Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [C:1]1([C:7]2[NH:8][C:9]3[CH:10]=[CH:11][CH:12]=[C:13]4[C:19](=[O:20])[NH:18][CH2:17][CH2:16][C:15]=2[C:14]=34)C=C[CH:4]=[CH:3][CH:2]=1.[S:21]1C=CC=C1B(O)O>>[S:21]1[CH:4]=[CH:3][CH:2]=[C:1]1[C:7]1[NH:8][C:9]2[CH:10]=[CH:11][CH:12]=[C:13]3[C:19](=[O:20])[NH:18][CH2:17][CH2:16][C:15]=1[C:14]=23
Reactant: O=C1NCCc2c(-c3ccccc3)[nH]c3cccc1c23
Reactant: OB(O)c1cccs1
Product: O=C1NCCc2c(-c3cccs3)[nH]c3cccc1c23

Procedure:
In a manner similar to that described for Compound 12, the tricyclic bromide (300 mg, 1.13 mmol) and thiophene-2-boronic acid (159 mg, 1.24 mmol) were coupled to yield 2-thiophen-2-yl-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one, 171 mg (56%) as a beige solid: m.p. 220.5-222.5° C.; 1H NMR (300 MHz d6-DMSO) 3.08 (m, 2H), 3.48 (m, 2H), 7.23 (m, 2H), 7.52 (m, 2H), 7.69 (m, 2H), 8.05 (br t, 1H), 11.60 (br s, 1H). MS (electrospray, MH+) 269. Anal. (C15H12N2)S.0.8 H2O) C, H, N.
Reaction SMILES: [CH2:1]([NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH2:2][CH2:3][CH3:4].[OH:12][C:13]1[CH:14]=[CH:15][C:16]2[O:21][CH:20]=[C:19]([C:22](O)=[O:23])[O:18][C:17]=2[CH:25]=1>>[OH:12][C:13]1[CH:14]=[CH:15][C:16]2[O:21][CH:20]=[C:19]([C:22]([N:5]([CH2:1][CH2:2][CH2:3][CH3:4])[C:6]3[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=3)=[O:23])[O:18][C:17]=2[CH:25]=1
Reactant: O=C(O)C1=COc2ccc(O)cc2O1
Reactant: CCCCNc1ccccc1
Product: CCCCN(C(=O)C1=COc2ccc(O)cc2O1)c1ccccc1
Yield: 78 %

Procedure:
That compound is obtained in a yield of 78% starting from N-butylaniline and 7-hydroxy-1,4-benzodioxin-2-carboxylic acid.
Reaction SMILES: [NH:1]1[CH:5]=[CH:4][N:3]=[C:2]1[C:6]1[CH:7]=[CH:8][CH:9]=[C:10]([OH:15])[C:11]=1[C:12]([OH:14])=[O:13].O[N:17]1[CH:21]=[CH:20][CH:19]=[N:18]1.[H-].[Na+].Cl[N:25]1[CH2:30][N:29]([O:31][CH3:32])[CH2:28][N:27]([O:33][CH3:34])[CH2:26]1.P(=O)(O)(O)O>O1CCCC1>[NH:1]1[CH:5]=[CH:4][N:3]=[C:2]1[C:6]1[C:11]([C:12]([O:14][N:17]2[CH:21]=[CH:20][CH:19]=[N:18]2)=[O:13])=[C:10]([O:15][N:25]2[CH2:30][N:29]([O:31][CH3:32])[CH2:28][N:27]([O:33][CH3:34])[CH2:26]2)[CH:9]=[CH:8][CH:7]=1
Reactant: O=C(O)c1c(O)cccc1-c1ncc[nH]1
Reactant: CON1CN(Cl)CN(OC)C1
Reactant: On1cccn1
Agent: O=P(O)(O)O
Agent: [H-]
Agent: [Na+]
Solvent: C1CCOC1
Product: CON1CN(OC)CN(Oc2cccc(-c3ncc[nH]3)c2C(=O)On2cccn2)C1
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
1.75 g (10.8 mmol) of N,N'-carbonylbisimidazole is added to a solution of 1.88 g (10 mmol) of 6-imidazolylsalicylic acid in 30 ml of tetrahydrofuran. After the mixture has been stirred for 30 minutes at room temperature, 9.9 mmol of N-hydroxypyrazole is added and the mixture is stirred for a further 14 hours. The reaction mixture is then hydrolyzed with 300 ml of 1N phosphoric acid and the resulting mixture is extracted several times with methyl tert-butyl ether. The organic phases are dried over sodium sulfate and evaporated down under reduced pressure. The residue is taken up in 40 ml of dimethylformamide, and 280 mg of sodium hydride (85% strength in paraffin, 10 mmol) is added. After the mixture has been stirred for 30 minutes at room temperature, 1.58 g (9 mmol) of 1-chloro-3,5-dimethoxy-s-triazine is added and the whole is stirred for 14 hours. The batch is introduced into 300 ml of 0.1N phosphoric acid, and extracted with diethyl ether. The ether phase is dried over sodium sulfate and evaporated down, and the residue is purified by column chromatography.
Reaction SMILES: [Br:1][C:2]1[C:3](=[O:19])[NH:4][C:5](C)=[CH:6][C:7]=1[O:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13](F)=[CH:12][C:11]=1F.[F-].[Cs+].C(O[Si](OCC)(OCC)OCC)C.[C:35]([O:39][CH2:40][CH3:41])(=[O:38])[CH:36]=[CH2:37]>O1CCCC1>[CH2:9]([O:8][C:7]1[CH:6]=[CH:5][N:4]([CH2:37][CH2:36][C:35]([O:39][CH2:40][CH3:41])=[O:38])[C:3](=[O:19])[C:2]=1[Br:1])[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1
Reactant: Cc1cc(OCc2ccc(F)cc2F)c(Br)c(=O)[nH]1
Reactant: C=CC(=O)OCC
Agent: CCO[Si](OCC)(OCC)OCC
Agent: [Cs+]
Agent: [F-]
Solvent: C1CCOC1
Product: CCOC(=O)CCn1ccc(OCc2ccccc2)c(Br)c1=O
Temperature: 25 °C
Reaction time: 0.17 h
Yield: 91.6 %

Procedure:
3-bromo-4-[(2,4-difluorobenzyl)oxy]-6-methylpyridin-2(1H)-one (0.50 g, 1.78 mmol) and cesium fluoride (0.0027 g, 0.178 mmol) were suspended in tetrahydrofuran (10 mL) followed by dropwise addition of tetraethylortho silicate (0.37 g, 1.78 mmol) at room temperature. After stirring for 10 minutes at room temperature, ethyl acrylate (0.23 g, 2.32 mmol) was added dropwise and the reaction stirred at room temperature overnight. The reaction mixture was filtered through a pad of Celite®. The filtrate was concentrated and the resulting residue subjected to chromatography (silica gel, ethyl acetate with 10% methanol/hexanes) to afford a white solid (0.62 g, 92%). 1H NMR (400 MHz, CDCl3) δ 7.42 (d, J=7.79 Hz, 1H), 7.41-7.29 (m, 5H), 6.03 (d, J=7.65 Hz, 1H), 5.20 (s, 2H), 4.17 (t, J=5.98 Hz, 2H), 4.07 (q, J=7.16 Hz, 2H), 2.83 (t, J=5.98 Hz, 2H), 1.19 (t, J=7.18 Hz, 3H) ES-HRMS In/z 380.0523 (M+H C17H18BrNO4 requires 380.0492).
Reaction SMILES: [CH2:1]([CH:4]1[CH2:9][CH2:8][CH:7]([CH:10]2[CH2:15][CH2:14][CH:13]([C:16]#N)[CH2:12][CH2:11]2)[CH2:6][CH2:5]1)[CH2:2][CH3:3].[OH-:18].[K+].[OH2:20].Cl>C(O)C>[CH2:1]([CH:4]1[CH2:9][CH2:8][CH:7]([CH:10]2[CH2:15][CH2:14][CH:13]([C:16]([OH:20])=[O:18])[CH2:12][CH2:11]2)[CH2:6][CH2:5]1)[CH2:2][CH3:3]
Reactant: O
Reactant: CCCC1CCC(C2CCC(C#N)CC2)CC1
Reactant: [OH-]
Agent: Cl
Agent: [K+]
Solvent: CCO
Product: CCCC1CCC(C2CCC(C(=O)O)CC2)CC1

Procedure:
On the other hand, 50 g of 4-propyl-4'-cyanobicyclohexane was dissolved in 50 ml of C2H5OH, and 25 g of KOH and 15 ml of water was added to the resulting solution, after which the resulting mixture was refluxed for 8 hours and poured into dilute hydrochloric acid, and then the acidic solution was extracted with (C2H5)2O and the (C2H5)2O was distilled off. The residue was recrystallized from benzene to obtain 4-propyl-4'-bicyclohexanecarboxylic acid.
Reaction SMILES: ClC1C=CC(OC)=C(C=1)C(NC[CH2:11][C:12]1[CH:17]=[CH:16][C:15]([CH:18]([CH2:22][CH3:23])[C:19]([OH:21])=[O:20])=[CH:14][CH:13]=1)=O.CCC(C(O)=O)C1C=CC=CC=1.C=O.[ClH:41]>>[Cl:41][CH2:11][C:12]1[CH:17]=[CH:16][C:15]([CH:18]([CH2:22][CH3:23])[C:19]([OH:21])=[O:20])=[CH:14][CH:13]=1
Reactant: CCC(C(=O)O)c1ccc(CCNC(=O)c2cc(Cl)ccc2OC)cc1
Reactant: Cl
Agent: C=O
Agent: CCC(C(=O)O)c1ccccc1
Product: CCC(C(=O)O)c1ccc(CCl)cc1

Procedure:
The 2[4-(2-aminoethyl)-phenyl]-butyric acid hydrochloride used as starting material is prepared in the following manner: 2-phenylburyric acid is reacted with paraformaldehyde/hydrochloric acid to give 2-(4-chloromethylphenyl)-butyric acid (b.p. 173°-176° C./0.1 mm Hg). By the reaction thereof with potassium cyanide, there is obtained 2-(4-cyanomethylphenyl)-butyric acid (oil) which, after catalytic hydrogenation, gives 2-[4-(2-aminoethyl)-phenyl]-butyric acid hydrochloride; m.p. 128°-130° C.
Reaction SMILES: [CH3:1][S:2]([C:5]1[CH:6]=[C:7]([C:11]2[C:12]3[N:13]([N:17]=[C:18]([NH2:20])[N:19]=3)[CH:14]=[CH:15][CH:16]=2)[CH:8]=[CH:9][CH:10]=1)(=[O:4])=[O:3].Br[C:22]1[CH:27]=[CH:26][C:25]([N:28]2[CH2:33][CH2:32][N:31]([CH3:34])[CH2:30][CH2:29]2)=[CH:24][CH:23]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)CCCCC1>>[CH3:1][S:2]([C:5]1[CH:6]=[C:7]([C:11]2[C:12]3[N:13]([N:17]=[C:18]([NH:20][C:22]4[CH:23]=[CH:24][C:25]([N:28]5[CH2:33][CH2:32][N:31]([CH3:34])[CH2:30][CH2:29]5)=[CH:26][CH:27]=4)[N:19]=3)[CH:14]=[CH:15][CH:16]=2)[CH:8]=[CH:9][CH:10]=1)(=[O:3])=[O:4]
Reactant: CN1CCN(c2ccc(Br)cc2)CC1
Reactant: CS(=O)(=O)c1cccc(-c2cccn3nc(N)nc23)c1
Agent: c1ccc(P(C2CCCCC2)C2CCCCC2)c(-c2ccccc2P(C2CCCCC2)C2CCCCC2)c1
Product: CN1CCN(c2ccc(Nc3nc4c(-c5cccc(S(C)(=O)=O)c5)cccn4n3)cc2)CC1

Procedure:
[8-(3-Methanesulfonyl-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl]-[4-(4-methyl-piperazin-1-yl)-phenyl]-amine was prepared from 8-(3-methanesulfonyl-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-ylamine (75.0 mg, 0.260 mmol) and 1-(4-bromo-phenyl)-4-methyl-piperazine (80.0 mg, 0.314 mmol) with 2,2′-bis-dicyclohexylphosphanyl-biphenyl (30.0 mg, 0.0549 mmol) as the ligand in a manner analogous to Step 2d and was isolated as a yellow foam (0.068 g, 56%). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.66 (s, 1H), 8.45 (d, J=6.5 Hz, 1H), 8.38 (d, J=7.7 Hz, 1H), 7.99 (d, J=7.7 Hz, 1H), 7.73 (d, J=6.9 Hz, 1H), 7.66 (d, J=7.4 Hz, 1H), 7.50 (d, J=7.7 Hz, 1H), 7.00-6395 (m, 3H), 6.70 (s, 1H), 3.19-0.314 (m, 4H), 3.12 (s, 3H), 2.62-2.57 (m, 4H), 2.36 (s, 3H). MS=463 (MH)+.
Reaction SMILES: C(O)(C(F)(F)F)=O.[Cl:8][C:9]1[CH:10]=[CH:11][C:12]([CH2:24][CH:25]([NH:29][C:30]2[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][CH:31]=2)[CH:26]([F:28])[F:27])=[C:13]([CH:23]=1)[CH2:14][NH:15]C(=O)OC(C)(C)C>C(Cl)Cl>[NH2:15][CH2:14][C:13]1[CH:23]=[C:9]([Cl:8])[CH:10]=[CH:11][C:12]=1[CH2:24][CH:25]([NH:29][C:30]1[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][CH:31]=1)[CH:26]([F:28])[F:27]
Reactant: COc1ccc(NC(Cc2ccc(Cl)cc2CNC(=O)OC(C)(C)C)C(F)F)cc1
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: COc1ccc(NC(Cc2ccc(Cl)cc2CN)C(F)F)cc1
Yield: 137.9 %

Procedure:
TFA (5.2 mL) was added to a stirred solution of tert-butyl 5-chloro-2-{3,3-difluoro-2-[(4-methoxyphenyl)amino]propyl}benzylcarbamate (0.516 g, 1.17 mmol) in CH2Cl2 (5.2 mL). After 1 h the solvent was evaporated in vacuo and the residue was partitioned between EtOAc and saturated aqueous Na2CO3. The EtOAc layer was dried (Na2SO4) and evaporated in vacuo to give N-{1-[2-(aminomethyl)-4-chlorobenzyl]-2,2-difluoroethyl}-N-(4-methoxyphenyl)amine (0.550 g) as a foam; MS m/z=341.1.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[C:6]2=O.O.NN.O>C(OCC)(=O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[CH2:6]2
Reactant: COc1ccc2c(c1)C(=O)C(=O)N2
Agent: NN
Solvent: CCOC(C)=O
Solvent: O
Product: COc1ccc2c(c1)CC(=O)N2
Temperature: 25 °C
Yield: 15.2 %

Procedure:
Concentrated sulfuric acid (45 mL) containing 5 mL of water was warmed to 60° C. and 8.6 g of N-(2-hydroximinoacetyl)anisidine was added in one portion. The stirred mixture was heated to 93° C. for 10 minutes and then allowed to cool to room temperature. The mixture was poured into 500 g of ice and extracted 3 times with ethyl acetate. The combined extracts were dried over anhydrous sodium sulfate and concentrated to give 5.1 g (65% yield) of 5-methoxyisatin as a dark red solid. 5-Methoxyisatin (5.0 g) and 30 mL of hydrazine hydrate were heated to reflux for 15 minutes. The reaction mixture was cooled to room temperature and 50 mL of water was added. The mixture was extracted 3 times with 25 mL of ethyl acetate each time, the organic layers combined, dried over anhydrous sodium sulfate and concentrated to give a yellow solid. The solid was stirred in ethyl acetate and 1.1 g of insoluble material was removed by vacuum filtration and saved. This material proved to be 2-hydrazinocarbonylmethyl-4-anisidine. The filtrate was concentrated and chromatographed on silica gel eluting with ethyl acetate:hexane (1:1) to give 0.7 g of 5-methoxy-2-oxindole as a yellow solid. The 1.1 g of 2-hydrazinocarbonylmethyl-4-anisidine was refluxed for 1 hour in 20 mL of 1N sodium hydroxide. The mixture was cooled, acidified to pH 2 with concentrated hydrochloric acid and extracted 3 times with 25 mL of ethyl acetate each time. The organic extracts were combined, washed with brine, dried over anhydrous sodium sulfate and concentrated to give 0.8 g of 5-methoxy-2-oxindole as a yellow solid. The combined yield was 1.5 g or 33%.
Reaction SMILES: CCCCCC.C([Li])CCC.[CH3:12][S:13][CH:14]([S:17][CH3:18])[S:15][CH3:16].[OH:19][C@H:20]1[CH2:42][CH2:41][C@@:40]2([CH3:43])[C:22](=[CH:23][CH2:24][C@@H:25]3[C@@H:39]2[CH2:38][CH2:37][C@@:36]2([CH3:44])[C@H:26]3[CH2:27][CH2:28][C@@H:29]2[C@H:30]([CH3:35])[CH2:31][CH2:32][CH:33]=[O:34])[CH2:21]1>O1CCCC1>[OH:19][C@H:20]1[CH2:42][CH2:41][C@@:40]2([CH3:43])[C:22](=[CH:23][CH2:24][C@@H:25]3[C@@H:39]2[CH2:38][CH2:37][C@@:36]2([CH3:44])[C@H:26]3[CH2:27][CH2:28][C@@H:29]2[C@H:30]([CH3:35])[CH2:31][CH2:32][CH:33]([OH:34])[C:14]([S:17][CH3:18])([S:15][CH3:16])[S:13][CH3:12])[CH2:21]1
Reactant: CSC(SC)SC
Reactant: C[C@H](CCC=O)[C@H]1CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C
Agent: [Li]CCCC
Solvent: C1CCOC1
Solvent: CCCCCC
Product: CSC(SC)(SC)C(O)CC[C@@H](C)[C@H]1CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C
Reaction time: 0.67 h
Yield: 70.5 %

Procedure:
Under an argon atmosphere at -78° C., 10.4 ml (17.7 mmoles) of a hexane solution of n-butyllithium was added to a solution of 2.4 ml (18.0 mmoles) of tris(methylthio)methane in 40 ml of tetrahydrofuran (THF for short), and the mixture was stirred for 40 minutes at the same temperature. To the mixture was added dropwise 15 ml of a THF solution of 798 mg (1.8 mmoles) of 3β-hydroxychol-5-en-24-al [compound of formula(VI)], and the mixture was stirred at -78° C. for 40 minutes. The mixture was extracted with ether in a customary manner, and the resulting residue was dissolved in a mixture of 10 ml of THF and 5 ml of methanol. Four drops of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 100 minutes. The mixture was extracted with ether in a customary manner, and the resulting crude product was purified by silica gel column chromatography [31 g; eluted with hexane/ethyl acetate (10:1)] to give 651 mg of the captioned compound having a melting point of141° to 143° C. (recrystallized from methanol).
Reaction SMILES: [CH2:1]([N:3]1[C:12]2[C:7](=[CH:8][C:9]([F:14])=[C:10](F)[CH:11]=2)[C:6](=[O:15])[C:5]([C:16]([OH:18])=[O:17])=[CH:4]1)[CH3:2].[N:19]1[CH:24]=[CH:23][CH:22]=[C:21]([CH:25]2[CH2:30][NH:29][CH2:28][CH2:27][NH:26]2)[CH:20]=1.N1C=CC=CC=1>CCOCC>[CH2:1]([N:3]1[C:12]2[C:7](=[CH:8][C:9]([F:14])=[C:10]([N:29]3[CH2:28][CH2:27][NH:26][CH:25]([C:21]4[CH:20]=[N:19][CH:24]=[CH:23][CH:22]=4)[CH2:30]3)[CH:11]=2)[C:6](=[O:15])[C:5]([C:16]([OH:18])=[O:17])=[CH:4]1)[CH3:2]
Reactant: c1cncc(C2CNCCN2)c1
Reactant: CCn1cc(C(=O)O)c(=O)c2cc(F)c(F)cc21
Solvent: c1ccncc1
Solvent: CCOCC
Product: CCn1cc(C(=O)O)c(=O)c2cc(F)c(N3CCNC(c4cccnc4)C3)cc21
Temperature: 25 °C
Yield: 39.7 %

Procedure:
A mixture of 177 mg of 1-ethyl-6,7-difluoro-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid, 342 mg of 2-(3-pyridinyl)piperazine and 5 ml of pyridine was heated at 90°-95° C. in a pressure bottle for 5 hours, then cooled at room temperature, then at 0° C. Ether was added to triturate the mixture, then the solid was collected and washed with methanol and ether. This solid was redissolved in a hot mixture of chloroform and methanol, filtered and triturated with ether. The precipitate was collected and dried in vacuo, giving 110 mg of the desired product.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:26]=[CH:25][CH:24]=[CH:23][C:4]=1[C:5]([NH:7][CH2:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:21]=[CH:20][C:19]([OH:22])=[CH:18][CH:17]=2)=[CH:12][CH:11]=1)=[O:6].Br[C:28]([CH3:33])([CH3:32])[C:29]([OH:31])=[O:30]>C(Cl)(Cl)Cl.CO>[CH3:32][C:28]([O:22][C:19]1[CH:20]=[CH:21][C:16]([C:13]2[CH:14]=[CH:15][C:10]([CH2:9][CH2:8][NH:7][C:5](=[O:6])[C:4]3[CH:23]=[CH:24][CH:25]=[CH:26][C:3]=3[O:2][CH3:1])=[CH:11][CH:12]=2)=[CH:17][CH:18]=1)([CH3:33])[C:29]([OH:31])=[O:30]
Reactant: COc1ccccc1C(=O)NCCc1ccc(-c2ccc(O)cc2)cc1
Reactant: CC(C)(Br)C(=O)O
Solvent: CO
Solvent: ClC(Cl)Cl
Product: COc1ccccc1C(=O)NCCc1ccc(-c2ccc(OC(C)(C)C(=O)O)cc2)cc1

Procedure:
0.5 gm (1.4 millimols) of 4-[2-(2-methoxy-benzamido)-ethyl]-4'-hydroxy-biphenyl were heated at 90°-130° C for 90 minutes with 0.025 gm of 2-bromo-2-methyl-propionic acid. The reaction product was isolated by chromatography on silicagel with chloroform/methanol (9:1) as the eluant. M.P. 133° C. M + H = 433;
Reaction SMILES: [CH3:1][C:2]1([CH3:22])[CH:14]=[C:13]2[C:5](=[C:6]3[C:11](=[CH:12]2)[CH:10]=[CH:9][C:8]2[CH:15]=[CH:16][C:17](B(O)O)=[CH:18][C:7]3=2)[CH:4]=[CH:3]1.Br[C:24]1[CH:25]=[C:26]([C:31]2[N:36]=[C:35]([C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)[N:34]=[C:33]([C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)[N:32]=2)[CH:27]=[C:28](Br)[CH:29]=1.C([O-])([O-])=O.[K+].[K+].[N:55]1[CH:60]=[CH:59][CH:58]=[CH:57][C:56]=1[C:61]1[CH:66]=[CH:65][C:64](B(O)O)=[CH:63][CH:62]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(O)C.C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:22])[CH:14]=[C:13]2[C:5](=[C:6]3[C:11](=[CH:12]2)[CH:10]=[CH:9][C:8]2[CH:15]=[CH:16][C:17]([C:24]4[CH:25]=[C:26]([C:31]5[N:36]=[C:35]([C:37]6[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=6)[N:34]=[C:33]([C:43]6[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=6)[N:32]=5)[CH:27]=[C:28]([C:64]5[CH:63]=[CH:62][C:61]([C:56]6[CH:57]=[CH:58][CH:59]=[CH:60][N:55]=6)=[CH:66][CH:65]=5)[CH:29]=4)=[CH:18][C:7]3=2)[CH:4]=[CH:3]1
Reactant: OB(O)c1ccc(-c2ccccn2)cc1
Reactant: Brc1cc(Br)cc(-c2nc(-c3ccccc3)nc(-c3ccccc3)n2)c1
Reactant: CC1(C)C=CC2=c3c(ccc4ccc(B(O)O)cc34)=CC2=C1
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: Cc1ccccc1
Solvent: CCO
Product: CC1(C)C=CC2=c3c(ccc4ccc(-c5cc(-c6ccc(-c7ccccn7)cc6)cc(-c6nc(-c7ccccc7)nc(-c7ccccc7)n6)c5)cc34)=CC2=C1
Temperature: 80 °C
Reaction time: 3 h
Yield: 38 %

Procedure:
In a stream of argon, 185 mg (0.644 mmol) of 9,9-dimethyl-2-benzo[c]fluoreneboronic acid, 300 mg (0.644 mmol) of 2-(3,5-dibromophenyl)-4,6-diphenyl-1,3,5-triazine and 7.44 mg (0.00644 mmol) of tetrakis(triphenylphosphine)palladium were suspended in a mixed solvent composed of 24 mL of toluene and 3 mL of ethanol, and the resultant suspension was heated to 50° C. To the suspension, 1.93 ml (1.93 mmol) of an aqueous 1M K2CO3 solution was gradually added dropwise, and the mixture was stirred for 3 hours. The resultant reaction mixture was heated to 80° C. and further stirred for 3 hours. The reaction mixture was cooled to room temperature, and then, 256 mg (1.29 mmol) of 4-(2-pyridyl)phenylboronic acid and 2.90 mL (2.90 mmol) of an aqueous 1M K2CO3 solution were added to the reaction mixture. The resultant mixture was heated to 80° C., and maintained at that temperature for 24 hours while being stirred. The obtained reaction mixture was cooled to room temperature, and then distilled under a reduced pressure to remove all volatile materials. Methanol was added to the concentrate, and the thus-deposited solid was collected by filtration. The obtained crude product was purified by silica gel chromatography using a hexane/chloroform (1:2) mixed solvent as an eluent to give 172 mg of the target 2-[5-(9,9-dimethylbenzo[c]fluoren-2-yl)-4′-(2-pyridyl)biphenyl-3-yl]-4,6-diphenyl-1,3,5-triazine as a white solid (yield: 38.0%).
Reaction SMILES: [C:1]([O:13][CH3:14])(=[O:12])[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.C(O)[CH2:16][CH2:17][OH:18].O.[C:21]([O-])(=[O:23])[CH3:22].[La+3].C([O-])(=O)C.C([O-])(=O)C>>[C:6]([O:8][CH2:9][CH2:16][CH2:17][OH:18])(=[O:7])[C:5]1[CH:10]=[CH:11][C:2]([C:1]([O:13][CH2:14][CH2:22][CH2:21][OH:23])=[O:12])=[CH:3][CH:4]=1
Reactant: CC(=O)[O-]
Reactant: COC(=O)c1ccc(C(=O)OC)cc1
Reactant: OCCCO
Agent: [La+3]
Solvent: O
Product: O=C(OCCCO)c1ccc(C(=O)OCCCO)cc1

Procedure:
This example demonstrates the transesterification reaction of dimethyl terephthalate with 1,3-propanediol using lanthanum acetate monohydrate as the transesterification catalyst (150 ppm La based on final polymer) to form bis(3-hydroxypropyl) terephthalate.
Reaction SMILES: [C:1]([C:3]1[N:4]=[CH:5][C:6]([NH:18][C@H:19]([CH2:23][CH:24]([CH3:26])[CH3:25])[C:20]([NH2:22])=[O:21])=[N:7][C:8]=1[NH:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]#[N:17])=[CH:12][CH:11]=1)#[N:2].[OH-:27].[Na+].[OH:29]O.CC(O)=O>CCO.CS(C)=O>[NH2:22][C:20](=[O:21])[C@H:19]([NH:18][C:6]1[N:7]=[C:8]([NH:9][C:10]2[CH:11]=[CH:12][C:13]([C:16](=[O:29])[NH2:17])=[CH:14][CH:15]=2)[C:3]([C:1]([NH2:2])=[O:27])=[N:4][CH:5]=1)[CH2:23][CH:24]([CH3:26])[CH3:25]
Reactant: OO
Reactant: [OH-]
Reactant: CC(C)C[C@@H](Nc1cnc(C#N)c(Nc2ccc(C#N)cc2)n1)C(N)=O
Agent: [Na+]
Solvent: CCO
Solvent: CC(=O)O
Solvent: CS(C)=O
Product: CC(C)C[C@@H](Nc1cnc(C(N)=O)c(Nc2ccc(C(N)=O)cc2)n1)C(N)=O
Temperature: 25 °C
Reaction time: 1 h

Procedure:
The compound (R)-2-(5-cyano-6-(4-cyanophenylamino)pyrazin-2-ylamino)-4-methylpentanamide (57 mg, 0.163 mmol) was dissolved in EtOH (2 mL) and DMSO (1 mL), aq. 1N NaOH (1.0 mL) and aq. H2O2 (30%, 1.0 mL) were added. The mixture was stirred at room temperature for 60 min. HOAc (0.5 mL) was added. The mixture was then concentrated in vacuo. The residue was purified by HPLC to give the titled compound (46 mg). MS 386.4 (M+H); UV 206.0, 269.5, 325.6 nm; t 0.475 min.
Reaction SMILES: [CH:1]1([CH2:4][OH:5])[CH2:3][CH2:2]1.CC(C)([O-])C.[K+].[Cl:12][C:13]1[CH:14]=[C:15]([NH:20][C:21]2[C:30]3[C:25](=[CH:26][C:27](F)=[C:28]([N+:31]([O-:33])=[O:32])[CH:29]=3)[N:24]=[CH:23][N:22]=2)[CH:16]=[CH:17][C:18]=1[F:19].Cl>CN(C)C=O.O>[Cl:12][C:13]1[CH:14]=[C:15]([NH:20][C:21]2[C:30]3[C:25](=[CH:26][C:27]([O:5][CH2:4][CH:1]4[CH2:3][CH2:2]4)=[C:28]([N+:31]([O-:33])=[O:32])[CH:29]=3)[N:24]=[CH:23][N:22]=2)[CH:16]=[CH:17][C:18]=1[F:19]
Reactant: O=[N+]([O-])c1cc2c(Nc3ccc(F)c(Cl)c3)ncnc2cc1F
Reactant: OCC1CC1
Agent: CC(C)(C)[O-]
Agent: Cl
Agent: [K+]
Solvent: O
Solvent: CN(C)C=O
Product: O=[N+]([O-])c1cc2c(Nc3ccc(F)c(Cl)c3)ncnc2cc1OCC1CC1
Temperature: 10 °C
Reaction time: 0.5 h

Procedure:
29.36 g of cyclopropylmethanol are dissolved in 310 ml of N,N-dimethylformamide and cooled to about 10° C. in an ice bath. Then 41.58 g of potassium tert. butoxide are added batchwise, while the temperature should remain below 15° C. The reaction mixture is then stirred for another 30 minutes at 10° C., after which time 31.19 g of 4-[(3-chloro-4-fluoro-phenyl)amino]-7-fluoro-6-nitro-quinazoline are added batchwise, while again the temperature should not exceed 15° C. The deep red reaction mixture is stirred for another hour at 15° C. For working up, the mixture is poured onto 2.5 l of water and neutralised with 2N hydrochloric acid. The yellowish precipitate formed is suction filtered, washed with water and dried at 50° C. in a drying cupboard.
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[C:21]3[C:20](=O)[CH2:19][CH2:18][CH2:17][C:16]=3[NH:15][C:14]3[CH2:13][CH2:12][CH2:11][C:10](=[O:23])[C:9]2=3)=[CH:4][CH:3]=1.C(O)C.[BH4-].[Na+]>N1C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[C:9]3[C:10](=[O:23])[CH2:11][CH2:12][CH2:13][C:14]=3[NH:15][C:16]3[CH2:17][CH2:18][CH2:19][CH2:20][C:21]2=3)=[CH:4][CH:3]=1
Reactant: O=C1CCCC2=C1C(c1ccc(Cl)cc1)C1=C(CCCC1=O)N2
Agent: [BH4-]
Agent: [Na+]
Solvent: CCO
Solvent: c1ccncc1
Product: O=C1CCCC2=C1C(c1ccc(Cl)cc1)C1=C(CCCC1)N2
Yield: 17.4 %

Procedure:
To a stirred 70° C. mixture of 9-(4-chlorophenyl)-3,4,6,7,9,10-hexahydro-1,8(2H,5H)-acridinedione (6.0 g), ethanol (160 mL) and pyridine (50 mL) was added sodium borohydride (7.5 g, 198.4 mmole) in two portions over six hours. The solvent was removed; the resulting yellow solid washed well with water and dried in vacuo. Chromatography (methylene chloride/ethyl acetate; 85/15) and recrystallization from ethanol provided the title compound (1.0 g) as a white solid, mp 253°-254° C.; NMR: 1.41-1.51 (m,3, CH2), 1.60-1.88 (m,5, CH2), 2.07-2.14 (m,4, CH2), 2.38-2.41 (m,2, CH2), 4.16 (s,1, CH), 7.16 (d,2, J=8.4, Ar), 7.25 (d,2, J=8.4, Ar), 8.39 (s,1, NH); (CI, CH4) MS: m/z=314(M+1). Analysis for C19H20ClNO: Calculated C, 72.72; H, 6.37; N, 4.46; Found: C, 72.35; H, 6.60; N, 4.29.