Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [Cl:1][C:2]1[N:3]=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][C:8]([C:12]1[CH:13]=[N:14][N:15]([CH2:17][CH:18]3[CH2:22][O:21]C(C)(C)[O:19]3)[CH:16]=1)=[CH:7][CH:6]=2.Cl>C1COCC1.C(Cl)Cl>[Cl:1][C:2]1[N:3]=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][C:8]([C:12]1[CH:13]=[N:14][N:15]([CH2:17][CH:18]([OH:19])[CH2:22][OH:21])[CH:16]=1)=[CH:7][CH:6]=2
Reactant: CC1(C)OCC(Cn2cc(-c3ccc4cnc(Cl)cc4c3)cn2)O1
Agent: Cl
Solvent: ClCCl
Solvent: C1CCOC1
Product: OCC(O)Cn1cc(-c2ccc3cnc(Cl)cc3c2)cn1
Temperature: 25 °C
Reaction time: 16 h

Procedure:
To a solution of 3-chloro-6-(1-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-1H-pyrazol-4-yl)isoquinoline (Preparation 29, 40 mg, 0.116 mmol) in THF (6 mL) at 0° C. was added hydrochloric acid (2.5M, 0.30 mL) and the reaction was stirred at room temperature for 16 hours. The solution was diluted with DCM, washed with saturated NaHCO3 solution, dried over Na2SO4 and concentrated in vacuo to afford the title compound as a yellow oil that was used directly in the next step (23 mg, 65%).
Reaction SMILES: [CH2:1]([O:3][C:4](=[O:19])[CH:5]([CH2:10][C:11](=O)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6](=[O:9])[CH2:7][CH3:8])[CH3:2].[OH-].[Na+].CCOCC>C(O)C>[CH2:1]([O:3][C:4]([CH:5]1[CH2:10][C:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:7]([CH3:8])[C:6]1=[O:9])=[O:19])[CH3:2]
Reactant: CCOC(=O)C(CC(=O)c1ccccc1)C(=O)CC
Agent: [Na+]
Agent: [OH-]
Solvent: CCOCC
Solvent: CCO
Product: CCOC(=O)C1CC(c2ccccc2)=C(C)C1=O
Temperature: 50 °C
Reaction time: 8 h
Yield: 77.8 %

Procedure:
A solution of the diketoester 20a (12 g, 45.8 mmol) in dry ethanol (150 ml) was added dropwise to a solution of sodium hydroxide (1.83 g, 45.8 mmol) in dry ethanol (75 ml) with vigorous stirring. The solution was heated to 50° C. and stirred overnight at that temperature. Ether (1.5 L) was added and the organic phase was washed with 2 N HCl (3×300 ml) and dried over anhydrous sodium sulfate. The solvent was removed in vacuo to give an oil that was purified by flash column chromatography (6% EtOAc/hexane) to give the cyclic β-ketoester 21a (8.7 g, 78%) as a yellow oil: TLC Rf=0.40 (silica gel, 25% EtOAc/hexane); 1H NMR (400 MHz, CDCl3) δ 7.56-7.52 (m, 2H), 7.50-7.42 (m, 3H), 4.26 (q, J=7.2 Hz, 2H), 3.58 (dd, J=3.2 Hz, 7.6 Hz, 1H), 3.38-3.31 (m, 1H), 3.15-3.07 (m, 1H), 1.99 (s, 3H), 1.32 (t, J=7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 202.6, 169.6, 166.5, 135.8, 134.9, 130.2, 128.9, 127.9, 61.9, 51.3, 33.7, 14.5, 10.5; HRMS calcd for C15H16O3+Na+ 267.0997; found 267.0974 [M+Na+].
Reaction SMILES: [NH:1]1[C:9]2[C:4](=[CH:5][C:6]([NH:10][C:11]3[C:20]4[C:15](=[CH:16][C:17]([O:22][CH3:23])=[C:18](I)[CH:19]=4)[N:14]=[CH:13][N:12]=3)=[CH:7][CH:8]=2)[CH:3]=[CH:2]1.[C:24]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1)#[CH:25].C(NCC)C>CN(C=O)C>[NH:1]1[C:9]2[C:4](=[CH:5][C:6]([NH:10][C:11]3[C:20]4[C:15](=[CH:16][C:17]([O:22][CH3:23])=[C:18]([C:25]#[C:24][C:26]5[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=5)[CH:19]=4)[N:14]=[CH:13][N:12]=3)=[CH:7][CH:8]=2)[CH:3]=[CH:2]1
Reactant: COc1cc2ncnc(Nc3ccc4[nH]ccc4c3)c2cc1I
Reactant: C#Cc1ccccn1
Solvent: CN(C)C=O
Solvent: CCNCC
Product: COc1cc2ncnc(Nc3ccc4[nH]ccc4c3)c2cc1C#Cc1ccccn1

Procedure:
The title compound was synthesized according to the method of Example 2 using (1H-indol-5-yl)-(6-iodo-7-methoxy-quinazolin-4-yl)-amine (135 mg, 0.486 mmol), 2-ethynyl-pyridine (185 mg, 1.45 mmol) and diethylamine (605 mg, 8.27 mmol) in 2 mL., of DMF.
Reaction SMILES: [F:1][C:2]1[CH:26]=[C:25]([N+:27]([O-])=O)[CH:24]=[CH:23][C:3]=1[O:4][C:5]1[CH:10]=[CH:9][N:8]=[C:7]2[CH:11]=[C:12]([NH:14][C:15]3[CH:20]=[CH:19][CH:18]=[C:17]([O:21][CH3:22])[CH:16]=3)[S:13][C:6]=12.[NH4+].[Cl-]>[Fe].CCO.O>[NH2:27][C:25]1[CH:24]=[CH:23][C:3]([O:4][C:5]2[CH:10]=[CH:9][N:8]=[C:7]3[CH:11]=[C:12]([NH:14][C:15]4[CH:20]=[CH:19][CH:18]=[C:17]([O:21][CH3:22])[CH:16]=4)[S:13][C:6]=23)=[C:2]([F:1])[CH:26]=1
Reactant: COc1cccc(Nc2cc3nccc(Oc4ccc([N+](=O)[O-])cc4F)c3s2)c1
Agent: [Fe]
Agent: [Cl-]
Agent: [NH4+]
Solvent: O
Solvent: CCO
Product: COc1cccc(Nc2cc3nccc(Oc4ccc(N)cc4F)c3s2)c1
Reaction time: 1 h
Yield: 74 %

Procedure:
A solution of 448 (408 mg, 0.99 mmol) and NH4Cl (45 mg, 084 mmol) in 2:1 mixture of EtOH/water (15 mL) was treated with iron powder (472 mg, 8.43 mmol) and heated to reflux under vigorous stirring for 1 hour. The reaction mixture was then filtered through celite and concentrated yielding 449 which was used without further purification (278 mg, 74% yield). LCMS: (M+H) 382.0.
Reaction SMILES: [CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[C:9]#[CH:10].[CH3:11][C:12]1[CH:19]=[C:18]([CH3:20])[CH:17]=[CH:16][C:13]=1[CH2:14][SH:15].[Na]>>[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1/[CH:9]=[CH:10]\[CH:14]([S:15][CH:9](/[CH:10]=[CH:9]\[C:3]1[CH:4]=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[CH3:1])[C:3]1[CH:4]=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[CH3:1])[C:13]1[CH:16]=[CH:17][C:18]([CH3:20])=[CH:19][C:12]=1[CH3:11]
Reactant: C#Cc1ccc(C)cc1C
Reactant: Cc1ccc(CS)c(C)c1
Agent: [Na]
Product: Cc1ccc(/C=C\C(SC(/C=C\c2ccc(C)cc2C)c2ccc(C)cc2C)c2ccc(C)cc2C)c(C)c1

Procedure:
A solution of 2,4-dimethylphenylacetylene (0.02 mol) and 2,4-dimethylbenzyl mercaptan (0.02 mol) and metallic sodium (0.02 g atom) is subjected to the General Procedure to form (Z)-2,4-dimethylstyryl-2,4-dimethylbenzylsulfide. The title compound is obtained following oxidation of the sulfide, according to the General Procedure.
Reaction SMILES: [O:1]1[C@H:3]2[CH2:4][C@H:5]3[C@:18]([CH3:20])([CH2:19][C@@H:2]12)[C@@H:17]1[C@H:8]([C@H:9]2[C@@:13]([CH2:15][C@H:16]1[NH:21][C:22]([O:24][CH2:25][C:26]([Cl:29])([Cl:28])[Cl:27])=[O:23])([CH3:14])[C@@H:12]([C:30]([O:32][CH3:33])=[O:31])[CH2:11][CH2:10]2)[CH2:7][CH2:6]3.S(=O)(=O)(O)[OH:35]>O1CCOCC1.O>[OH:1][C@H:2]1[CH2:19][C@@:18]2([CH3:20])[C@@H:5]([CH2:6][CH2:7][C@@H:8]3[C@@H:17]2[C@H:16]([NH:21][C:22]([O:24][CH2:25][C:26]([Cl:28])([Cl:29])[Cl:27])=[O:23])[CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][CH2:11][C@@H:12]2[C:30]([O:32][CH3:33])=[O:31])[CH2:4][C@@H:3]1[OH:35]
Reactant: O=S(=O)(O)O
Reactant: COC(=O)[C@H]1CC[C@H]2[C@@H]3CC[C@H]4C[C@@H]5O[C@@H]5C[C@]4(C)[C@H]3[C@H](NC(=O)OCC(Cl)(Cl)Cl)C[C@]12C
Solvent: O
Solvent: C1COCCO1
Product: COC(=O)[C@H]1CC[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](O)C[C@]4(C)[C@H]3[C@H](NC(=O)OCC(Cl)(Cl)Cl)C[C@]12C
Temperature: 25 °C
Reaction time: 18 h

Procedure:
Methyl 2α,3α-epoxy-11α-(2,2,2-trichloroethoxycarbonylamino)-5α-androstane-17β-carboxylate (522 mg) in dioxan (5 ml) was treated with 2N sulphuric acid (1 ml) and stirred at ambient temperature for 18 h. The mixture was diluted with water (50 ml) and extracted with ethyl acetate (3×). The extract was washed with water, dried and evaporated to give a foam. This was purified by preparative t.l.c. in ethyl acetate/petrol (1:1) and crystallised from ether to give the title compound (217 mg) m.p. 228°-230°, [α]D +27.6.
Reaction SMILES: [F:1][C:2]1[CH:33]=[C:32]([F:34])[CH:31]=[CH:30][C:3]=1[O:4][C:5]1[N:10]=[C:9]2[N:11](COCC[Si](C)(C)C)[N:12]=[C:13]([CH:14]=[CH:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[C:8]2=[CH:7][N:6]=1.Cl>CO.CCOCC>[F:1][C:2]1[CH:33]=[C:32]([F:34])[CH:31]=[CH:30][C:3]=1[O:4][C:5]1[N:10]=[C:9]2[NH:11][N:12]=[C:13]([CH:14]=[CH:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[C:8]2=[CH:7][N:6]=1
Reactant: C[Si](C)(C)CCOCn1nc(C=Cc2ccccc2)c2cnc(Oc3ccc(F)cc3F)nc21
Agent: Cl
Solvent: CO
Solvent: CCOCC
Product: Fc1ccc(Oc2ncc3c(C=Cc4ccccc4)n[nH]c3n2)c(F)c1
Temperature: 25 °C
Reaction time: 8 h
Yield: 132 %

Procedure:
6-(2,4-Difluoro-phenoxy)-3-styryl-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazolo[3,4-d]pyrimidine (42 mg, 0.08 mmol) was dissolved in 1 mL MeOH and treated with 1.1 mL of 10% HCl in Et2O. The reaction mixture was stirred overnight at room temperature, and then concentrated under reduced pressure. The residue was purified by preparative TLC (4:1 hexanes/EtOAc) to yield 0.037 g of 6-(2,4-difluoro-phenoxy)-3-styryl-1H-pyrazolo[3,4-d]pyrimidine. Mass Spec. M+H=351.
Reaction SMILES: [N:1]1[NH:2][C:3]2[CH:4]=[CH:5][CH:6]=[C:7]3[CH2:13][CH2:12][C:11]4=[C:14]([CH:18]=[O:19])[CH:15]=[CH:16][CH:17]=[C:10]4[C:9]=1[C:8]=23.P([O-])(O)(O)=[O:21].[Na+].Cl[O-].[Na+].Cl>CS(C)=O.O>[N:1]1[NH:2][C:3]2[CH:4]=[CH:5][CH:6]=[C:7]3[CH2:13][CH2:12][C:11]4=[C:14]([C:18]([OH:21])=[O:19])[CH:15]=[CH:16][CH:17]=[C:10]4[C:9]=1[C:8]=23
Reactant: O=Cc1cccc2c1CCc1cccc3[nH]nc-2c13
Reactant: O=P([O-])(O)O
Agent: Cl
Agent: [Na+]
Agent: [O-]Cl
Solvent: CS(C)=O
Solvent: O
Product: O=C(O)c1cccc2c1CCc1cccc3[nH]nc-2c13
Reaction time: 0.5 h
Yield: 93.9 %

Procedure:
85 mg of 6,7-dihydro-2H-benzo[6,7]cyclohepta[cd]indazole-8-carboxaldehyde prepared in Example 2 was dissolved in 8 ml of dimethyl sulfoxide. To the reaction mixture was added a solution of 0.75 g of sodium dihydrogenphosphate in 4 ml water. Further, a solution of 0.25 g of sodium hypochlorite in 1 ml water was added dropwise at room temperature, followed by stirring for 0.5 hour. To the reaction mixture was added 0.01 N hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was purified and separated by silica gel column chromatography (ethyl acetate:hexane=1:1), to give 85 mg of the title compound as a colorless powder.
Reaction SMILES: [Br:1][C:2]1[CH:10]=[C:6]([C:7]([OH:9])=O)[C:5]([OH:11])=[CH:4][CH:3]=1.[CH3:12][O:13][C:14]1[CH:20]=[CH:19][C:18]([C:21]([F:24])([F:23])[F:22])=[CH:17][C:15]=1[NH2:16]>>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([OH:11])=[C:6]([CH:10]=1)[C:7]([NH:16][C:15]1[CH:17]=[C:18]([C:21]([F:23])([F:24])[F:22])[CH:19]=[CH:20][C:14]=1[O:13][CH3:12])=[O:9]
Reactant: COc1ccc(C(F)(F)F)cc1N
Reactant: O=C(O)c1cc(Br)ccc1O
Product: COc1ccc(C(F)(F)F)cc1NC(=O)c1cc(Br)ccc1O
Yield: 71.3 %

Procedure:
Using 5-bromosalicylic acid and 2-methoxy-5-(trifluoromethyl)aniline as the raw materials, the same operation as the Example 1(1) gave the title compound.
Reaction SMILES: [C:1]([C:9]1[CH:24]=[CH:23][C:12]([CH2:13][O:14][C:15]2[CH:16]=[C:17]([CH:20]=[CH:21][CH:22]=2)[CH:18]=O)=[CH:11][CH:10]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[S:25]1[CH2:31][C:29](=[O:30])[NH:28][C:26]1=[S:27].C([O-])(=O)C.[Na+]>C(O)(=O)C>[C:1]([C:9]1[CH:24]=[CH:23][C:12]([CH2:13][O:14][C:15]2[CH:16]=[C:17]([CH:18]=[C:31]3[S:25][C:26](=[S:27])[NH:28][C:29]3=[O:30])[CH:20]=[CH:21][CH:22]=2)=[CH:11][CH:10]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: O=Cc1cccc(OCc2ccc(C(=O)c3ccccc3)cc2)c1
Reactant: O=C1CSC(=S)N1
Agent: CC(=O)[O-]
Agent: [Na+]
Solvent: CC(=O)O
Product: O=C1NC(=S)SC1=Cc1cccc(OCc2ccc(C(=O)c3ccccc3)cc2)c1
Yield: 58.9 %

Procedure:
The 3-(4-benzoylbenzyloxy)benzaldehyde (2.0 g, 6.3 mmol) was coupled with rhodanine (1.06 g, 8.0 mmol) in the presence of sodium acetate (1.89 g, 22 mmol) and acetic acid (75 ml) essentially as previously described to yield 1.6 grams (59.0%) of the deisred title product. mp 212.5°-213.5° C. NMR. FDMS (M+) 431.
Reaction SMILES: [NH2:1][CH2:2][CH2:3][CH2:4][N:5]1[C:13]2[C:12]([CH3:14])=[C:11]([CH3:15])[N:10]=[C:9]([NH2:16])[C:8]=2[N:7]=[C:6]1[CH2:17][O:18][CH2:19][CH3:20].[C:21](Cl)(=[O:25])[CH:22]([CH3:24])[CH3:23]>>[NH2:16][C:9]1[C:8]2[N:7]=[C:6]([CH2:17][O:18][CH2:19][CH3:20])[N:5]([CH2:4][CH2:3][CH2:2][NH:1][C:21](=[O:25])[CH:22]([CH3:24])[CH3:23])[C:13]=2[C:12]([CH3:14])=[C:11]([CH3:15])[N:10]=1
Reactant: CCOCc1nc2c(N)nc(C)c(C)c2n1CCCN
Reactant: CC(C)C(=O)Cl
Product: CCOCc1nc2c(N)nc(C)c(C)c2n1CCCNC(=O)C(C)C
Yield: 59.2 %

Procedure:
Using the method of Example 19, 1-(3-aminopropyl)-2-(ethoxymethyl)-6,7-dimethyl-1H-imidazo[4,5-c]pyridin-4-amine (1.00 g, 3.6 mmol) was reacted with isobutyryl chloride (0.42 mL, 40 mmol) to provide 0.74 g of N-{3-[4-amino-2-(ethoxymethyl)-6,7-dimethyl-1H-imidazo[4,5-c]pyridin-1-yl]propyl}-2-methylpropanamide as an off white solid, m.p. 179.1-179.7° C.
Reaction SMILES: Cl[CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([S:9][CH:10]2[CH2:14][CH2:13][CH2:12][CH2:11]2)[N:4]=1.C([O:17][C:18](=[O:30])[CH2:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24]([OH:27])=[C:23]([O:28][CH3:29])[CH:22]=1)C>>[CH:10]1([S:9][C:5]2[N:4]=[C:3]([CH2:2][O:27][C:24]3[CH:25]=[CH:26][C:21]([CH2:20][CH2:19][C:18]([OH:30])=[O:17])=[CH:22][C:23]=3[O:28][CH3:29])[CH:8]=[CH:7][CH:6]=2)[CH2:14][CH2:13][CH2:12][CH2:11]1
Reactant: ClCc1cccc(SC2CCCC2)n1
Reactant: CCOC(=O)CCc1ccc(O)c(OC)c1
Product: COc1cc(CCC(=O)O)ccc1OCc1cccc(SC2CCCC2)n1
Yield: 59 %

Procedure:
2-Chloromethyl-6-cyclopentylsulfanyl-pyridine (33 mg, 0.14 mmol) obtained in Step C of Preparation Example 27 and 3-(4-hydroxy-3-methoxy-phenyl)-propionic acid ethyl ester (36 mg, 0.15 mmol) obtained in Step C of Preparation Example 38 were used to react sequentially in the same manner as in Steps A and B of Example 1 to obtain the title compound (32 mg, 69%).
Reaction SMILES: [CH3:1][C:2]1([CH3:14])[CH2:7][O:6][C:5]2([CH2:12][CH2:11][CH:10]([OH:13])[CH2:9][CH2:8]2)[O:4][CH2:3]1.[H-].[Na+].Cl[C:18]1[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][N:19]=1>CN(C=O)C>[CH3:1][C:2]1([CH3:14])[CH2:3][O:4][C:5]2([CH2:8][CH2:9][CH:10]([O:13][C:18]3[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][N:19]=3)[CH2:11][CH2:12]2)[O:6][CH2:7]1
Reactant: N#Cc1ccc(Cl)nc1
Reactant: CC1(C)COC2(CCC(O)CC2)OC1
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: CC1(C)COC2(CCC(Oc3ccc(C#N)cn3)CC2)OC1
Temperature: 25 °C
Reaction time: 1 h
Yield: 91.6 %

Procedure:
Add dropwise a solution of 3,3-dimethyl-1,5-dioxa-spiro[5.5]undecan-9-ol, (1445 mg, 7.22 mmol) in DMF (2.1 mL) to a suspension of sodium hydride (433 mg, 10.82 mmol) in DMF (8.6 mL). Let the reaction mixture stir at room temperature for 1 h, then heat while stirring at 50° C. for 20 min. Add dropwise a solution of 6-chloro-nicotinonitrile (1200 mg, 8.66 mmol) in DMF (4.5 mL). Continue the heating at 60° C. and stirring overnight. Concentrate the reaction mixture to remove DMF. Wash the residue with water (15 mL) and extract with EtOAc/hexanes (20 mL). Dry the organic layer over sodium sulfate, filter and concentrate. Purify the residue by flash chromatography (eluent CH2Cl2/hexanes 2/1) to give 2000 mg (92% yield) of the title compound.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]=[N:10][C:11]2[CH:19]=[C:15]([C:16](Cl)=[O:17])[C:14]([OH:20])=[CH:13][CH:12]=2)=[CH:5][CH:4]=1.[OH-].[NH4+:22]>C(O)(=O)C>[OH:20][C:14]1[CH:13]=[CH:12][C:11]([N:10]=[N:9][C:6]2[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)=[CH:19][C:15]=1[C:16]([NH2:22])=[O:17]
Reactant: COc1ccc(N=Nc2ccc(O)c(C(=O)Cl)c2)cc1
Reactant: [NH4+]
Agent: [OH-]
Solvent: CC(=O)O
Product: COc1ccc(N=Nc2ccc(O)c(C(N)=O)c2)cc1

Procedure:
5-(4-Methoxyphenylazo)salicoyl chloride (1 g) was carefully warmed with 0.880 ammonium hydroxide (10 ml) for 10 minutes. The mixture was then acidified with glacial acetic acid and the amide removed by filtration. The product was crystallized from ethanol (0.60 g), 65%, m.p. 231°-3°, λmax (methanol)=352 nm.
Reaction SMILES: [CH:1]#[CH:2].[Cl:3][SiH:4]([CH2:6][SiH:7]([Cl:9])[Cl:8])[Cl:5]>C1C=CC=CC=1>[Cl:3][Si:4]1([Cl:5])[CH:2]=[CH:1][Si:7]([Cl:9])([Cl:8])[CH2:6]1
Reactant: Cl[SiH](Cl)C[SiH](Cl)Cl
Reactant: C#C
Solvent: c1ccccc1
Product: Cl[Si]1(Cl)C=C[Si](Cl)(Cl)C1

Procedure:
Hydrosilation of acetylene with bis(dichlorosilyl)methane in the presence of Pt((CH2 =CHSiMe2)2O)2. Into the same apparatus as described in Example 1 were placed 18 μl of Pt((CH2 =CHSiMe2)2O)2 in 1,1,3,3-tetramethyl-1,3-divinyl-1,3-disiloxane (4 weight percent Pt) and 20 ml of dried benzene. Acetylene gas was blown into the flask at 90 ml/min for 5 hours. The products were vacuum distilled at 0.5 torr to yield a mixture comprising 3.32 g of 1,1,3,3-tetrachloro-1,3-disilacyclopent-4-ene (TCD-GC) area 6.2%); 1,1,3,3-tetrachloro-1,3-disilacyclopentane (TCD-GC area 47.9%); and 1,1,3,3,6,6,8,8-octachloro-1,3,6,8-tetrasilaoctane (TCD-GC area 27.1 %).
Reaction SMILES: C1(C)C=CC=CC=1.[Na].[CH3:9][CH:10]([CH3:19])[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O-])=[O:17]>CO>[CH3:9][CH:10]([CH3:19])[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][OH:17]
Reactant: CC(C)CCCCCC(=O)[O-]
Agent: [Na]
Solvent: CO
Solvent: Cc1ccccc1
Product: CC(C)CCCCCCO
Yield: 105.9 %

Procedure:
In a similar reaction as in 1 above, 100 ml toluene, sodium (39.5 g, 1.72 mole), 7-methyl-octanoate (52 g, 0.29 mole), and 260 ml anhydrous methanol reacted to yield 7-methyl-1-octanol (44.3 g, yield rate 85%); 7-methyl-1-octanol (44.3 g, 0.31 mole) reacted with chloro-chromic pyridine (100 g, 0.465 mole) to yield 7-methyl-octanaldehyde (31 g, yield rate 70%); and finally, 7-methyl-octanaldehyde (20 g, 0.14 mole), malonic acid (15 g, 0.14 mole), and 15 ml pyridine were added together and refluxed with heating for 3 hours. After cooling down 15 ml 30% sulfuric acid was added and the reaction mixture was stirred for 3 hours under ice bath and then extracted by diethyl ether. Diethyl ether was removed by evaporation and product was subject to vacuum fractional distillation and 122° C./1.5 mmHg fraction was collected as 9-methyl-2-decenoic acid (16 g, yield rate 80%).
Reaction SMILES: P(Cl)(Cl)(Cl)(Cl)[Cl:2].[CH2:7]([O:9][C:10](=[O:17])[CH2:11][C:12](=O)[CH2:13][CH2:14][CH3:15])[CH3:8].O>C1C=CC=CC=1>[CH2:7]([O:9][C:10](=[O:17])[CH:11]=[C:12]([Cl:2])[CH2:13][CH2:14][CH3:15])[CH3:8]
Reactant: CCCC(=O)CC(=O)OCC
Reactant: ClP(Cl)(Cl)(Cl)Cl
Solvent: c1ccccc1
Solvent: O
Product: CCCC(Cl)=CC(=O)OCC
Temperature: 0 °C

Procedure:
280 g of phosphorus pentachloride are added in portions over the course of 2 hours to a solution of 200 g of 3-oxo-hexanoic acid ethyl ester in 200 ml of absolute benzene whilst stirring at 0°C. 200 ml of water are then added dropwise with intense cooling so that the temperature never rises above 0°C. The mixture is stirred for a further 12 hours at 0°C. The organic phase is then separated off, washed with twice 100 ml of ice-cold 2 N sodium hydroxide solution and with twice 100 ml of water, dried over sodium sulphate and evaporated in vacuo. Fractional distillation of the evaporation residue gives, in the fraction boiling at 98°-102°C (20 mm), crude 3-chloro-2-hexenoic acid ethyl ester, which is used direct for further conversion.
Reaction SMILES: [Br:1][C:2]1[CH:3]=[C:4]([NH2:9])[C:5]([NH2:8])=[N:6][CH:7]=1.[N:10]1([CH2:16][CH2:17][O:18][C:19]2[CH:26]=[CH:25][C:22]([CH:23]=O)=[CH:21][CH:20]=2)[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]1>>[Br:1][C:2]1[CH:3]=[C:4]2[N:9]=[C:23]([C:22]3[CH:21]=[CH:20][C:19]([O:18][CH2:17][CH2:16][N:10]4[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]4)=[CH:26][CH:25]=3)[NH:8][C:5]2=[N:6][CH:7]=1
Reactant: O=Cc1ccc(OCCN2CCCCC2)cc1
Reactant: Nc1cc(Br)cnc1N
Product: Brc1cnc2[nH]c(-c3ccc(OCCN4CCCCC4)cc3)nc2c1

Procedure:
The title compound was prepared from 5-bromo-2,3-diaminopyridine and 4-[2-(1-piperidinyl)ethoxy]benzaldehyde.
Reaction SMILES: [Br:1][C:2]1[CH:3]=[C:4]([CH2:8][N:9]2[CH2:14][CH2:13][NH:12][C@@H:11]([CH3:15])[CH2:10]2)[CH:5]=[CH:6][CH:7]=1.Cl[C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:18].C(OCC)(=O)C.C([O-])(O)=O.[Na+]>CN(C1C=CN=CC=1)C.CS(C)=O>[Br:1][C:2]1[CH:3]=[C:4]([CH2:8][N:9]2[CH2:14][CH2:13][N:12]([C:17]([O:19][CH2:20][C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)=[O:18])[C@@H:11]([CH3:15])[CH2:10]2)[CH:5]=[CH:6][CH:7]=1
Reactant: C[C@H]1CN(Cc2cccc(Br)c2)CCN1
Reactant: O=C(Cl)OCc1ccccc1
Agent: CN(C)c1ccncc1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: CCOC(C)=O
Solvent: CS(C)=O
Product: C[C@H]1CN(Cc2cccc(Br)c2)CCN1C(=O)OCc1ccccc1
Temperature: 25 °C
Yield: 89.3 %

Procedure:
To a solution of (3S)-1-[(3-Bromophenyl)methyl]-3-methylpiperazine (250 mg, 0.5 mmol), TEA (0.5 ml, 3.5 mmol), and DMAP (12 mg, 0.1 mmol) in 1 mL of dry DMSO was added dropwise benzyl chloroformate (0.34 mL, 2.25 mmol) at 10° C. while stirring. The mixture was then heated and stirred at 50° C. for 1.5 h. After cooling to room temperature, 15 mL of ethyl acetate and 5 mL of saturated NaHCO3 were added. The organic layer was separated, concentrated under vacuum and purified by Gilson reverse phase HPLC, eluting with acetonitrile/water/0.1% TFA (10/90 to 70/30, v/v, over 12 min), to give the title compound (180 mg, 70%). LC/MS: m/z, 403 (M+H), 1.74 min.
Reaction SMILES: [Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH:10]([O:12][C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[C:15]([N+:22]([O-])=O)[CH:14]=1)[CH3:11].[H][H]>C(O)C.[Pt]=O>[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH:10]([O:12][C:13]1[CH:14]=[C:15]([NH2:22])[C:16]([NH2:19])=[CH:17][CH:18]=1)[CH3:11]
Reactant: [H][H]
Reactant: CC(Oc1ccc([N+](=O)[O-])c([N+](=O)[O-])c1)c1c(Cl)ccc(F)c1Cl
Agent: O=[Pt]
Solvent: CCO
Product: CC(Oc1ccc(N)c(N)c1)c1c(Cl)ccc(F)c1Cl
Yield: 62.7 %

Procedure:
In an autoclave, cover 36 mg of platinum oxide with 5 cm3 of ethanol; add a solution of 600 mg of 4-[1-(2,6-dichloro-3-fluorophenyl)ethoxy]-1,2-dinitrobenzene in 67 cm3 of ethanol. This mixture is hydrogenated under 200 kPa of hydrogen and at a temperature close to 20° C. After reaction for about twenty hours, the mixture is filtered and concentrated under vacuum under reduced pressure (0.2 kPa). After filtration on silica [eluent: dichloromethane/methanol (98/2 by volume)], we obtain 316 mg of 4-[1-(2,6-dichloro-3-fluorophenyl)ethoxy]benzene-1,2-diamine in the form of a brown resin, which has the following characteristics:
Reaction SMILES: [Cl:1][C:2]1[CH:10]=[CH:9][C:8]([I:11])=[CH:7][C:3]=1[C:4]([OH:6])=O.C(N1C=CN=C1)(N1C=CN=C1)=O.C(=O)=O.[CH3:27][O:28][C:29]1[CH:36]=[C:35]([O:37][CH3:38])[CH:34]=[CH:33][C:30]=1[CH2:31][NH2:32]>C1COCC1>[CH3:27][O:28][C:29]1[CH:36]=[C:35]([O:37][CH3:38])[CH:34]=[CH:33][C:30]=1[CH2:31][NH:32][C:4](=[O:6])[C:3]1[CH:7]=[C:8]([I:11])[CH:9]=[CH:10][C:2]=1[Cl:1]
Reactant: COc1ccc(CN)c(OC)c1
Reactant: O=C(O)c1cc(I)ccc1Cl
Agent: O=C(n1ccnc1)n1ccnc1
Agent: O=C=O
Solvent: C1CCOC1
Product: COc1ccc(CNC(=O)c2cc(I)ccc2Cl)c(OC)c1
Temperature: 25 °C
Reaction time: 16 h
Yield: 98.2 %

Procedure:
2-Chloro-5-iodobenzoic acid (2 g, 7.08 mmol) in 25 mL THF was treated with 1,1′-carbonyldiimidazole (1.15 g, 7.08 mmol) at ambient temperature until CO2 evolution ceased (˜20 min). 2,4-Dimethoxybenzylamine (1.18 g, 7.08 mmol) was added and stirred at ambient temperature for 16 h. The reaction mixture was concentrated to dryness, partitioned between EtOAc and saturated NaHCO3, the organic phase isolated, dried over MgSO4, filtered and concentrated to give N-{[2,4-bis(methyloxy)phenyl]methyl}-2-chloro-5-iodobenzamide (3.00 g, 6.95 mmol) as a pale yellow oil that crystallized on standing. 1H NMR (300 MHz, CDCl3) d 7.95 (d, J=2.2 Hz, 1H), 7.62 (dd, J=8.5, 2.2 Hz, 1H), 7.25 (m, 1H), 7.10 (m, 1H), 6.63 (m, 1H), 6.45 (m, 2H), 4.55 (d, J=5.7 Hz, 2H), 3.83 (s, 3H), 3.80 (s, 3H). LCMS ES+ 431.82, 433.77 (M+H).