After allowing the contents to cool to 30° C., filtration was carried out and the filtrate was dried in a vacuum desiccator at 150° C. for 10 hours, giving 35.85 g of the target tricarbonylbenzene-based hyperbranched polymer (abbreviated below as “HPmDAP”). FIG. 1 shows the 1H-NMR spectrum obtained for HPmDAP.
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([C:9]2[NH:10][C:11]3[C:16]([CH:17]=2)=[C:15]([F:18])[CH:14]=[CH:13][CH:12]=3)[CH:3]=1.[C:19]([O-])([O-])=O.[K+].[K+].C(Br)Br.O>CN(C=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]2[O:8][CH2:19][N:10]3[C:11]4[CH:12]=[CH:13][CH:14]=[C:15]([F:18])[C:16]=4[CH:17]=[C:9]3[C:4]=2[CH:3]=1
Reactant: O=C([O-])[O-]
Reactant: Oc1ccc(Cl)cc1-c1cc2c(F)cccc2[nH]1
Agent: [K+]
Solvent: BrCBr
Solvent: CN(C)C=O
Solvent: O
Product: Fc1cccc2c1cc1n2COc2ccc(Cl)cc2-1
Temperature: 80 °C
Reaction time: 2 h
Yield: 121.8 %

Procedure:
To a solution of 4-chloro-2-(4-fluoro-1H-indol-2-yl)phenol (40 mg, 0.15 mmol) in DMF (1 mL), K2CO3 (40 mg, 0.31 mmol) and CH2Br2 (53 mg, 0.31 mmol) were added at 25° C. The mixture was stirred at 80° C. for 2 hours, and cooled to 25° C. H2O (50 mL) was added, then the mixture was extracted with ethyl acetate and washed with brine, dried over Na2SO4. After concentrated, the resulting residue was purified using prep-TLC (petroleum ether:EtOAc=10:1) to provide the product of 2-chloro-11-fluoro-6H-benzo[5,6][1,3]oxazino[3,4-a]indole (50 mg, yield: 45%). 1H-NMR (CDCl3, 400 MHz) δ 7.68 (s, 1H), 7.14˜7.23 (m, 2H), 7.03˜7.09 (m, 2H), 6.90 (s, 1H), 6.81˜6.86 (m, 1H), 5.88 (s, 2H). MS (M+H)+: 274/276.
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[Cl:9].CC1(C)C(C)(C)OB([C:18]2[CH:28]=[CH:27][CH:26]=[CH:25][C:19]=2[C:20]([O:22][CH2:23][CH3:24])=[O:21])O1.C1(C)C=CC=CC=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH2:23]([O:22][C:20]([C:19]1[C:18]([C:2]2[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=2[Cl:9])=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:21])[CH3:24]
Reactant: CCOC(=O)c1ccccc1B1OC(C)(C)C(C)(C)O1
Reactant: Cc1ccc(Br)c(Cl)c1
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: O=P([O-])([O-])[O-]
Agent: [K+]
Solvent: Cc1ccccc1
Solvent: O
Product: CCOC(=O)c1ccccc1-c1ccc(C)cc1Cl
Temperature: 110 °C
Reaction time: 2 h
Yield: 126 %

Procedure:
Under an argon atmosphere, 4-bromo-3-chlorotoluene (200 g), ethyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (376 g), toluene (1000 ml), water (1000 ml), tripotassium phosphate (412 g) and dichlorobis(triphenylphosphine)palladium(II) (14 g) were added to a reaction vessel and the mixture was stirred at 110° C. for 2 hr. The reaction mixture was cooled to room temperature. The insoluble material was filtered off, and washed with water (500 ml) and toluene (500 ml). The filtrate was partitioned in a separatory funnel. The organic layer was washed twice with water (1000 ml), dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to give the title compound (337 g). The obtained residue was directly used for the next reaction without further purification.
Reaction SMILES: [CH2:1]([C:4]1[N:8]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]3[C:17]([C:22]([O:24]C(C)(C)C)=[O:23])=[CH:18][CH:19]=[CH:20][CH:21]=3)=[CH:12][CH:11]=2)[C:7]2[CH:29]=[C:30](C(O)=O)[CH:31]=[CH:32][C:6]=2[N:5]=1)[CH2:2][CH3:3].[C:36]([N:43]1[CH:47]=[CH:46][N:45]=[CH:44]1)(N1C=CN=C1)=O.C(N(CC)CC)C.CN[C:57]1[CH:63]=CC=[CH:60][C:58]=1N>O1CCCC1>[CH2:1]([C:4]1[N:8]([CH2:9][C:10]2[CH:11]=[CH:12][C:13]([C:16]3[C:17]([C:22]([OH:24])=[O:23])=[CH:18][CH:19]=[CH:20][CH:21]=3)=[CH:14][CH:15]=2)[C:7]2[CH:29]=[C:30]([C:44]3[N:43]([CH3:36])[C:47]4[CH:63]=[CH:57][CH:58]=[CH:60][C:46]=4[N:45]=3)[CH:31]=[CH:32][C:6]=2[N:5]=1)[CH2:2][CH3:3]
Reactant: CCCc1nc2ccc(C(=O)O)cc2n1Cc1ccc(-c2ccccc2C(=O)OC(C)(C)C)cc1
Reactant: CNc1ccccc1N
Reactant: O=C(n1ccnc1)n1ccnc1
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CCCc1nc2ccc(-c3nc4ccccc4n3C)cc2n1Cc1ccc(-c2ccccc2C(=O)O)cc1
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
A suspension of 940 mg (2.0 mMol) of tert.-butyl 4'-[(2-n-propyl-6-carboxy-benzimidazol-1-yl)-methyl]biphenyl-2-carboxylate and 320 mg (2.0 mMol) of carbonyldiimidazole in a solution of 1.0 ml of triethylamine in 30 ml of tetrahydrofuran is stirred for 30 minutes at ambient temperature, then 250 mg (2.0 mMol) of 2-methylaminoaniline are added and the mixture is stirred for a further 16 hours. It is then evaporated to dryness and the residue is refluxed in 20 ml of phosphorus oxychloride, with stirring, for 1 hour. The majority of the phosphorus oxychloride is then distilled off, the dark, greasy residue is decomposed with 30 ml of water, the strongly acidic suspension thus obtained is refluxed for about 1 hour, adjusted to pH 6 after cooling and then concentrated by evaporation. The crude product obtained is purified by column chromatography (120 g of silica gel, eluant: methylene chloride/methanol=15:1).
Reaction SMILES: [O:1]1[C:5]2([CH2:10][CH2:9][CH:8]([CH2:11][OH:12])[CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1.[Cl:13][C:14]1[C:15](F)=[CH:16][C:17]([F:27])=[C:18]([CH:26]=1)[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20].C(=O)([O-])[O-].[Cs+].[Cs+].C(OCC)(=O)C>CS(C)=O>[O:1]1[C:5]2([CH2:10][CH2:9][CH:8]([CH2:11][O:12][C:15]3[C:14]([Cl:13])=[CH:26][C:18]([C:19]([O:21][C:22]([CH3:23])([CH3:24])[CH3:25])=[O:20])=[C:17]([F:27])[CH:16]=3)[CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1
Reactant: CC(C)(C)OC(=O)c1cc(Cl)c(F)cc1F
Reactant: OCC1CCC2(CC1)OCCO2
Agent: O=C([O-])[O-]
Agent: [Cs+]
Solvent: CS(C)=O
Solvent: CCOC(C)=O
Product: CC(C)(C)OC(=O)c1cc(Cl)c(OCC2CCC3(CC2)OCCO3)cc1F
Temperature: 75 °C
Yield: 43.5 %

Procedure:
To a mixture of 1,4-dioxaspiro[4.5]decan-8-ylmethanol (5.00 g, 29.0 mmol) and tert-butyl 5-chloro-2,4-difluorobenzoate (7.22 g, 29.00 mmol) in anhydrous dimethyl sulfoxide (30 mL) was added cesium carbonate (18.90 g, 58.00 mmol) and the reaction mixture was heated at 70-80° C. for 4 hours. After cooling to ambient temperature, ethyl acetate was added (200 mL) and the mixture was washed with water (4×15 mL), brine (2×15 mL); dried over anhydrous sodium sulfate, and filtered. After concentration of the filtrate in vacuo, the residue was purified by silica gel column chromatography using 0-30% ethyl acetate in hexanes as eluent to afford the title compound as a colorless oil (5.06 g, 44%): 1H NMR (300 MHz, CDCl3) 7.85 (d, J=7.7 Hz, 1H), 6.60 (d, J=12.2 Hz, 1H), 3.95-3.93 (m, 4H), 3.83 (d, J=6.3 Hz, 2H), 1.98-1.87 (m, 4H), 1.84-1.71 (m, 4H), 1.64-1.56 (m, 1H), 1.56 (s, 9H).
Reaction SMILES: [Cl:1][C:2]1[C:10]([Cl:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=O.[CH3:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][N:14]1[CH:19]([C:22]1[CH:23]=[N:24][C:25]([CH3:28])=[N:26][CH:27]=1)[CH2:20][NH2:21]>>[Cl:1][C:2]1[C:10]([Cl:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([NH:21][CH2:20][CH:19]([N:14]1[CH2:15][CH2:16][CH2:17][CH2:18][CH:13]1[CH3:12])[C:22]1[CH:23]=[N:24][C:25]([CH3:28])=[N:26][CH:27]=1)=[O:6]
Reactant: O=C(O)c1cccc(Cl)c1Cl
Reactant: Cc1ncc(C(CN)N2CCCCC2C)cn1
Product: Cc1ncc(C(CNC(=O)c2cccc(Cl)c2Cl)N2CCCCC2C)cn1

Procedure:
From 2,3-dichlorobenzoic acid and 2-(2-methylpiperidin-1-yl)-2-(2-methylpyrimidin-5-yl)ethanamine.
Reaction SMILES: [CH3:1][Si:2]1([O:11]C)[CH:7]=[CH:6][Si:5]([CH3:10])(OC)[CH:4]=[CH:3]1.[OH-:13].[K+:14].[SiH4]>CO.O>[CH3:1][Si:2]1[CH2:7][CH2:6][Si:5]([CH3:10])=[CH:4][CH:3]=1.[SiH:2]([O-:11])=[O:13].[K+:14]
Reactant: [OH-]
Reactant: CO[Si]1(C)C=C[Si](C)(OC)C=C1
Agent: [K+]
Agent: [SiH4]
Solvent: O
Solvent: CO
Product: C[Si]1=CC=[Si](C)CC1
Product: O=[SiH][O-]

Procedure:
The impure sym-1,4-dimethyl-1,4-dimethoxy-1,4-disilacyclohexadiene is next reacted with potassium hydroxide dissolved in a methanol/water solution by slowly adding the silane to the KOH solution. The solution is then filtered and vacuum dried to remove most of the solvent. Tetrahydrofuran is then added, causing a precipitate to form. The precipitate is next filtered and washed with tetrahydrofuran and ether, and then recrystallized from isopropanol. A final wash of the solids with isopropanol and pentane gives pure 1,4-dimethyl- 1,4-disilacyclohexadiene- 1,4-di (potassium silanoate ). The 1,4-dimethyl-1,4-disilacyclohexadiene-,4-di(potassium silanoate) is next dissolved in ethanol. Concentrated hydrochloric acid is added to the solution, causing potassium chloride to precipitate out. Water and methylene chloride are then added to the solution, dissolving the potassium chloride and forming a two phase mixture. The organic phase is then decanted from the mixture. Upon evaporation of the methylene chloride at ambient temperature, an elastomer results. This elastomer is the new compound poly-1,4-oxo1,4-dimethyl- 1,4-disilacyclohexadiene.
Reaction SMILES: [CH:1]([NH:4][S:5]([C:8]1[CH:19]=[C:12]2[C:13]([O:15]C(=O)[NH:17][C:11]2=[CH:10][CH:9]=1)=[O:14])(=[O:7])=[O:6])([CH3:3])[CH3:2].[Cl:20]C1C=CC(S(Cl)(=O)=O)=CC=1C(O)=O>>[Cl:20][C:11]1[CH:10]=[CH:9][C:8]([S:5](=[O:7])(=[O:6])[NH:4][CH:1]([CH3:3])[CH3:2])=[CH:19][C:12]=1[C:13]([OH:15])=[O:14].[CH:1]([NH:4][S:5]([C:8]1[CH:19]=[C:12]([C:13]([OH:15])=[O:14])[C:11]([NH2:17])=[CH:10][CH:9]=1)(=[O:7])=[O:6])([CH3:3])[CH3:2]
Reactant: CC(C)NS(=O)(=O)c1ccc2[nH]c(=O)oc(=O)c2c1
Reactant: O=C(O)c1cc(S(=O)(=O)Cl)ccc1Cl
Product: CC(C)NS(=O)(=O)c1ccc(Cl)c(C(=O)O)c1
Product: CC(C)NS(=O)(=O)c1ccc(N)c(C(=O)O)c1

Procedure:
5-(N-Isopropylsulfamoyl)-isatoic anhydride, which is to be used as the starting material, can be obtained, for example, in a manner analogous to that described in Example 1, using 2-chloro-5-chlorosulfonyl-benzoic acid as the starting material, the product being obtained via 2-chloro-5-(N-isopropylsulfamoyl)-benzoic acid with a melting point of 170°-173° and 5-(N-isopropylsulfamoyl)-anthranilic acid with a melting point of 230°-232°; the product melts at 235°-237°.
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4](B2OC(C)(C)C(C)(C)O2)[CH:5]=[C:6]([F:9])[C:7]=1[Cl:8].Br[C:20]([C:22]([F:25])([F:24])[F:23])=[CH2:21].C([O-])([O-])=O.[Cs+].[Cs+].[OH:32][N:33]=[C:34](Cl)[C:35]1[CH:46]=[CH:45][C:38]2[B:39]([OH:44])[O:40][C:41]([CH3:43])([CH3:42])[C:37]=2[CH:36]=1>C1COCC1.CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]([C:20]2([C:22]([F:25])([F:24])[F:23])[O:32][N:33]=[C:34]([C:35]3[CH:46]=[CH:45][C:38]4[B:39]([OH:44])[O:40][C:41]([CH3:43])([CH3:42])[C:37]=4[CH:36]=3)[CH2:21]2)[CH:5]=[C:6]([F:9])[C:7]=1[Cl:8]
Reactant: C=C(Br)C(F)(F)F
Reactant: CC1(C)OB(c2cc(F)c(Cl)c(Cl)c2)OC1(C)C
Reactant: CC1(C)OB(O)c2ccc(C(Cl)=NO)cc21
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: O=C([O-])[O-]
Agent: [Cs+]
Solvent: CN(C)C=O
Solvent: C1CCOC1
Product: CC1(C)OB(O)c2ccc(C3=NOC(c4cc(F)c(Cl)c(Cl)c4)(C(F)(F)F)C3)cc21
Temperature: 70 °C
Reaction time: 12 h
Yield: 12 %

Procedure:
A mixture of 2-(3,4-dichloro-5-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.5 g, 1.73 mmol), 2-bromo-3,3,3-trifluoroprop-1-ene (0.38 g, 2.16 mmol), Cs2CO3 (1.8 mL, 2M, 3.6 mmol) and Pd(PPh3)2Cl2 (38 mg) in THF (10 mL) was heated at 70° C. in a sealed tube for 4 h. The mixture was cooled to rt, and then N,1-dihydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbimidoyl chloride (345 mg, 1.44 mmol) in DMF (20 mL) at rt and TEA (0.6 mL, 4.32 mmol) were added. The reaction mixture was stirred for 12 h, poured into ice-water and extracted with EA. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column eluted with PE-EA (10:1 to 3:1) and then purified by prep-TLC to give 80 mg of the title compound as a white solid (yield 10%). 1H NMR (400 MHz, DMSO-d6): δ 9.23 (s, 1 H), 7.77-7.69 (m, 5 H), 4.44 (d, J=18.8 Hz, 1 H), 4.32 (d, J=18.8 Hz, 1 H), 1.47 (s, 6 H) ppm; MS: m/z=462 (M+1, ESI+).
Reaction SMILES: Cl[C:2]1[C:7]([S:8]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[C:14]([O:19][CH3:20])[N:13]=2)(=[O:10])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1.FC1C=C(OC)C=C(F)C=1CN.C(N1C=CN=C1)(N1C=CN=C1)=O.C(N(CC)CC)C.[F:52][C:53]1[CH:82]=[C:81]([O:83][CH3:84])[CH:80]=[C:79]([F:85])[C:54]=1[CH2:55][N:56]1C2N=CC=CC=2S(=O)(=O)N(C2C=CC(OC)=C(OC)C=2)[C:57]1=[O:78]>>[F:52][C:53]1[CH:82]=[C:81]([O:83][CH3:84])[CH:80]=[C:79]([F:85])[C:54]=1[CH2:55][N:56]1[C:2]2[N:3]=[CH:4][CH:5]=[CH:6][C:7]=2[S:8](=[O:10])(=[O:9])[N:11]([C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[C:14]([O:19][CH3:20])[N:13]=2)[C:57]1=[O:78]
Reactant: COc1cc(F)c(CN2C(=O)N(c3ccc(OC)c(OC)c3)S(=O)(=O)c3cccnc32)c(F)c1
Reactant: COc1nc(NS(=O)(=O)c2cccnc2Cl)ccc1C
Agent: COc1cc(F)c(CN)c(F)c1
Agent: O=C(n1ccnc1)n1ccnc1
Solvent: CCN(CC)CC
Product: COc1cc(F)c(CN2C(=O)N(c3ccc(C)c(OC)n3)S(=O)(=O)c3cccnc32)c(F)c1

Procedure:
The title compound (110 mg, 0.23 mmol) was prepared in two steps from 2-chloro-N-(6-methoxy-5-methylpyridin-2-yl)pyridine-3-sulfonamide (IntC11) (320 mg, 1.02 mmol) and 2,6-difluoro-4-methoxybenzylamine (212 mg, 1.22 mmol); followed by 1,1′-carbonyldiimidazole (403 mg, 2.49 mmol) and triethylamine (173 uL, 1.24 mmol) using the methods of (95).
Reaction SMILES: [CH3:1][C:2]1[NH:3][CH:4]=[CH:5][C:6](=[O:16])[C:7]=1[O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[CH2:17](O)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.Cl>O1CCCC1.CCOCC.C(OC(=O)C)C>[CH3:1][C:2]1[C:7]([O:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[C:6]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:5]=[CH:4][N:3]=1
Reactant: Cc1[nH]ccc(=O)c1OCc1ccccc1
Reactant: OCc1ccccc1
Agent: CCOC(=O)/N=N/C(=O)OCC
Agent: Cl
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: CCOC(C)=O
Solvent: CCOCC
Solvent: C1CCOC1
Product: Cc1nccc(OCc2ccccc2)c1OCc1ccccc1
Reaction time: 8 h

Procedure:
To 154.8 g of the product of Example 2, 86.4 g benzylalcohol and 210 g triphenylphosphine suspended in 1.5 liters (dry) tetrahydrofurane was added a solution of 139.2g diethylazodicarboxylate in 500 ml tetrahydrofuran within 20 minutes. The temperature rose to 53° C. for several hours. After 4.5 hours a clear solution was obtained. After standing overnight, a solution of HCl in ether (28 g) was added. Hydrochlorides of Example 3 and 3 A crystallized from the solution. After cooling they were isolated by filtration and washed with ether and petroleum ether. 230 g of the mixture of HCL salts of 3 and 3A was suspended in 2 liters of ethyl acetate and 1 liter of water. The pH was adjusted to 7.0 with concentrated NaOH solution. The organic phase and two organic was phases were combined and dried over Na2SO4. Filtration and distilling off the solvent yielded an oily residue which was passed through a column with 600 g SiO2. Ethylacetate as eluent. Only the title compound of Example 3B, 151.8 g, was eluted from the column. Eluation of 3A is possible with CH3OH. M.P.=92° C. (title comp. 3)