Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [S:1]1[CH2:5][CH2:4][CH:3]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][NH:11][C:12](=[O:17])[C:13]([O:15]C)=[O:14])[S:2]1.CO.[OH-].[Na+]>O1CCCC1>[S:1]1[CH2:5][CH2:4][CH:3]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][NH:11][C:12](=[O:17])[C:13]([OH:15])=[O:14])[S:2]1
Reactant: COC(=O)C(=O)NCCCCCC1CCSS1
Agent: [Na+]
Agent: [OH-]
Solvent: CO
Solvent: C1CCOC1
Product: O=C(O)C(=O)NCCCCCC1CCSS1
Yield: 73.3 %

Procedure:
The reaction was effected as described in Example 49, but using 92 mg of methyl N-[5-(1,2-dithiolan-3-yl)pentyl]oxcalamidate (prepared as described in Example 65), 4 ml of methanol, 1 ml of tetrahydrofuran and 0.6 ml of a 1N aqueous solution of sodium hydroxide. The solvent was removed from the reaction mixture by distillation under reduced pressure. Water was added to the residue. The resulting mixture was neutralized by the addition of 2N aqueous hydrochloric acid, after which it was extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and then dried over anhydrous sodium sulfate. Ethyl acetate was removed from the extract by distillation under reduced pressure. The residue was dissolved in dioxane, after which it was lyophilised, to give 64 mg of the title compound as a pale yellow amorphous substrate, melting at 75 to 79° C.
Reaction SMILES: Br[C:2]1[CH:3]=[C:4]([N:8]2[CH2:16][CH:15]3[CH2:17][N:11]4[CH2:12][CH:13]([CH2:18][CH:9]2[CH2:10]4)[CH2:14]3)[CH:5]=[N:6][CH:7]=1.[NH:19]1[C:27]2[C:22](=[C:23](B(O)O)[CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20]1>>[NH:19]1[C:27]2[C:22](=[C:23]([C:2]3[CH:3]=[C:4]([N:8]4[CH2:16][CH:15]5[CH2:17][N:11]6[CH2:12][CH:13]([CH2:18][CH:9]4[CH2:10]6)[CH2:14]5)[CH:5]=[N:6][CH:7]=3)[CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20]1
Reactant: OB(O)c1cccc2[nH]ccc12
Reactant: Brc1cncc(N2CC3CC4CC2CN(C4)C3)c1
Product: c1cc(-c2cncc(N3CC4CC5CC3CN(C5)C4)c2)c2cc[nH]c2c1

Procedure:
The title compound was prepared from the product of Example 65A and 1H-indol-4-ylboronic acid according to General Method B: LC-MS Method D (ESI+) m/z 344.0 (M+H)+, retention time 1.27 minutes.
Reaction SMILES: [CH3:1][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([CH:8]=[C:9]([C:11]3[CH:17]=[CH:16][C:14]([NH2:15])=[CH:13][CH:12]=3)[N:10]=2)[CH:7]=1.[CH3:18][O:19][C:20]1[CH:28]=[CH:27][C:23]([C:24](Cl)=[O:25])=[CH:22][CH:21]=1.C(Cl)Cl.CO>N1C=CC=CC=1>[CH3:18][O:19][C:20]1[CH:28]=[CH:27][C:23]([C:24]([NH:15][C:14]2[CH:16]=[CH:17][C:11]([C:9]3[N:10]=[C:5]4[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][N:6]4[CH:8]=3)=[CH:12][CH:13]=2)=[O:25])=[CH:22][CH:21]=1
Reactant: COc1ccc(C(=O)Cl)cc1
Reactant: Cc1ccc2nc(-c3ccc(N)cc3)cn2c1
Solvent: ClCCl
Solvent: CO
Solvent: c1ccncc1
Product: COc1ccc(C(=O)Nc2ccc(-c3cn4cc(C)ccc4n3)cc2)cc1
Yield: 79.3 %

Procedure:
Prepared as described in the Amide Coupling section using 4-(6-methylimidazo[1,2-a]pyridin-2-yl)aniline (70 mg, 0.314 mmol) and 4-methoxybenzoyl chloride (54 mg, 0.314 mmol) in dry pyridine (5 ml) to give the title compound (89 mg, 79%) as a pale yellow solid after work-up and flash chromatography (15:1 DCM/MeOH).
Reaction SMILES: Cl[C:2]1[N:7]=[CH:6][N:5]=[C:4]([NH2:8])[CH:3]=1.[C:9]1(B(O)O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C(=O)([O-])[O-].[Na+].[Na+].C(O)C>C(COC)OC.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>[C:9]1([C:2]2[N:7]=[CH:6][N:5]=[C:4]([NH2:8])[CH:3]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1
Reactant: Nc1cc(Cl)ncn1
Reactant: OB(O)c1ccccc1
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: O
Solvent: COCCOC
Solvent: CCO
Product: Nc1cc(-c2ccccc2)ncn1
Temperature: 125 °C
Yield: 39.2 %

Procedure:
A mixture of 6-chloropyrimidin-4-amine (0.32 g, 2.5 mmol), phenylboronic acid (0.38 g, 3.13 mmol), saturated aqueous sodium carbonate (0.80 g, 7.50 mmol) and bis(triphenylphosphine)palladium(II) chloride (0.035 g, 0.05 mmol) were suspended in a mixture of dimethoxyethane (15 mL)/ethanol (2 mL)/water (2 mL). The mixture was heated in the microwave at 125° C. for 20 min then concentrated in vacuo. The residue was purified by column chromatography (10-60% ethyl acetate/hexanes) to afford 6-phenylpyrimidin-4-amine (167 mg, 0.98 mmol, 39% yield) as an off-white solid. MS (LC/MS) R.T.=0.99; [M+H]+=172.23.
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=O.C(O)(=O)[CH2:11][C:12]([OH:14])=[O:13].N1C=CC=CC=1.N1CCCCC1>O>[F:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)/[CH:5]=[CH:11]/[C:12]([OH:14])=[O:13]
Reactant: O=C(O)CC(=O)O
Reactant: O=Cc1cccc(F)c1
Solvent: O
Solvent: C1CCNCC1
Solvent: c1ccncc1
Product: O=C(O)/C=C/c1cccc(F)c1
Reaction time: 8 h
Yield: 84 %

Procedure:
A mixture of 3-fluorobenzaldehyde (40 g), malonic acid (47 g), and an ethanolic solution (150 ml) containing pyridine (10 g) and piperidine (5 g) was heated at reflux with stirring for 8 hours. The reaction mixture was chilled and water (300 ml) was added, giving crystalline trans 3-fluorocinnamic acid which was removed by filtration, washed with water and dried. The trans 3-fluorocinnamic acid, m.p. 162°-163° C., was obtained in 84% yield (44.6 g).
Reaction SMILES: [Br:1][C:2]1[CH:7]=[C:6]([NH:8][S:9]([C:12]2[CH:17]=[CH:16][C:15]([NH:18]C(=O)C)=[CH:14][CH:13]=2)(=[O:11])=[O:10])[CH:5]=[C:4]([Br:22])[N:3]=1.Cl>[OH-].[Na+]>[NH2:18][C:15]1[CH:16]=[CH:17][C:12]([S:9]([NH:8][C:6]2[CH:7]=[C:2]([Br:1])[N:3]=[C:4]([Br:22])[CH:5]=2)(=[O:11])=[O:10])=[CH:13][CH:14]=1
Reactant: CC(=O)Nc1ccc(S(=O)(=O)Nc2cc(Br)nc(Br)c2)cc1
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Product: Nc1ccc(S(=O)(=O)Nc2cc(Br)nc(Br)c2)cc1
Yield: 86.5 %

Procedure:
6.2 g (0.0138 mol) of N-[4-(2,6-dibromo-pyridin-4-yl-sulfamoyl)-phenyl]-acetamide were dissolved in 138 ml of 1N NaOH and boiled at reflux for 2 hours. After cooling the mixture was adjusted to pH 6 with 2N HCl and the precipitate which separated was filtered off. The material on the suction filter was washed well with water and dried. It was subsequently chromatographed on silica gel with ethyl acetate/hexane 1:2→1:1. There were obtained 4.86 g (86%) of 4-amino-N-(2,6-dibromo-pyridin-4-yl)-benzenesulfonamide as beige crystals; m.p.: 220-222° C.
Reaction SMILES: COC(=O)C1C(=CC([O:14][C:15]2[CH:20]=[CH:19][C:18]([NH:21][C:22](=[O:33])[C:23]3[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][C:24]=3[Br:32])=[CH:17][C:16]=2[NH:34][C:35](=[O:46])[C:36]2[CH:41]=[CH:40][C:39]([N+:42]([O-:44])=[O:43])=[CH:38][C:37]=2[Br:45])=CC=1)C(OC)=O.[CH3:48][O:49][C:50](=[O:70])[C:51]1[C:52](=[CH:57][C:58](OC2C=CC(N)=CC=2N)=[CH:59][CH:60]=1)[C:53]([O:55][CH3:56])=[O:54].BrC1C=CC([N+]([O-])=O)=CC=1C(Cl)=O>>[CH3:56][O:55][C:53](=[O:54])[C:52]1[C:51](=[C:60]([O:14][C:15]2[CH:20]=[CH:19][C:18]([NH:21][C:22](=[O:33])[C:23]3[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][C:24]=3[Br:32])=[CH:17][C:16]=2[NH:34][C:35](=[O:46])[C:36]2[CH:41]=[CH:40][C:39]([N+:42]([O-:44])=[O:43])=[CH:38][C:37]=2[Br:45])[CH:59]=[CH:58][CH:57]=1)[C:50]([O:49][CH3:48])=[O:70]
Reactant: COC(=O)c1ccc(Oc2ccc(N)cc2N)cc1C(=O)OC
Reactant: COC(=O)c1ccc(Oc2ccc(NC(=O)c3ccc([N+](=O)[O-])cc3Br)cc2NC(=O)c2ccc([N+](=O)[O-])cc2Br)cc1C(=O)OC
Agent: O=C(Cl)c1cc([N+](=O)[O-])ccc1Br
Product: COC(=O)c1cccc(Oc2ccc(NC(=O)c3ccc([N+](=O)[O-])cc3Br)cc2NC(=O)c2ccc([N+](=O)[O-])cc2Br)c1C(=O)OC

Procedure:
4-[2,4-Bis-(2-bromo-4-nitrobenzoylamino)phenoxy]phthalic acid dimethyl ester (Compound 113) from 4-(2,4-diaminophenoxy)phthalic acid dimethyl ester (0.53 g) and 2-bromo-5-nitrobenzoyl chloride (1.0 g). The crude product purified on silica gel column (eluent: methylene chloride:methanol (5:1)) to give 4-([2,4-bis-(2-bromo-4-nitrobenzoylamino)phenoxy]phthalic acid dimethyl ester as brownish crystals (yield: 0.81 g 63%). Mp: 138-142° C. LC/MS: 794 (M+Na), 773 (MH+), 740 (M—OMe). CHN: Calculated: C: 46.66; H: 2.61; N: 7.25; Br: 20.69. Found C: 47.05; H: 2.94; N: 6.85; Br: 20.22.
Reaction SMILES: [Cl:1][C:2]1[C:6]([C:7]([N:9]([CH3:11])[CH3:10])=[O:8])=[CH:5][NH:4][C:3]=1[C:12]([O:14]C)=O.[OH-].[Li+].CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C.[NH2:51][CH2:52][C:53]1[C:54]([F:70])=[C:55]([O:60][C:61]2[CH:62]=[C:63]([CH:66]=[C:67]([Cl:69])[CH:68]=2)[C:64]#[N:65])[C:56]([Cl:59])=[CH:57][CH:58]=1.C(=O)(O)[O-].[Na+]>C1COCC1.O.CN(C=O)C>[Cl:1][C:2]1[C:6]([C:7]([N:9]([CH3:10])[CH3:11])=[O:8])=[CH:5][NH:4][C:3]=1[C:12]([NH:51][CH2:52][C:53]1[CH:58]=[CH:57][C:56]([Cl:59])=[C:55]([O:60][C:61]2[CH:62]=[C:63]([C:64]#[N:65])[CH:66]=[C:67]([Cl:69])[CH:68]=2)[C:54]=1[F:70])=[O:14]
Reactant: N#Cc1cc(Cl)cc(Oc2c(Cl)ccc(CN)c2F)c1
Reactant: COC(=O)c1[nH]cc(C(=O)N(C)C)c1Cl
Agent: CN(C)C(On1nnc2cccnc21)=[N+](C)C
Agent: F[P-](F)(F)(F)(F)F
Agent: O=C([O-])O
Solvent: CCN(C(C)C)C(C)C
Solvent: C1CCOC1
Solvent: O
Product: CN(C)C(=O)c1c[nH]c(C(=O)NCc2ccc(Cl)c(Oc3cc(Cl)cc(C#N)c3)c2F)c1Cl
Temperature: 35 °C
Reaction time: 8 h
Yield: 6.3 %

Procedure:
To a solution of methyl 3-chloro-4-[(dimethylamino)carbonyl]-1H-pyrrole-2-carboxylate (0.038 g, 0.165 mmol) in THF (3 mL) and water (1 mL) was added lithium hydroxide (0.039 g, 1.648 mmol). The reaction mixture was stirred overnight at 35° C. The solvent was evaporated and the resulting solid placed under high vacuum. To the intermediate mixture was added DMF (1 mL), HATU (0.075 g, 0.198 mmol), DIPEA (0.043 ml, 0.247 mmol) and 3-{[3-(aminomethyl)-6-chloro-2-fluorophenyl]oxy}-5-chlorobenzonitrile (0.051 g, 0.165 mmol). The solution was stirred for 2 h at RT. Purication was accomplished by HPLC. The desired fractions were neutralized with saturated sodium bicarbonate, extracted with EtOAc (3×5 mL), the organic layers combined, dried over sodium sulfate, filtered and evaporated to afford 3-chloro-N2-({4-chloro-3-[(3-chloro-5-cyanophenyl)oxy]-2-fluorophenyl}methyl)-N4,N4-dimethyl-1H-pyrrole-2,4-dicarboxamide (0.0053 g, 6% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6): δ ppm 12.16 (br. s., 1H) 8.13 (t, 1H) 7.83 (d, 1H) 7.46-7.54 (m, 3 H) 7.38 (t, 1H) 7.16 (d, 1H) 4.56 (d, 2H) 2.95 (s, 6H). MS: m/z 509.1 (M+1).
Reaction SMILES: C([O:3][C:4]([C:6]1[CH:11]=[C:10]([Br:12])[CH:9]=[C:8]([CH3:13])[N:7]=1)=[O:5])C>Cl>[Br:12][C:10]1[CH:9]=[C:8]([CH3:13])[N:7]=[C:6]([C:4]([OH:5])=[O:3])[CH:11]=1
Reactant: CCOC(=O)c1cc(Br)cc(C)n1
Agent: Cl
Product: Cc1cc(Br)cc(C(=O)O)n1
Yield: 116.8 %

Procedure:
A solution of 4-bromo-6-methyl-pyridine-2-carboxylic acid ethyl ester (2.42 g, 9.91 mmol) in 6 N aq. HCl (100 mL) is stirred at 65° C. for 18 h. The solvent is evaporated and the residue is dried under HV, suspended in DCM, filtered and dried again under HV to give 4-bromo-6-methyl-pyridine-2-carboxylic acid (2.50 g) as a hydrochloride salt in form of a white powder; LC-MS: tR=0.46 min, [M+1]+=215.93.
Reaction SMILES: [CH2:1]([C:4]1[C:5]([Cl:13])=[C:6]2[CH:12]=[CH:11][NH:10][C:7]2=[N:8][CH:9]=1)[CH:2]=[CH2:3].[H-].[Na+].[S:16](Cl)([C:19]1[CH:25]=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=1)(=[O:18])=[O:17]>CN(C=O)C>[CH2:1]([C:4]1[C:5]([Cl:13])=[C:6]2[CH:12]=[CH:11][N:10]([S:16]([C:19]3[CH:25]=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=3)(=[O:18])=[O:17])[C:7]2=[N:8][CH:9]=1)[CH:2]=[CH2:3]
Reactant: Cc1ccc(S(=O)(=O)Cl)cc1
Reactant: C=CCc1cnc2[nH]ccc2c1Cl
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: C=CCc1cnc2c(ccn2S(=O)(=O)c2ccc(C)cc2)c1Cl
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 99.4 %

Procedure:
5-Allyl-4-chloro-1H-pyrrolo[2,3-b]pyridine (2.24 g, 11.6 mmol) in DMF (25 mL) was cooled to about 0° C. then treated with 60 wt % NaH (0.558 g, 13.9 mmol). The mixture was stirred for about 30 min then TsCl (2.44 g, 12.8 mmol) was added. The mixture was stirred for about 15 min at about 0° C. then warmed to rt for about 30 min. The solvents were evaporated under reduced pressure then the residue was stirred with DCM (40 mL) and saturated aqueous NaHCO3 (35 mL) for about 15 min. The layers were separated then the aqueous layer was extracted with DCM (20 mL). The combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo to give 5-allyl-4-chloro-1-tosyl-1H-pyrrolo[2,3-b]pyridine (4.0 g, 111%, crude): LC/MS (Table 2, Method a) Rt=3.18 min; MS m/z 347 (M+H)+.
Reaction SMILES: [CH3:1][O:2][C:3](=[O:26])[C:4]1[CH:9]=[C:8]([CH:10]=[CH:11][C:12]2[CH:17]=[C:16]([O:18][CH3:19])[CH:15]=[CH:14][C:13]=2[O:20][CH3:21])[CH:7]=[CH:6][C:5]=1[NH:22][C:23](=[O:25])[CH3:24]>C(OCC)(=O)C.[Pd]>[CH3:1][O:2][C:3](=[O:26])[C:4]1[CH:9]=[C:8]([CH2:10][CH2:11][C:12]2[CH:17]=[C:16]([O:18][CH3:19])[CH:15]=[CH:14][C:13]=2[O:20][CH3:21])[CH:7]=[CH:6][C:5]=1[NH:22][C:23](=[O:25])[CH3:24]
Reactant: COC(=O)c1cc(C=Cc2cc(OC)ccc2OC)ccc1NC(C)=O
Agent: [Pd]
Solvent: CCOC(C)=O
Product: COC(=O)c1cc(CCc2cc(OC)ccc2OC)ccc1NC(C)=O
Reaction time: 8 h

Procedure:
150 mg of 5-[2-(2,5-dimethoxyphenyl)ethenyl]-2-acetylamino benzoic acid methylester are dissolved in 10 ml of ethyl acetate. After addition of 25 mg of palladium (10% on charcoal) the mixture is stirred overnight under an atmosphere of hydrogen and filtered over celite. The filtrate is evaporated in vacuo to obtain the title compound as colourless crystals. mp:81-83°.
Reaction SMILES: [H-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[NH:18][C:13]3=[N:14][CH:15]=[CH:16][CH:17]=[C:12]3[N:11]=2)=[CH:6][CH:5]=1.Cl[CH2:20][C:21]([NH2:23])=[O:22]>O>[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[N:11]([CH2:20][C:21]([NH2:23])=[O:22])[C:12]3[C:13]([N:18]=2)=[N:14][CH:15]=[CH:16][CH:17]=3)=[CH:6][CH:5]=1
Reactant: NC(=O)CCl
Reactant: Clc1ccc(-c2nc3cccnc3[nH]2)cc1
Agent: [H-]
Agent: [Na+]
Solvent: O
Product: NC(=O)Cn1c(-c2ccc(Cl)cc2)nc2ncccc21
Temperature: 25 °C
Reaction time: 8 h
Yield: 86 %

Procedure:
Under nitrogen flow, sodium hydride (0.96 g, 0.0234 mole, 60% in oil) was washed with hexanes (~70 ml) and decanted. Dimethylformamide was added (100 ml) and the 2-(4-chlorophenyl)-3H-imidazo[4,5-b]pyridine (5.0 g, 0.022 mole) was added in portions. The reaction mixture was heated at 70°-85° C. for 11/2 hours. Chloroacetamide (2.06 g, 0.022 mole) was added and the reaction mixture was stirred overnight at room temperature. The reaction mixture was added to water (~600 ml) and the precipitate was collected by filtration, washed with water, and dried under high vacuum overnight at 50° C. NMR indicated a 14% yield of the isomer: 2-(4-chlorophenyl)-3H-imidazo[4,5-b]pyridine-3-acetamide and an 86% yield of the title compound. The solid was dissolved in pyridine, filtered, and diluted with water to produce crystalline produce with refrigeration. The solid was collected by filtration, washed with water and dried under high vacuum at 90° C. overnight to give 2.3 g (36.5%) of the title compound, mp 280°-283° C. with decomposition.
Reaction SMILES: [H-].[Na+].[Cl:3][C:4]1[CH:11]=[CH:10][C:7]([CH:8]=O)=[CH:6][C:5]=1[F:12].[CH2:13]1COCC1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:3][C:4]1[CH:11]=[CH:10][C:7]([CH:8]=[CH2:13])=[CH:6][C:5]=1[F:12]
Reactant: O=Cc1ccc(Cl)c(F)c1
Reactant: C1CCOC1
Agent: C[P+](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: [Br-]
Agent: [H-]
Product: C=Cc1ccc(Cl)c(F)c1
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 47 %

Procedure:
Sodium hydride (8.549 g, 213.7 mmol, 60% suspension in mineral oil) was added portionwise to a cold (0° C.) solution of 4-chloro-3-fluorobenzaldehyde (26.07 g, 164.4 mmol) and methyltriphenylphosphonium bromide (70.48 g, 197.3 mmol) in THF (400 mL). The reaction mixture was allowed to warm up to room temperature overnight. The solids were removed by filtration, and the filter cake was washed with ether. The filtrate was concentrated (water bath about 20° C.), and the residue was suspended in hexanes and stirred for 30 minutes. The solids (mostly PPh3O) were removed by filtration, and the filter cake was washed with hexanes. The filtrate was concentrated, and the crude product was purified by column chromatography, eluting with hexanes/ethyl acetate (25:1) to give 1-chloro-2-fluoro-4-vinylbenzene (12.1 g, 47%) as an oil. 1H NMR (400 MHz, CDCl3) δ 7.33 (m, 1H), 7.18 (m, 1H), 7.10 (m, 1H), 6.63 (m, 1H), 5.74 (d, J=17.4 Hz, 1H), 5.32 (d, J=10.8 Hz, 1H).
Reaction SMILES: [Br:1]N1C(=O)CCC1=O.[CH3:9][O:10][C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][C:18]=1[CH3:19])[C:14]#[N:15]>C(Cl)(Cl)(Cl)Cl.[W].C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:1][CH2:19][C:18]1[CH:17]=[CH:16][C:13]([C:14]#[N:15])=[CH:12][C:11]=1[O:10][CH3:9]
Reactant: O=C1CCC(=O)N1Br
Reactant: COc1cc(C#N)ccc1C
Agent: [W]
Agent: O=C(OOC(=O)c1ccccc1)c1ccccc1
Solvent: ClC(Cl)(Cl)Cl
Product: COc1cc(C#N)ccc1CBr
Yield: 65 %

Procedure:
N-Bromosuccinimide (3.2 g.) and benzoyl peroxide (0.005 g.) were added to a solution of 3-methoxy-4-methylbenzonitrile (2.65 g.) in dry carbon tetrachloride (90 ml.). The mixture was heated to reflux for 15 minutes using a 250 watt tungsten lamp. The cooled reaction mixture was diluted with petroleum ether (b.p. 60°-80° C., 90 ml.), insoluble material removed by filtration, and the filtrate evaporated. The solid residue was recrystallized from a mixture of dichloromethane and petroleum ether to give 4-bromomethyl-3-methoxybenzonitrile (W) (2.64 g., 65%) as a white solid, m.p. 87°-91° C.
Reaction SMILES: F[C:2]1[CH:3]=[C:4]([OH:11])[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].[CH2:12]1[O:21][C:20]2[CH:19]=[CH:18][C:16]([NH2:17])=[CH:15][C:14]=2[O:13]1>>[CH2:12]1[O:21][C:20]2[CH:19]=[CH:18][C:16]([NH:17][C:2]3[CH:3]=[C:4]([OH:11])[CH:5]=[CH:6][C:7]=3[N+:8]([O-:10])=[O:9])=[CH:15][C:14]=2[O:13]1
Reactant: O=[N+]([O-])c1ccc(O)cc1F
Reactant: Nc1ccc2c(c1)OCO2
Product: O=[N+]([O-])c1ccc(O)cc1Nc1ccc2c(c1)OCO2
Temperature: 120 °C
Reaction time: 5 h

Procedure:
0.86 g of 3-fluoro-4-nitrophenol and 2.25 g of 3,4-methylenedioxyaniline were mixed and stirred for 5 hours at 120° C. The raw mixture was chromatographed on silica gel.
Reaction SMILES: [Br:1][CH2:2][CH2:3][CH:4]=[CH2:5].[CH3:6][SiH:7]([CH3:9])[Cl:8]>CC(O)C.C1(C)C=CC=CC=1.O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl>[Br:1][CH2:2][CH2:3][CH2:4][CH2:5][Si:7]([CH3:9])([CH3:6])[Cl:8]
Reactant: C[SiH](C)Cl
Reactant: C=CCCBr
Agent: Cl[Pt](Cl)(Cl)Cl
Agent: Cl
Solvent: Cc1ccccc1
Solvent: CC(C)O
Solvent: O
Product: C[Si](C)(Cl)CCCCBr
Temperature: 60 °C
Yield: 75.7 %

Procedure:
Hexachloroplatinic acid hexahydrate (0.02 g, 0.039 mmole) was dissolved in a minimum of 2-propanol. This solution was dissolved in 75 ml toluene under argon. 2-propanol and water were removed by azeotropically distilling 25 ml of the toluene. The resulting solution was stirred and 6.17 g (0.046 mole) of 4-bromo-1-butene was added at 40° C. 4.32 g (0.046 mole) of dimethylchlorosilane was slowly added and the solution was heated to 60° C. and allowed to react for four hours. The mixture was distilled to remove the toluene. Further vacuum distillation yielded 8.0 g of product with a b.p. of 92°-95° C. at 5 mm Hg pressure. 'H NMR confirmed the structure.
Reaction SMILES: [S:1]([O:11][CH2:12][C:13]([O:15]CC)=[O:14])([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].[OH-].[Na+]>C(O)C>[S:1]([O:11][CH2:12][C:13]([OH:15])=[O:14])([C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[CH:9][CH:10]=1)(=[O:2])=[O:3]
Reactant: CCOC(=O)COS(=O)(=O)c1ccc(C)cc1
Agent: [Na+]
Agent: [OH-]
Solvent: CCO
Product: Cc1ccc(S(=O)(=O)OCC(=O)O)cc1
Temperature: 25 °C
Reaction time: 3 h

Procedure:
A solution of ethyl 2-(tosyloxy)acetate (2, 860 mg, 3.33 mmol) in ethanol (4 ml) was treated at room temperature with 5% NaOH aqueous solution (2 ml). The resulting mixture was stirred at room temperature for 3 h. The ethanol was removed in vacuo and aqueous 5% HCl solution (2.7 ml) was added. The aqueous mixture was extracted with chloroform and the organic extracts dried (Na2SO4), filtered and the solvent removed under reduced pressure. The remaining white solid was recrystallized from hexane/ethyl acetate as a white powder (476 mg, 62%). [This reaction was repeated on 2× scale (1.449 g, 94%)]. δH (400 MHz, MeOD) 2.45 (3H, s, Me), 4.58 (2H, s, CH2), 7.44 (2H, d, J=8.2 Hz, ArH), 7.82 (2H, d, J=8.2 Hz, ArH); δc (100.6 MHz, MeOD) 20.4, 64.7, 128.0, 129.9, 133.0, 145.6, 168.2; MS (ES+) 247.8 (100%, [M+H2O]+); MS (ES−) 170.1 (100%, TsO−).
Reaction SMILES: [O-2].[Cd+2:2].[CH2:3]([C:15]([OH:17])=[O:16])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]>>[CH2:3]([C:15]([O-:17])=[O:16])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14].[Cd+2:2].[CH2:3]([C:15]([O-:17])=[O:16])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]
Reactant: CCCCCCCCCCCCC(=O)O
Agent: [Cd+2]
Agent: [O-2]
Product: CCCCCCCCCCCCC(=O)[O-]
Temperature: 90 °C

Procedure:
Cadmium oxide (0.127 g, 1 mmol) and dodecylcarboxylic acid (0.500 g) were reacted at 220° C. for 10 min, cooled to 90° C., then a cadmium dodecylcarboxylate (precursor) was formed. Into said system, toluene (10 ml), trioctylphosphine oxide (3.866 g) and trioctylphosphine (3.7 g) were added. Then a 0.05M aqueous solution of sodium sulfide (10 ml) was added. After the system was reacted at 90° C. for 3 h, a clear yellow sol containing CdS nanoparticles was obtained. Said sol has a typical exciton absorption peak of the CdS nanoparticles, can result in a quantum size effect and emit a fairly strong blue light under the irradiation of a UV lamp.
Reaction SMILES: [CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH2:15][C:16]([OH:18])=O)[CH:12]=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[O:19]1[CH:23]=[CH:22][CH:21]=[CH:20]1.FC(F)(F)C(OC(=O)C(F)(F)F)=O>C(Cl)Cl>[O:19]1[CH:23]=[CH:22][CH:21]=[C:20]1[C:16](=[O:18])[CH2:15][C:11]1[CH:12]=[CH:13][CH:14]=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[CH:10]=1
Reactant: c1ccoc1
Reactant: O=C(O)Cc1cccc(OCc2ccccc2)c1
Solvent: O=C(OC(=O)C(F)(F)F)C(F)(F)F
Solvent: ClCCl
Product: O=C(Cc1cccc(OCc2ccccc2)c1)c1ccco1
Temperature: 25 °C
Reaction time: 48 h
Yield: 95 %

Procedure:
3-Benzyloxyphenylacetic acid (3.5 kg, 14.45 mol) was dissolved in CH2Cl2 (35 L), and furan (3.0 kg, 44 mol) and trifluoroacetic anhydride (4.55 kg, 21.65 mol) were added to the solution. The reaction was kept being stirred at room temperature for 2 days. The reaction was quenched with saturated NaHCO3 to pH=6.9, and the organic reagent in the mixture was evaporated. The residue was extracted with EtOAc, and the organic layer was washed with brine, dried over MgSO4, and evaporated. The resulting residue was purified by chromatography on a silica gel column using hexane-EtOAc as eluent to give the 1-(furan-2-yl)-2-(3-benzyloxyphenyl)ethan-1-one as yellow oil: 4 kg (yield: 95%)
Reaction SMILES: [O:1]=[CH:2][C:3]1[CH:11]=[CH:10][C:8]([OH:9])=[C:5]([O:6][CH3:7])[CH:4]=1.[Br:12]Br>C(O)(=O)C>[Br:12][C:10]1[CH:11]=[C:3]([CH:4]=[C:5]([O:6][CH3:7])[C:8]=1[OH:9])[CH:2]=[O:1]
Reactant: COc1cc(C=O)ccc1O
Reactant: BrBr
Solvent: CC(=O)O
Product: COc1cc(C=O)cc(Br)c1O
Temperature: 25 °C
Reaction time: 24 h
Yield: 88.1 %

Procedure:
To a solution of vanillin (30.40 g, 0.20 mol) in glacial acetic acid (200 ml) was added bromine (46.79 g, 0.29 mol) in glacial acetic acid (20 ml) at 100 over a period of 1 h. Additional acetic acid (100 ml) was added to the thickening mixture and the reaction was stirred for 24 h at ambient temperature. The reaction was diluted with ice-water (300 ml) and then the precipitate was filtered and washed with water and dried in vacuo to give the desired compound (40.69 g, 89%).