Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [NH2:1][C:2]1[C:3]([CH3:13])=[C:4]([CH:9]=[C:10]([F:12])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[CH2:14]([N:21]1[C@@H:26]([CH3:27])[CH2:25][C:24](=O)[CH2:23][C@H:22]1[CH3:29])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>C1COCC1.C(O)(C(F)(F)F)=O>[CH2:14]([N:21]1[C@H:26]([CH3:27])[CH2:25][CH:24]([NH:1][C:2]2[C:3]([CH3:13])=[C:4]([CH:9]=[C:10]([F:12])[CH:11]=2)[C:5]([O:7][CH3:8])=[O:6])[CH2:23][C@H:22]1[CH3:29])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: C[C@@H]1CC(=O)C[C@H](C)N1Cc1ccccc1
Reactant: COC(=O)c1cc(F)cc(N)c1C
Agent: CC(=O)O[BH-](OC(C)=O)OC(C)=O
Agent: O=C([O-])O
Agent: [Na+]
Solvent: C1CCOC1
Solvent: O=C(O)C(F)(F)F
Product: COC(=O)c1cc(F)cc(NC2C[C@@H](C)N(Cc3ccccc3)[C@H](C)C2)c1C
Temperature: 60 °C
Reaction time: 1 h
Yield: 30.3 %

Procedure:
To a stirred solution of methyl 3-amino-5-fluoro-2-methylbenzoate (520 mg, 2.84 mmol) in THF (20 mL) and TFA (813 uL) was added (2R,6S)-1-benzyl-2,6-dimethylpiperidin-4-one (679 mg, 3.12 mmol) at 0° C. The mixture was stirred at 60° C. for 1 hour under nitrogen atmosphere. Then the mixture was cooled to 0° C. in an ice bath, sodium triacetoxyborohydride (1.27 g, 5.68 mmol) was added. The reaction mixture was stirred at rt for 2 hours. Then aq. NaHCO3 was added at 0° C. until pH8-9, and the content was extracted with ethylacetate. The organic layer was dried over MgSO4 and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (NH—SiO2; heptane/ethylacetate=5/1) to give titled compound as a colorless oil (331 mg, 30% yield.). 1H-NMR (400 MHz, CDCl3) δppm; 7.35-7.39 (m, 2H), 7.27-7.30 (m, 2H), 7.21-7.26 (m, 1H), 6.76 (dd, J=2.4, 9.2 Hz, 1H), 6.45 (dd, J=2.4, 11.2 Hz, 1H), 3.94 (d, J=14.4 Hz, 1H), 3.87 (s, 3H), 3.58-3.65 (m, 2H), 3.46 (d, J=14.4 Hz, 1H), 3.06-3.12 (m, 1H), 2.94-3.01 (m, 1H), 2.21 (s, 3H), 2.02-2.07 (m, 1H), 1.82-1.89 (m, 1H), 1.15-1.22 (m, 1H), 1.12 (d, J=6.0 Hz, 3H), 1.09 (d, J=7.2 Hz, 3H).
Reaction SMILES: [CH2:1]([C:3]1[N:4]([C:14]2[CH:19]=[CH:18][C:17]([CH2:20][CH2:21][NH:22][C:23](=O)[O-:24])=[CH:16][CH:15]=2)[CH:5]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[N:7]=1)[CH3:2].[F:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=1[S:33]([NH2:36])(=[O:35])=[O:34]>>[F:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=1[S:33]([NH:36][C:23]([NH:22][CH2:21][CH2:20][C:17]1[CH:16]=[CH:15][C:14]([N:4]2[CH:5]=[C:6]([C:8]3[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=3)[N:7]=[C:3]2[CH2:1][CH3:2])=[CH:19][CH:18]=1)=[O:24])(=[O:35])=[O:34]
Reactant: CCc1nc(-c2ccccc2)cn1-c1ccc(CCNC(=O)[O-])cc1
Reactant: NS(=O)(=O)c1ccccc1F
Product: CCc1nc(-c2ccccc2)cn1-c1ccc(CCNC(=O)NS(=O)(=O)c2ccccc2F)cc1

Procedure:
The title compound was prepared according to the procedure described in step 2 of Example 18 from 2-[4-(2-ethyl-4-phenyl-1H-imidazol-1-yl)phenyl]ethylcarbamate and 2-fluorobenzenesulfonamide. MS (ESI) n/z 500 [M+H]+, 498 [M−H]−, 1H-NMR (CDCl3) δ 1.23 (3H, t, J=6.0 Hz), 2.71 (2H, q, J=6.0 Hz), 2.84 (2H, t, J=6.0 Hz), 3.44-3.52 (2H, m), 6.58 (1H, br), 7.18-7.30 (7H, m), 7.37 (2H, t, J=9.0 Hz), 7.59-7.65 (1H, m), 7.78 (2H, d, J=6.0 Hz), 7.84-7.90 (2H, m).
Reaction SMILES: [N:1]1([CH2:8][C:9]2[S:13][C:12]([C:14](=[N:16][OH:17])[NH2:15])=[CH:11][CH:10]=2)[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C(O[C:21](=O)[CH2:22][NH:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])C>>[C:27]([O:26][C:24]([NH:23][CH2:22][C:21]1[O:17][N:16]=[C:14]([C:12]2[S:13][C:9]([CH2:8][N:1]3[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]3)=[CH:10][CH:11]=2)[N:15]=1)=[O:25])([CH3:30])([CH3:29])[CH3:28]
Reactant: CCOC(=O)CNC(=O)OC(C)(C)C
Reactant: NC(=NO)c1ccc(CN2CCCCCC2)s1
Product: CC(C)(C)OC(=O)NCc1nc(-c2ccc(CN3CCCCCC3)s2)no1
Yield: 41.8 %

Procedure:
Using 1.7 g of 5-(hexahydro-1H-azepin-1-yl)methyl-2-thiopheneamidoxime and 2.0 g of N-t-butoxycarbonylglycine ethyl ester, 1.1 g of the title compound was obtained in the same manner as described in the step 1) of Example 56.
Reaction SMILES: [C:1]([C:4]1[CH:5]=[C:6]([C:10]2[CH:15]=[CH:14][C:13](OS(C(F)(F)F)(=O)=O)=[CH:12][CH:11]=2)[CH:7]=[CH:8][CH:9]=1)(=[O:3])[CH3:2].[N:24]1[CH:29]=[CH:28][CH:27]=[C:26]([CH2:30][CH2:31][CH:32]([OH:35])[C:33]#[CH:34])[CH:25]=1.O>CN(C)C=O.C(N(CC)CC)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>[C:1]([C:4]1[CH:5]=[C:6]([C:10]2[CH:15]=[CH:14][C:13]([C:34]#[C:33][CH:32]([OH:35])[CH2:31][CH2:30][C:26]3[CH:25]=[N:24][CH:29]=[CH:28][CH:27]=3)=[CH:12][CH:11]=2)[CH:7]=[CH:8][CH:9]=1)(=[O:3])[CH3:2]
Reactant: C#CC(O)CCc1cccnc1
Reactant: CC(=O)c1cccc(-c2ccc(OS(=O)(=O)C(F)(F)F)cc2)c1
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Solvent: CCN(CC)CC
Solvent: CN(C)C=O
Solvent: O
Product: CC(=O)c1cccc(-c2ccc(C#CC(O)CCc3cccnc3)cc2)c1
Yield: 64.4 %

Procedure:
3'-Acetyl-4-trifluoromethanesulfonyloxybiphenyl (2.0 g), (±)-5-(3-pyridyl)pent-1-yn-3-ol (1.4 g), bis(triphenylphosphine)palladium(II) chloride (0.2 g) in N,N-dimethylformamide (8 ml) and triethylamine (4.5 ml) were heated at 90° C. for 2 hours with stirring under nitrogen. After cooling the reaction was poured into water and extracted with dichloromethane. The organic solution was washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography over silica eluting with ethanol:dichloromethane (3:97) to give the sub-title compound as a pale yellow gum (1.33 g).
Reaction SMILES: [Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:12][C:11]([C:13]([OH:15])=O)=[N:10][C:9]=2[C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=2[Cl:23])=[CH:4][CH:3]=1.C(N(C(C)C)CC)(C)C.[CH:33]1[CH:38]=[N:37][C:36]2N(O)N=N[C:35]=2[CH:34]=1.F[P-](F)(F)(F)(F)F.ClC1N(C)CC[NH+]1C.C(N)CCCC>ClCCl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:12][C:11]([C:13]([NH:37][CH2:36][CH2:35][CH2:34][CH2:33][CH3:38])=[O:15])=[N:10][C:9]=2[C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=2[Cl:23])=[CH:4][CH:3]=1
Reactant: O=C(O)c1nc(-c2ccc(Cl)cc2Cl)c(-c2ccc(Br)cc2)s1
Reactant: On1nnc2cccnc21
Agent: CN1CC[NH+](C)C1Cl
Agent: F[P-](F)(F)(F)(F)F
Solvent: CCCCCN
Solvent: ClCCl
Solvent: CCN(C(C)C)C(C)C
Product: CCCCCNC(=O)c1nc(-c2ccc(Cl)cc2Cl)c(-c2ccc(Br)cc2)s1
Temperature: 0 °C
Reaction time: 8 h
Yield: 69.4 %

Procedure:
Part B: 5-(4-Bromophenyl)-4-(2,4-dichlorophenyl)thiazole-2-carboxylic acid (0.50 gram, 1.17 mmol) and diisopropylethylamine (DIPEA) (1.02 mL, 5.85 mmol) are dissolved in dichloromethane (5 mL) and cooled to 0° C. 7-Aza-1-hydroxybenzotriazole (HOAt) (0.11 gram, 0.81 mmol) and 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate (CIP) (0.50 gram, 1.76 mmol) are added, followed by addition of n-pentylamine (0.15 gram, 1.76 mmol) and the resulting mixture is stirred at room temperature overnight. Flash chromatographic purification (dichloromethane) gives 5-(4-bromophenyl)-4-(2,4-dichlorophenyl)-N-(n-pentyl)thiazole-2-carboxamide as an amorphous solid (0.28 gram, 48% yield).
Reaction SMILES: [F:1][C:2]1[CH:10]=[CH:9][C:8]([CH:11]=[O:12])=[CH:7][C:3]=1[C:4](O)=[O:5].S(Cl)(Cl)=O.[CH3:17][NH:18][CH3:19]>C(Cl)Cl>[F:1][C:2]1[CH:10]=[CH:9][C:8]([CH:11]=[O:12])=[CH:7][C:3]=1[C:4]([N:18]([CH3:19])[CH3:17])=[O:5]
Reactant: CNC
Reactant: O=Cc1ccc(F)c(C(=O)O)c1
Solvent: ClCCl
Solvent: O=S(Cl)Cl
Product: CN(C)C(=O)c1cc(C=O)ccc1F
Temperature: 0 °C
Reaction time: 1 h
Yield: 76 %

Procedure:
The solution of 2-fluoro-5-formylbenzoic acid (3 g, 17.8 mmol) in methylene chloride (10 mL) was added thionyl chloride (2.0 mL, 26.7 mmol) slowly at 0° C. Then the cold reaction mixture was heated to reflux for 3 h. The solution was cooled to 0° C., added dimethylamine (40 wt. % solution in water, 5 mL) slowly, and then stirred at room temperature for 1 h. The solution was washed with water and brine, the organic layer was dried with Na2SO4 and the solvent was removed to get the desired product (2.4 g, yield 76%). LC-MS (ESI) m/z: 196 (M+1)+.
Reaction SMILES: [CH2:1]([N:4]1[C:8]2=[C:9]([Cl:13])[N:10]=[CH:11][CH:12]=[C:7]2[C:6]([CH3:14])=[C:5]1[CH3:15])[CH:2]=[CH2:3].[CH3:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21][NH2:22])=[CH:19][CH:18]=1>>[ClH:13].[CH2:1]([N:4]1[C:8]2=[C:9]([NH:22][CH2:21][C:20]3[CH:23]=[CH:24][C:17]([CH3:16])=[CH:18][CH:19]=3)[N:10]=[CH:11][CH:12]=[C:7]2[C:6]([CH3:14])=[C:5]1[CH3:15])[CH:2]=[CH2:3]
Reactant: C=CCn1c(C)c(C)c2ccnc(Cl)c21
Reactant: Cc1ccc(CN)cc1
Product: C=CCn1c(C)c(C)c2ccnc(NCc3ccc(C)cc3)c21
Product: Cl
Yield: 29 %

Procedure:
In accordance with the same procedures as in Step 3 of Example 198, except for using 1-allyl-7-chloro-2,3-dimethyl-1H-pyrrolo[2,3-c]pyridine prepared in Step 1 and 4-methylbenzylamine, the titled compound was obtained as a white solid. (Yield: 29%)
Reaction SMILES: [C:1]([OH:7])(=[O:6])[CH2:2][C:3]([OH:5])=O.[CH2:8]([K])[CH3:9].CCN(CC)CC.[Mg+2].[Cl-].[Cl-].[C:21]1(C(Cl)=O)[C:30]2[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH:24]=[CH:23][CH:22]=1>C(#N)C>[CH2:8]([O:7][C:1](=[O:6])[CH2:2][C:3]([C:29]1[C:30]2[C:25](=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:26]=[CH:27][CH:28]=1)=[O:5])[CH3:9]
Reactant: O=C(O)CC(=O)O
Reactant: CC[K]
Reactant: O=C(Cl)c1cccc2ccccc12
Agent: [Cl-]
Agent: [Mg+2]
Solvent: CC#N
Solvent: CCN(CC)CC
Product: CCOC(=O)CC(=O)c1cccc2ccccc12
Temperature: 25 °C
Reaction time: 2.5 h
Yield: 66.1 %

Procedure:
A suspension of ethyl potassium malon ate (3.4 g, 20.0 mmol) in acetonitrile (30.6 mL) was treated with Et3N (3.11 mL, 22.3 mmol) and MgCl2 (2.38 g, 25.0 mmol). The resulting suspension was stirred at rt for 2.5 h, then treated with 1-naphthoylchloride (1.55 mL, 10.3 mmol) and stirred under Ar at rt overnight. The acetonitrile was removed in vacuo, toluene (14 mL) was added and the suspension was concentrated again. The residue was suspended in toluene (14 mL) and washed with 12% Aq. HCl (14.1 mL). The organic layer was removed, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified via flash chromatography (SiO2, 10% EtOAc/Heptane) to afford 3-Naphthalen-1-yl-3-oxo-propionic acid ethyl ester (1.65 g, 66%) as a 3.5:1 mixture of keto/enol isomers: 1H NMR (CDCl3, chemical shifts in ppm relative to TMS): 1.21 (t, 3H, ketone isomer, J=7.1 Hz), 1.36 (3h, enol isomer, J=7.1 Hz), 4.11 (s, 2H, ketone isomer), 4.20 (q, 2H, ketone isomer, J=7.4 Hz), 4.32 (q, 2H, enol isomer, J=7.4 Hz), 5.50 (s, 1H, enol isomer), 7.46-7.68 (m, 3H), 7.88 (d, 1H, J=8.1 Hz), 7.92 (d, 1H, J=7.3 Hz), 8.03 (d, 1H, J=8.1 Hz), 8.36 (d, 1H, enol isomer, J=8.1 Hz), 8.76 (d, 1H, J=8.1 Hz); Field Desorption Mass Spectrometry: m/z 242.
Reaction SMILES: N1C=CC=CC=1.[O:7]1[CH2:12][CH2:11]OCC1.[Cl:13][P:14]1[O:19]C(=O)[C:17]2[CH:21]=[CH:22][CH:23]=C[C:16]=2[O:15]1>O1CCOCC1>[Cl:13][P:14]1(=[O:19])[O:15][CH2:16][C:17]2[CH:21]=[CH:22][CH:23]=[CH:11][C:12]=2[O:7]1
Reactant: O=C1OP(Cl)Oc2ccccc21
Reactant: C1COCCO1
Solvent: c1ccncc1
Product: O=P1(Cl)OCc2ccccc2O1

Procedure:
Add into a vial first 2 mL of pyridine/dioxane, 3:1 v/v followed by 100 μL of 1 M 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one solution in dry dioxane to give a 50 mM solution of the phosphitylating reagent, e.g. 2-chloro-4H-1,3,2-benzodioxaphosphorin-2-one, in dioxane/pyridine, 3:1 (v/v). Homogenize the solution by gently shaking. Start the reaction by drawing the 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one solution through the synthesis column from the vial.
Reaction SMILES: [NH2:1][C:2]1[C:3]([NH:19][C:20]2[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][CH:21]=2)=[CH:4][C:5]([O:8][C:9]2[CH:10]=[C:11]([NH:15][C:16](=[O:18])[CH3:17])[CH:12]=[CH:13][CH:14]=2)=[N:6][CH:7]=1.[C:27]([CH2:29][C:30](OCC)=O)#[N:28]>>[C:27]([CH2:29][CH:30]1[NH:1][C:2]2[CH:7]=[N:6][C:5]([O:8][C:9]3[CH:10]=[C:11]([NH:15][C:16](=[O:18])[CH3:17])[CH:12]=[CH:13][CH:14]=3)=[CH:4][C:3]=2[N:19]1[C:20]1[CH:21]=[CH:22][C:23]([OH:26])=[CH:24][CH:25]=1)#[N:28]
Reactant: CC(=O)Nc1cccc(Oc2cc(Nc3ccc(O)cc3)c(N)cn2)c1
Reactant: CCOC(=O)CC#N
Product: CC(=O)Nc1cccc(Oc2cc3c(cn2)NC(CC#N)N3c2ccc(O)cc2)c1
Temperature: 195 °C
Yield: 78 %

Procedure:
The product from Step 3 (2.9 g, 8.3 mmol) and ethyl cyanoacetate (6 mL) were combined and heated to 195° C. in a sealed tube. The reaction mixture was cooled and the crude material was purified by chromatography (0-10% methanol in EtOAc) to give the title compound (2.6 g, 78%). MS (ES+) m/e 400 [M+H]+.
Reaction SMILES: [O:1]1[C:6]2[CH:7]=[CH:8][CH:9]=[C:10]([N:11]([CH2:15][CH2:16][OH:17])[CH2:12][CH2:13][OH:14])[C:5]=2[O:4][CH2:3][CH2:2]1.C(N(CC)CC)C.[S:25](Cl)([CH3:28])(=[O:27])=[O:26]>C(Cl)Cl>[O:1]1[C:6]2[CH:7]=[CH:8][CH:9]=[C:10]([N:11]([CH2:15][CH2:16][O:17][S:25]([CH3:28])(=[O:27])=[O:26])[CH2:12][CH2:13][O:14][S:25]([CH3:28])(=[O:27])=[O:26])[C:5]=2[O:4][CH2:3][CH2:2]1
Reactant: OCCN(CCO)c1cccc2c1OCCO2
Reactant: CS(=O)(=O)Cl
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: CS(=O)(=O)OCCN(CCOS(C)(=O)=O)c1cccc2c1OCCO2
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
To a solution of II (39.6 g, 0.165 mol) and triethyl amine (69 mL, 0.5 mol) in methylene chloride (250 mL), chilled to 5° C. in an ice-bath, is added a solution of mesyl chloride (38 mL, 0.5 mol) in methylene chloride (50 mL). The addition is carried out over 0.5 h at temperature not exceeding 18° C. The ice-bath is removed and resulting suspension is stirred at ambient temperature for 1 h. At that time, TLC and HPLC showed disappearance of starting material. The reaction mixture is washed with water (1×150 mL) and 5% aqueous NaHCO3 solution (1×150 mL), dried with MgSO4 and concentrated to afford III as red oil, crude yield 67.0 g (102%). 1H NMR (CDCl3) δ6.85 (m, 1H), 6.63 (m, 2H), 4.28 (m, 8H), 3.55 (t, J=7.5 Hz, 4H), 2.97 (s, 6H).
Reaction SMILES: [CH3:1][Si:2]([CH3:26])([CH3:25])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[CH:11]=[C:10]([C:12]2[N:17]3[CH:18]=[CH:19][N:20]=[C:16]3[CH:15]=[C:14]([C:21]([O:23]C)=O)[N:13]=2)[CH:9]=[N:8]1.CCO.O.[NH2:31][NH2:32]>>[CH3:26][Si:2]([CH3:1])([CH3:25])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[CH:11]=[C:10]([C:12]2[N:17]3[CH:18]=[CH:19][N:20]=[C:16]3[CH:15]=[C:14]([C:21]([NH:31][NH2:32])=[O:23])[N:13]=2)[CH:9]=[N:8]1
Reactant: NN
Reactant: COC(=O)c1cc2nccn2c(-c2cnn(COCC[Si](C)(C)C)c2)n1
Solvent: CCO
Solvent: O
Product: C[Si](C)(C)CCOCn1cc(-c2nc(C(=O)NN)cc3nccn23)cn1
Yield: 92.7 %

Procedure:
In a 20 mL flask, methyl 5-(1-((2-(trimethylsilyl)-ethoxy)methyl)-1H-pyrazol-4-yl)imidazo[1,2-c]pyrimidine-7-carboxylate (Example 122; Step C) (50 mg, 0.13 mmol) was dissolved in EtOH (540 μL, 0.13 mmol). To this was added a large excess of hydrazine hydrate (104 μL, 3.3 mmol). The reaction mixture was refluxed for 1 hour, and then concentrated down to dryness. The residue was diluted in EtOAc and washed with water and brine. The organic layer was dried with MgSO4, filtered and concentrated in vacuo to afford 5-(1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazol-4-yl)imidazo[1,2-c]pyrimidine-7-carbohydrazide (45 mg, 90% yield) as a yellow oil. MS (apci) m/z=374.4 (M+H).
Reaction SMILES: [ClH:1].[Br:2][CH2:3][C:4]1[O:12][C:11]2[CH:10]=[CH:9][N:8]=[CH:7][C:6]=2[CH:5]=1.[CH:13]1[CH:18]=[CH:17][C:16]([P:19]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[CH:15][CH:14]=1>C1COCC1.CCO>[ClH:1].[Br-:2].[O:12]1[C:11]2[CH:10]=[CH:9][N:8]=[CH:7][C:6]=2[CH:5]=[C:4]1[CH2:3][P+:19]([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:16]1[CH:15]=[CH:14][CH:13]=[CH:18][CH:17]=1
Reactant: BrCc1cc2cnccc2o1
Reactant: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Agent: Cl
Solvent: CCO
Solvent: C1CCOC1
Product: [Br-]
Product: c1ccc([P+](Cc2cc3cnccc3o2)(c2ccccc2)c2ccccc2)cc1

Procedure:
A solution of 2-bromomethylfuro[3,2-c]pyridine hydrochloride (Preparation 5, 2.12 g, 8.5 mmol) and PPh3 (2.24 g, 8.5 mmol) in anhydrous THF-EtOH (1:1, 80 mL) was heated under reflux for 3 d. The solvents were removed under reduced pressure, then the residual solid was triturated with hot THF to furnish the title compound: RT=2.32 min.
Reaction SMILES: C(OC([N:8]([CH:10]1[CH2:14][CH2:13][N:12]([S:15]([C:18]2[C:19]3[C:20]([Br:29])=[CH:21][N:22]=[C:23]([Cl:28])[C:24]=3[CH:25]=[CH:26][CH:27]=2)(=[O:17])=[O:16])[CH2:11]1)[CH3:9])=O)(C)(C)C.C(OC([NH:37]C1CCN(S(C2C3C(Cl)=CN=C(Cl)C=3C=CC=2)(=O)=O)C1)=O)(C)(C)C>>[NH2:37][C:23]1[C:24]2[CH:25]=[CH:26][CH:27]=[C:18]([S:15]([N:12]3[CH2:13][CH2:14][CH:10]([NH:8][CH3:9])[CH2:11]3)(=[O:17])=[O:16])[C:19]=2[C:20]([Br:29])=[CH:21][N:22]=1.[ClH:28]
Reactant: CC(C)(C)OC(=O)NC1CCN(S(=O)(=O)c2cccc3c(Cl)ncc(Cl)c23)C1
Reactant: CN(C(=O)OC(C)(C)C)C1CCN(S(=O)(=O)c2cccc3c(Cl)ncc(Br)c23)C1
Product: CNC1CCN(S(=O)(=O)c2cccc3c(N)ncc(Br)c23)C1
Product: Cl

Procedure:
Intermediate 24 is used in the method of Example 39 instead of Intermediate 26 to obtain the title compound as hydrochloride.
Reaction SMILES: C(OC(=O)[NH:7][CH2:8][CH:9]1[CH2:13][CH2:12][CH2:11][N:10]1[C:14]1[CH:15]=[C:16]2[C:25](=[CH:26][CH:27]=1)[O:24][CH2:23][C:22]1[N:17]2[CH:18]([CH3:37])[C:19](=[O:36])[N:20](COCC[Si](C)(C)C)[N:21]=1)(C)(C)C.[C:39]([OH:45])([C:41]([F:44])([F:43])[F:42])=[O:40]>C(Cl)Cl>[F:42][C:41]([F:44])([F:43])[C:39]([OH:45])=[O:40].[NH2:7][CH2:8][CH:9]1[CH2:13][CH2:12][CH2:11][N:10]1[C:14]1[CH:15]=[C:16]2[C:25](=[CH:26][CH:27]=1)[O:24][CH2:23][C:22]1[N:17]2[CH:18]([CH3:37])[C:19](=[O:36])[NH:20][N:21]=1
Reactant: CC1C(=O)N(COCC[Si](C)(C)C)N=C2COc3ccc(N4CCCC4CNC(=O)OC(C)(C)C)cc3N21
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: CC1C(=O)NN=C2COc3ccc(N4CCCC4CN)cc3N21
Temperature: 25 °C
Reaction time: 1 h

Procedure:
A mixture of crude {1-[4-methyl-3-oxo-2-(2-trimethylsilanyl-ethoxymethyl)-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-yl]-pyrrolidin-2-ylmethyl}-carbamic acid tert-butyl ester (0.117 mol) in DCM (2 mL) and TFA (1 mL) was stirred for 1 h at ambient temperature. The solvent was removed in vacuo and the residue was re-dissolved in MeOH (2 mL) and aqueous ammonium hydroxide (25%, 0.5 mL). The mixture was stirred for 2 h then purified by preparative HPLC (Table 3, Method 20) to give 6-(2-aminomethyl-pyrrolidin-1-yl)-4-methyl-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one trifluoroacetic acid as white solid (0.0068 g, 13% for 2 steps). LC/MS (Table 1, Method 4) Rt=1.111 min; MS m/z: 316 [M+H]+
Reaction SMILES: [C:1]1([C:10]2[C:11](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:12]([OH:14])=[O:13])[C:2](=[CH:6][CH:7]=[CH:8][CH:9]=1)[C:3]([OH:5])=O>S(=O)(=O)(O)O>[CH:8]1[CH:9]=[C:1]2[C:10]3[C:11]([C:12]([OH:14])=[O:13])=[CH:15][CH:16]=[CH:17][C:18]=3[C:3](=[O:5])[C:2]2=[CH:6][CH:7]=1
Reactant: O=C(O)c1ccccc1-c1ccccc1C(=O)O
Agent: O=S(=O)(O)O
Product: O=C(O)c1cccc2c1-c1ccccc1C2=O
Temperature: 70 °C

Procedure:
The following steps are suitable for synthesizing some charge transport materials of this invention involving a linking reaction as described in the following. In the first step, diphenic acid or its derivative is dissolved in large access of concentrated sulfuric acid and the solution is heated at approximately 70° C. for about 10 minutes. The product, 9-fluorenone-4-carboxylic acid or its derivative, is isolated. In the second step, 9-fluorenone-4-carboxylic acid or its derivative is chlorinated with thionyl chloride to form 9-fluorenone-4-carbonyl chloride or its derivative. Then, 9-fluorenone-4-carbonyl chloride or its derivative reacts with a diol, a dithiol, a diamine, a hydroxylamine, a hydroxythiol, or a thioamine in the presence of triethylamine. Non-limiting examples of suitable dithiol are 4,4′-thiobisbenzenethiol, 1,4-benzenedithiol, 1,3-benzenedithiol, sulfonyl-bis(benzenethiol), 2,5-dimecapto-1,3,4-thiadiazole, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol. Non-limiting examples of suitable diols are 2,2′-bi-7-naphtol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 10,10-bis(4-hydroxyphenyl)anthrone, 4,4′-sulfonyldiphenol, bisphenol, 4,4′-(9-fluorenylidene)diphenol, 1,10-decanediol, 1,5-pentanediol, diethylene glycol, 4.4′-(9-fluorenylidene)-bis(2-phenoxyethanol), bis(2-hydroxyethyl) terephthalate, bis[4-(2-hydroxyethoxy)phenyl] sulfone, hydroquinone-bis (2-hydroxyethyl)ether, and bis(2-hydroxyethyl) piperazine. Non-limiting examples of suitable diamine are diaminoarenes, and diaminoalkanes. Non-limiting examples of suitable hydroxylamine are p-aminophenol and fluoresceinamine. Non-limiting examples of suitable hydroxythiol are monothiohydroquinone and 4-mercapto-1-butanol. Non-limiting example of suitable thioamine is p-aminobenzenethiol. The intermediate product is isolated and dried. Then, the intermediate product is reacted with malononitrile in the presence of piperidine to form the dimeric electron transport material, which can be purified and dried.
Reaction SMILES: [CH3:1][CH2:2][CH3:3].C=CC.[CH:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1>>[C:7]1([CH:2]([CH3:3])[CH3:1])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1
Reactant: c1ccccc1
Reactant: CCC
Solvent: C=CC
Product: CC(C)c1ccccc1

Procedure:
An integrated process is disclosed for (i) catalytically cracking (FCC) a heavy hydrocarbon feedstock, (ii) obtaining a combined propane/propylene stream, and (iii) reacting the propylene of the combined propane/propylene stream with benzene to produce a cumene product stream. The integrated process comprises contacting a heavy hydrocarbon feedstock with a hydrocarbon cracking catalyst in a fluidized reactor zone to produce a hydrocarbon effluent stream that includes propane and propylene. The process then further comprises separating the combined propane/propylene stream from the hydrocarbon effluent stream, passing the combined propane/propylene stream to an alkylation reactor, and reacting at least some of the propylene of the combined propane/propylene stream with benzene in the alkylation reactor to produce cumene.
Reaction SMILES: [CH3:1][C@@:2]12[C:8]([CH3:10])([CH3:9])[C@@H:5]([CH2:6][CH2:7]1)[C:4](=O)[C:3]2=O.COP([CH2:19][C:20]([C:22]1[CH:23]=[N:24][N:25]([CH3:30])[C:26]=1[CH:27]1[CH2:29][CH2:28]1)=O)(=O)OC.O.[NH2:32][NH2:33]>>[CH:27]1([C:26]2[N:25]([CH3:30])[N:24]=[CH:23][C:22]=2[C:20]2[CH:19]=[C:4]3[C:3]([C@:2]4([CH3:1])[C:8]([CH3:10])([CH3:9])[C@H:5]3[CH2:6][CH2:7]4)=[N:33][N:32]=2)[CH2:29][CH2:28]1
Reactant: COP(=O)(CC(=O)c1cnn(C)c1C1CC1)OC
Reactant: CC1(C)[C@H]2CC[C@]1(C)C(=O)C2=O
Reactant: NN
Solvent: O
Product: Cn1ncc(-c2cc3c(nn2)[C@@]2(C)CC[C@@H]3C2(C)C)c1C1CC1

Procedure:
yellow foam. MS (ESI): 309.1 (MH+). Prepared from (1S,4R)-1,7,7-trimethyl-bicyclo[2.2.1]heptane-2,3-dione, [2-(5-Cyclopropyl-1-methyl-1H-pyrazol-4-yl)-2-oxo-ethyl]-phosphonic acid dimethyl ester, hydrazine monohydrate.
Reaction SMILES: [C:1]([NH:5][C:6]([C:8]1[C:9]2[CH2:10][C@H:11]3[CH2:23][C@H:12]3[C:13]=2[N:14]([C:16]2[CH:21]=[C:20](Br)[CH:19]=[CH:18][N:17]=2)[N:15]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[Cl-:24].[Li+]>CC(N(C)C)=O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:1]([NH:5][C:6]([C:8]1[C:9]2[CH2:10][C@H:11]3[CH2:23][C@H:12]3[C:13]=2[N:14]([C:16]2[CH:21]=[C:20]([Cl:24])[CH:19]=[CH:18][N:17]=2)[N:15]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]
Reactant: [Cl-]
Reactant: CC(C)(C)NC(=O)c1nn(-c2cc(Br)ccn2)c2c1C[C@H]1C[C@@H]21
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: [Br-]
Agent: [Li+]
Solvent: CC(=O)N(C)C
Product: CC(C)(C)NC(=O)c1nn(-c2cc(Cl)ccn2)c2c1C[C@H]1C[C@@H]21
Temperature: 180 °C
Yield: 51.5 %

Procedure:
A mixture of (1aR,5aR)-2-(4-bromo-pyridin-2-yl)-1a,2,5,5a-tetrahydro-1H-2,3-diaza-cyclopropa[a]pentalene-4-carboxylic acid tert-butylamide (0.010 g, 0.027 mmol) and lithium chloride (5.65 mg, 0.133 mmol) in DMA (1 mL) was heated in a heavy-walled sealed tube under microwave irradiation at 160 for 1 hour. Lithium chloride (20 mg) and tetrabutylammonium bromide (5 mg) were added. The reaction was heated in a heavy-walled sealed tube under microwave irradiation at 180° C. for 10 h. The mixture was purified by preparative HPLC to give the title compound as a white solid (4.6 mg). LCMS m/z=331.3 [M+H]+.