Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [H-].[Na+].[CH3:3][S:4]([CH:7]([CH3:13])[C:8]([O:10][CH2:11][CH3:12])=[O:9])(=[O:6])=[O:5].[Br:14][CH2:15][CH2:16]Br>CN(C=O)C>[Br:14][CH2:15][CH2:16][C:7]([CH3:13])([S:4]([CH3:3])(=[O:5])=[O:6])[C:8]([O:10][CH2:11][CH3:12])=[O:9]
Reactant: CCOC(=O)C(C)S(C)(=O)=O
Reactant: BrCCBr
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: CCOC(=O)C(C)(CCBr)S(C)(=O)=O
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 50 %

Procedure:
Sodium hydride (60% dispersion in mineral oil, 2.33 g, 58.3 mmol) was washed with hexanes (2×10 mL) in a 100 mL two neck round bottom flask under nitrogen then suspended in DMF (30 mL). The suspension was treated dropwise with ethyl 2-(methylsulfonyl)propanoate (10.0 g, 55.49 mmol) in DMF (10 mL). The mixture was stirred 30 min at RT, cooled to 0° C., and treated drop-wise with 1,2-dibromoethane (5.17 mL, 58.8). The mixture was allowed to warm to room temperature while stirring overnight. The mixture was quenched with saturated aq ammonium chloride (100 mL) and extracted with diethyl ether (4×50 mL). Combined organics were washed with 50% saturated sodium chloride (4×50 mL), dried (MgSO4), and concentrated in vacuo. Crude material was purified via silica chromatography (350 g, 230-400 mesh) and an eluent of EtOAc in hexanes (10-20%) to afford the title compound as a pale yellow oil (7.9 g, 50%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.33 (t, J=7.05 Hz, 3 H) 1.64 (s, 3 H) 2.49-2.59 (m, 1 H) 2.78 (ddd, J=13.89, 10.16, 6.64 Hz, 1 H) 3.05 (s, 3 H) 3.33-3.41 (m, 1 H) 3.46-3.54 (m, 1 H) 4.22-4.37 (m, 2 H).
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([OH:8])[CH:5]=[CH:6][CH:7]=1.Br[CH2:10][C:11]([NH2:13])=[O:12].C([O-])([O-])=O.[K+].[K+].C([O-])([O-])=O.[Cs+].[Cs+]>CC(C)=O>[F:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][CH:7]=1)[O:8][CH2:10][C:11]([NH2:13])=[O:12]
Reactant: NC(=O)CBr
Reactant: Oc1cccc(F)c1
Agent: O=C([O-])[O-]
Agent: [Cs+]
Agent: [K+]
Solvent: CC(C)=O
Product: NC(=O)COc1cccc(F)c1
Temperature: 25 °C
Yield: 29.9 %

Procedure:
A mixture of 3-fluorophenol (11.2 g, 100 mmol), 2-bromoacetamide (13.8 g, 100 mmol), K2CO3 (13.82 g, 100 mmol) and Cs2CO3 (32.58 g, 100 mmol) in acetone (150 mL) was refluxed overnight. The mixture was cooled to rt and filtered and the filtrate was concentrated in vacuo. The residue was purified by a silica gel column chromatography (PE/EtOAc (V/V)=1:1) to give the title compound as a white solid (5.06 g, 30%).
Reaction SMILES: [Cl:1][C:2]1[C:10]2[C:9]3[CH:11]=[C:12]([C:16]#[N:17])[N+:13]([O-])=[CH:14][C:8]=3[N:7]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:6]=2[N:5]=[CH:4][CH:3]=1.ClC1C=CC2C3C=C(C#N)[N+]([O-])=CC=3N(COCC[Si](C)(C)C)C=2N=1.C(N(CC)CC)C>C(#N)C>[Cl:1][C:2]1[C:10]2[C:9]3[CH:11]=[C:12]([C:16]#[N:17])[N:13]=[CH:14][C:8]=3[N:7]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:6]=2[N:5]=[CH:4][CH:3]=1
Reactant: C[Si](C)(C)CCOCn1c2c[n+]([O-])c(C#N)cc2c2c(Cl)ccnc21
Agent: C[Si](C)(C)CCOCn1c2c[n+]([O-])c(C#N)cc2c2ccc(Cl)nc21
Solvent: CC#N
Solvent: CCN(CC)CC
Product: C[Si](C)(C)CCOCn1c2cnc(C#N)cc2c2c(Cl)ccnc21

Procedure:
A solution of 4-chloro-9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile-7-oxide with 2-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile-7-oxide (6.5:1, 220 mg, 0.59 mmol), 1,1′-[bis(diphenylphosphino)ferrocene]dichloropalladium(II) (17 mg, 0.02 mmol), and triethylamine (0.24 mL, 1.8 mmol) in acetonitrile (3.1 mL) was heated under microwave irradiation at 130° C. for 20 minutes. The cooled reaction mixture was concentrated in vacuo and purified by flash chromatography (silica, 40 g, ISCO, 5-85% ethyl acetate in heptane) to afford the title compound as a 6.5:1 mixture of the title compound with 2-chloro-9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile as an off-white solid (180 mg, 80%). The mixture was used in subsequent steps without any further purification. 1H NMR (CDCl3, 400 MHz): 9.20 (d, J=0.9 Hz, 1H), 8.74 (d, J=0.9 Hz, 1H), 8.60 (d, J=5.3 Hz, 1H), 7.39 (d, J=5.3 Hz, 1H), 6.02 (s, 2H), 3.60 (t, J=8.0 Hz, 2H), 0.94 (t, J=8.0 Hz, 2H), −0.08 (s, 9H).
Reaction SMILES: [Br-].[O:2]=[C:3]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5](=[O:12])[N:4]1[CH2:13][CH2:14][CH2:15][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cl:35][C:36]1[CH:37]=[C:38]([CH:41]=[CH:42][CH:43]=1)[CH:39]=O.CC(C)([O-])C.[K+]>O1CCCC1>[Cl:35][C:36]1[CH:37]=[C:38](/[CH:39]=[CH:15]\[CH2:14][CH2:13][N:4]2[C:5](=[O:12])[C:6]3[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=3)[C:3]2=[O:2])[CH:41]=[CH:42][CH:43]=1
Reactant: O=Cc1cccc(Cl)c1
Reactant: O=C1c2ccccc2C(=O)N1CCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: CC(C)(C)[O-]
Agent: [Br-]
Agent: [K+]
Solvent: C1CCOC1
Product: O=C1c2ccccc2C(=O)N1CC/C=C\c1cccc(Cl)c1
Temperature: -75 °C
Reaction time: 0.33 h
Yield: 81.7 %

Procedure:
To a stirred suspension of (3-(1,3-dioxoisoindolin-2-yl)propyl)triphenylphosphonium bromide (17.6 g, 33.2 mmol) in tetrahydrofuran (170 mL) at ambient temperature was added 3-chlorobenzaldehyde (3.76 mL, 33.2 mmol), and the resulting mixture was cooled with a dry-ice acetone bath to −75° C. Solid potassium t-butoxide (3.72 g, 33.2 mmol) was added, and stirring was continued in the bath for an additional 20 minutes; the temperature was −80° C. The cooling bath was removed, and when the internal temperature reached −30° C., the flask was placed in a water-ice bath. The temperature eventually settled at 10° C. and was maintained for 2 hours. The reaction mixture was poured into a separatory funnel containing water (250 mL), and this was extracted with ethyl acetate (250 mL) The organic layer was dried over sodium sulfate and concentrated. The residue was purified by chromatography on silica gel, eluting with 90/10 hexanes/ethyl acetate, to afford (Z)-2-(4-(3-chlorophenyl)but-3-enyl)isoindoline-1,3-dione as a white solid (8.46 g, 82% yield).
Reaction SMILES: [C:1]([OH:11])(=O)[CH:2]=[CH:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.S(Cl)([Cl:14])=O>>[C:1]([Cl:14])(=[O:11])[CH:2]=[CH:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1
Reactant: O=S(Cl)Cl
Reactant: O=C(O)C=Cc1ccccc1
Product: O=C(Cl)C=Cc1ccccc1
Temperature: 60 °C
Reaction time: 8 h

Procedure:
The cinnamic acid (5 g, 19.7 mmol) and thionyl chloride (5 eq) were put in MC and stirred at 60° C. overnight. Then, the reaction mixture was removed of the unreacted thionyl chloride and the solvent under vacuum to obtain cinnamoyl chloride.
Reaction SMILES: Br[C:2]1[N:3]=[CH:4][C:5]([NH2:8])=[N:6][CH:7]=1.[NH:9]1[CH2:13][CH2:12][CH2:11][CH2:10]1>C(OCC)(=O)C>[N:9]1([C:2]2[N:3]=[CH:4][C:5]([NH2:8])=[N:6][CH:7]=2)[CH2:13][CH2:12][CH2:11][CH2:10]1
Reactant: C1CCNC1
Reactant: Nc1cnc(Br)cn1
Solvent: CCOC(C)=O
Product: Nc1cnc(N2CCCC2)cn1
Reaction time: 2 h
Yield: 43.7 %

Procedure:
A mixture of 5-bromopyrazin-2-amine (1.2 g, 6.9 mmol) and pyrrolidine (4 mL, 48 mmol) was microwaved at 180° C., 200 W for 2 h. The reaction was diluted into 125 mL ethyl acetate and extracted with water (3×50 mL) and brine (50 mL). It was dried over sodium sulfate, filtered and concentrated. The crude product was purified by column chromatography (0 to 3% methanol/methylene chloride) to afford 5-(pyrrolidin-1-yl)pyrazin-2-amine (495 mg, 3. mmol, 43.7% yield). 1H NMR (400 MHz, DMSO-d6) δ ppm 7.52 (1H, d, J=1.51 Hz), 7.36 (1H, d, J=1.76 Hz), 5.21 (2H, s), 3.24-3.29 (4H, m), 1.90 (4H, ddd, J=6.48, 3.53, 3.34 Hz). MS (LC/MS) R.T.=0.52; [M+H]+=165.29.
Reaction SMILES: [H-].[Na+].[C:3]([O:10][CH3:11])(=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].[Br:12][C:13]([CH2:15]Br)=[CH2:14]>CN(P(N(C)C)(N(C)C)=O)C>[Br:12][C:13](=[CH2:14])[CH2:15][CH:4]([C:3]([O:10][CH3:11])=[O:9])[C:5]([O:7][CH3:8])=[O:6]
Reactant: C=C(Br)CBr
Reactant: COC(=O)CC(=O)OC
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)P(=O)(N(C)C)N(C)C
Product: C=C(Br)CC(C(=O)OC)C(=O)OC
Temperature: 50 °C
Reaction time: 1 h
Yield: 64.9 %

Procedure:
To a suspension of sodium hydride (5.0 g, 125 mmol) in HMPA (50 ml, distilled from calcium hydride) was added a solution of dimethyl malonate (11.7 ml, 100 mmol) in HMPA (5 ml) at 0° C. under argon. The mixture was heated to 50° C. and stirred 1 hour. Following this the solution was again cooled to 0° C., and a solution of 2,3-dibromopropene (122 ml, 100 mmol) in HMPA (5 ml) was added to the reaction mixture. Next, the solution was warmed to 40° C. and stirred for 1 hour. The reaction mixture was quenched with aq. HCl (10%, 88 ml) and extracted with ether (3×45 ml). The organic fractions were collected, dried over MgSO−4, and the solvent was removed in vacuo. The crude oil was purified via silica gel chromatography (eluants: chloroform/hexane) to obtain the titled product as a colorless oil (16.3 g, 65%). 1H-NMR (300 MHz, CDCl3) δ 5.70 (d, J=1.8 Hz, 1H), 5.48 (d, J=1.8 Hz, 1H), 3.63 (t, J=7.5 Hz, 1H), 3.76 (s, 6H), 3.04 (d, J=7.5 Hz, 2H).
Reaction SMILES: [CH:1](=O)[CH2:2][CH2:3][CH2:4][CH:5]=[O:6].Cl.[CH2:9]([NH2:16])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[CH2:17]([C:24](O)=O)[C:18](CC(O)=O)=O.C([O-])(=O)C.[Na+]>O>[CH2:9]([N:16]1[CH:3]2[CH2:2][CH2:1][CH2:24][CH:17]1[CH2:18][C:5](=[O:6])[CH2:4]2)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1
Reactant: O=C(O)CC(=O)CC(=O)O
Reactant: NCc1ccccc1
Reactant: O=CCCCC=O
Agent: CC(=O)[O-]
Agent: Cl
Agent: [Na+]
Solvent: O
Product: O=C1CC2CCCC(C1)N2Cc1ccccc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 79.6 %

Procedure:
To a solution in water (400 ml) of pentandial (84.5 g) and benzylamine hydrochloride (36.3 g), cooled at 0° C. 30.8 g of 1,3-acetonedicarboxylic acid are added. 70 ml of an aqueous solution of sodium acetate at 10% are then added. The obtained mixture is kept under stirring at room temperature for one hour and then heated for 4 hours to 50° C. The mixture is then acidified at pH 2 with a 10% w. HCl aqueous solution and then washed with diethyl ether. The pH is then brought to 6 with sodium bicarbonate and the aqueous phase extracted with dichloromethane. The organic extracts are anhydrified on sodium sulphate and the solvent evaporated to obtain 38.5 g of the compound 9-benzyl-9-azabicyclo[3.3.1]nonan-3-one (6a) as a light coloured solid.
Reaction SMILES: [N+:1]([C:4]1[C:10]([CH3:11])=[CH:9][CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2].Br[C:13]1[CH:18]=[CH:17][C:16]([CH2:19][CH2:20][OH:21])=[CH:15][CH:14]=1.C([O-])([O-])=O.[K+].[K+]>[Cu]I.O>[CH3:11][C:10]1[C:4]([N+:1]([O-:3])=[O:2])=[C:5]([CH:7]=[CH:8][CH:9]=1)[NH:6][C:13]1[CH:18]=[CH:17][C:16]([CH2:19][CH2:20][OH:21])=[CH:15][CH:14]=1
Reactant: Cc1cccc(N)c1[N+](=O)[O-]
Reactant: OCCc1ccc(Br)cc1
Agent: [Cu]I
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Product: Cc1cccc(Nc2ccc(CCO)cc2)c1[N+](=O)[O-]
Temperature: 200 °C
Yield: 20.7 %

Procedure:
A mixture of 2-nitro-3-methylaniline (Newman, M. S.; Kannan R. J. Org. Chem., 1976, 41, 3356., 1.9 g, 12.4 mmol), 4-bromophenylethyl alcohol (2.5 g, 12.4 mmol), K2CO3 (1.7 g, 12.4 mmol) and CuI (230 mg, 1.24 mmol) was placed in a sealed tube and heated at 200° C. for 2 h. After cooling, the mixture was poured into water (100 mL) and extracted with ethyl acetate (300 mL). The organic layer was washed with 2N aqueous NaOH (100 mL) and brine (100 mL), then dried (Na2SO4), and concentrated. Purification by flash column chromatography on silica gel eluting with hexane/ethyl acetate (1:1) to afford 700 mg (21%) of the title compound as an orange oil: 1H-NMR (CDCl3) δ 7.77 (1H, br.s), 7.09-7.45 (6H, m), 6.69 (1H, d, J=6.3 Hz), 3.83 (2H, t, J=6.6 Hz), 2.82 (2H, t, J=6.6 Hz), 2.59 (3H, s).
Reaction SMILES: [C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][C:11]2[N:15]([CH3:16])[C:14]3[CH:17]=[CH:18][C:19]([N+:21]([O-])=O)=[CH:20][C:13]=3[N:12]=2)=[CH:5][CH:4]=1)#[N:2]>C1COCC1.[Pd]>[NH2:21][C:19]1[CH:18]=[CH:17][C:14]2[N:15]([CH3:16])[C:11]([CH2:10][CH2:9][C:6]3[CH:7]=[CH:8][C:3]([C:1]#[N:2])=[CH:4][CH:5]=3)=[N:12][C:13]=2[CH:20]=1
Reactant: Cn1c(CCc2ccc(C#N)cc2)nc2cc([N+](=O)[O-])ccc21
Agent: [Pd]
Solvent: C1CCOC1
Product: Cn1c(CCc2ccc(C#N)cc2)nc2cc(N)ccc21

Procedure:
2-[2-(4-Cyanophenyl)-ethyl]-1-methyl-5-nitro-benzimidazole (5.5 g, 18 mmol) in 150 mL THF/75 mL methanol is hydrogenated in the presence of 1.0 g of 5% Pd/C at ambient temperature and normal pressure. The catalyst is filtered off, the filtrate is evaporated down until not completely dry, diluted with 100 mL acetonitrile and evaporated down to a residual volume of 30 mL. The crystal slurry is cooled and filtered. The crystals are washed with cold acetonitrile and ether.
Reaction SMILES: [NH:1]([C:8]1[CH:16]=[C:15]([C:17](O)=[O:18])[C:14]([NH:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[CH:13][C:9]=1[C:10](O)=[O:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.P(=O)(O)(O)O.CO>O.[Fe]>[CH:24]1[CH:25]=[C:26]2[C:17]([C:15]3[C:14]([NH:20][C:21]2=[CH:22][CH:23]=1)=[CH:13][C:9]1[C:10]([C:7]2[C:2]([NH:1][C:8]=1[CH:16]=3)=[CH:3][CH:4]=[CH:5][CH:6]=2)=[O:11])=[O:18]
Reactant: O=C(O)c1cc(Nc2ccccc2)c(C(=O)O)cc1Nc1ccccc1
Agent: [Fe]
Agent: O=P(O)(O)O
Solvent: O
Solvent: CO
Product: O=c1c2ccccc2[nH]c2cc3c(=O)c4ccccc4[nH]c3cc12
Temperature: 85 °C
Reaction time: 0.33 h
Yield: 94.2 %

Procedure:
To 270 g of polyphosphoric acid (117.4% phosphoric acid) heated at 80°-95° C. was added 60 g (0.17 mole) of 2,5-dianilinoterephthalic acid containing about 583 ppm (about 0.63 mmole) of iron. The iron content, relative to 2,5-dianilinoterephthalic acid, was less than 0.4 mole percent. The mixture was heated at 120°-125° C. for four hours. After the viscous solution was cooled to 90°-95° C., the acid strength was adjusted to 107% by the dropwise addition of 75% phosphoric acid (65 g). The resultant melt was stirred for 20 minutes and then slowly poured into a mixture of 60 g of methanol and 40 g of water at 35° C. The temperature of the resultant slurry was allowed to rise during the addition to about 64° C., with the temperature being controlled during addition by external cooling and adjustment of melt addition rate. The slurry was heated at reflux (68°-72° C.) for one hour and diluted with 600 g of water. After the slurry was stirred for 30 minutes, the solid component was collected by filtration and washed with water until acid-free. The resultant presscake was reslurried in 1000 g of water and 5 g of 50% sodium hydroxide, then heated for 85° C. for two hours. After being cooled to 60° C., the slurry was filtered and washed with water until free of alkali. After the presscake was reslurried in 800 g water, a solution containing 37 g of water, 1.6 g of 50% sodium hydroxide, and 3.15 g of naphthenic acid was added. The slurry was heated to 140°-145° C. for two hours in a closed system (e.g., a pressure reactor). After the slurry was cooled to 60°-70° C., the pH was adjusted to 4.5-5.0 with phosphoric acid, stirred for one hour, collected by filtration, and washed with water. The wet cake can be oven dried or used as is for specific applications. Here, the wet cake was dried in an oven at 60° C. to give about 50 g of quinacridone as a brilliant violet solid.
Reaction SMILES: [NH:1]([C:8]1[CH:16]=[C:15]([C:17](O)=[O:18])[C:14]([NH:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[CH:13][C:9]=1[C:10](O)=[O:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.P(=O)(O)(O)O.CO>O>[CH:24]1[CH:25]=[C:26]2[C:17]([C:15]3[C:14]([NH:20][C:21]2=[CH:22][CH:23]=1)=[CH:13][C:9]1[C:10]([C:7]2[C:2]([NH:1][C:8]=1[CH:16]=3)=[CH:3][CH:4]=[CH:5][CH:6]=2)=[O:11])=[O:18]
Reactant: O=C(O)c1cc(Nc2ccccc2)c(C(=O)O)cc1Nc1ccccc1
Agent: O=P(O)(O)O
Solvent: CO
Solvent: O
Product: O=c1c2ccccc2[nH]c2cc3c(=O)c4ccccc4[nH]c3cc12
Temperature: 55 °C
Reaction time: 0.33 h
Yield: 86.7 %

Procedure:
To 300 g of polyphosphoric acid (117% phosphoric acid) heated to 80° C. was added 68.2 g of 2,5-dianilinoterephthalic acid. The reaction mixture was heated at 120°-125° C. for two hours. After the melt was cooled to 90°-95° C., the acid strength was adjusted to 112% by the dropwise addition of phosphoric acid. The resultant melt was stirred for 20 minutes and then slowly poured into 453 g of methanol at 24° C. During the drown, the temperature was allowed to increase to 55° C., with the temperature being controlled by external cooling and adjustment of melt addition rate. The slurry was heated at reflux (68°-72° C.) for one hour, diluted with water, and stirred at 60° C. for 30 minutes. The solid component was collected by filtration and washed with water until acid free. The resultant presscake was reslurried in water. After adjustment of the pH to about 7, 7.5 g of 50% sodium hydroxide was added and the resultant slurry was heated at 90°-95° C. for one hour. The slurry was cooled, filtered, and washed with water until alkali free, then reslurried in water (595 g total, including water from the presscake). After adjustment of the pH to 9.0-9.5, 3.2 g of a cycloaliphatic carboxylic acid was added. The resultant slurry was heated at about 140°-145° C. for two hours in a closed system, cooled, acidified with phosphoric acid, and stirred. The solid component was collected by filtration and washed with water. The wet cake can be dried or used as is for specific applications. Here, the wet cake was dried in an oven at 60° C. to give approximately 53 g of quinacridone as a violet pigment.
Reaction SMILES: O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[NH:15]([C:22]1[CH:30]=[C:29]([C:31](O)=[O:32])[C:28]([NH:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[CH:27][C:23]=1[C:24](O)=[O:25])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C1(C)C=CC(NC2C=C(C(O)=O)C(NC3C=CC(C)=CC=3)=CC=2C(O)=O)=CC=1>>[CH:38]1[CH:39]=[C:40]2[C:31]([C:29]3[C:28]([NH:34][C:35]2=[CH:36][CH:37]=1)=[CH:27][C:23]1[C:24]([C:21]2[C:16]([NH:15][C:22]=1[CH:30]=3)=[CH:17][CH:18]=[CH:19][CH:20]=2)=[O:25])=[O:32]
Reactant: O=C(O)c1cc(Nc2ccccc2)c(C(=O)O)cc1Nc1ccccc1
Agent: Cc1ccc(Nc2cc(C(=O)O)c(Nc3ccc(C)cc3)cc2C(=O)O)cc1
Agent: O=P12OP3(=O)OP(=O)(O1)OP(=O)(O2)O3
Product: O=c1c2ccccc2[nH]c2cc3c(=O)c4ccccc4[nH]c3cc12
Temperature: 85 °C

Procedure:
382 parts of polyphosphoric acid, containing 85.0% P2O5, are introduced into a pressure vessel. Then 64.9 parts of 2,5-dianilinoterephthalic acid and 11.5 parts of 2,5-di(4-toluidino)terephthalic acid are introduced with stirring at from 80 to 90° C. and the mixture is heated at 125° C. for 1 hour during which ring closure takes place to form the quinacridone. The reaction mixture is then introduced into a second pressure vessel where it is hydrolyzed under pressure and with stirring with a mixture of 1721 parts of 30% phosphoric acid at 140° C. During this hydrolysis the temperature rises to 155° C. The mixture is stirred at 155° C. for 0.5 hour. Then it is cooled to 60° C. and the mixed crystal pigment is filtered off with suction, washed to neutrality with water and dried at 80° C.
Reaction SMILES: [I:1][C:2]1[CH:3]=[N:4][NH:5][CH:6]=1.[C:7]1([C:13](Cl)([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C(N(CC)CC)C>CN(C=O)C>[C:13]([N:4]1[CH:3]=[C:2]([I:1])[CH:6]=[N:5]1)([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1
Reactant: Ic1cn[nH]c1
Reactant: ClC(c1ccccc1)(c1ccccc1)c1ccccc1
Solvent: CN(C)C=O
Solvent: CCN(CC)CC
Product: Ic1cnn(C(c2ccccc2)(c2ccccc2)c2ccccc2)c1
Reaction time: 8 h

Procedure:
The title compound was prepared by combining 4-iodopyrazole (10 g, 52 mmol), triphenylmethyl chloride (14.4 g, 51.6 mmol), triethylamine (NEt3) (7.2 mL, 52 mmol), and DMF (80 mL). After stirring overnight, the mixture was poured onto ice water. The precipitated solid was collected and recrystallized to give the title compound as a solid, mp 193-194° C.
Reaction SMILES: [N:1]12[C:7](=[O:8])[CH2:6][CH:5]1[CH2:4][C:3](=[O:9])[CH:2]2[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11].C(N(CC)CC)C.[CH2:27]=[C:28]=[O:29]>>[C:28]([O:9][C:3]1[CH2:4][CH:5]2[N:1]([C:7](=[O:8])[CH2:6]2)[C:2]=1[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])(=[O:29])[CH3:27]
Reactant: C=C=O
Reactant: O=C1CC2CC(=O)N2C1C(=O)OCc1ccccc1
Solvent: CCN(CC)CC
Product: CC(=O)OC1=C(C(=O)OCc2ccccc2)N2C(=O)CC2C1

Procedure:
A solution of benzyl 1-azabicyclo[3.2.0]heptan-3,7-dione-2-carboxylate (13 mg, 0.05 mmol) in anhydrous CH2CL2 (1 ml) is cooled in an ice-bath and treated with triethylamine (Et3N) (7 μl, 0.05 mmol). Ketene is passed through the resulting solution for 10 mins. The solvent and excess ketene are removed in vacuo to leave crude benzyl 3-acetoxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate
Reaction SMILES: [C:1]1([O:7][CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:9](OC(=O)C)(=[O:11])[CH3:10]>>[CH3:8][O:7][C:1]1[CH:6]=[CH:5][C:4]([C:9](=[O:11])[CH3:10])=[CH:3][CH:2]=1
Reactant: CC(=O)OC(C)=O
Reactant: COc1ccccc1
Product: COc1ccc(C(C)=O)cc1

Procedure:
The reaction between anisole and acetic anhydride was performed in substantially the same manner as in Example 49, except that each of the compounds as synthesized in Examples 42 and 43 was individually used as the Lewis acid catalyst. The yields of the reaction product (i.e., p-methoxyacetophenone) are shown in Table 2.
Reaction SMILES: N1CCCCC1.FC(F)OC1C=C(C=CC=1OC(F)F)C=O.C(CC(N[C:30]1[CH:38]=[CH:37][CH:36]=[CH:35][C:31]=1[C:32]([OH:34])=[O:33])=O)(O)=O>C1(C)C=CC=CC=1>[C:32]([OH:34])(=[O:33])[C:31]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:30]=1
Reactant: O=C(O)CC(=O)Nc1ccccc1C(=O)O
Agent: O=Cc1ccc(OC(F)F)c(OC(F)F)c1
Solvent: Cc1ccccc1
Solvent: C1CCNCC1
Product: O=C(O)c1ccccc1
Temperature: 25 °C
Yield: 230.5 %

Procedure:
Piperidine (100 μL, 1.01 mmol) was added to a suspension of 3,4-bis(difluoromethoxy)benzaldehyde (240 mg, 1.01 mmol) and 2-[(carboxyacetyl)amino]benzoic acid (204 mg, 0.92 mmol) in toluene (5.0 mL). The reaction flask was fitted with a Dean-Stark apparatus and heated to reflux for 30 min. The reaction was then cooled to rt and the resulting suspension was filtered and washed with toluene. The piperidinium salt was dissolved in MeOH (5 mL) and water (2 mL) and the solution was acidified with 50% aqueous AcOH. The crude product was collected by filtration and recrystallised from EtOH/water, filtered and washed with water to afford (E)-2-[[3,4-bis(difluoromethoxy)phenyl)-1-oxo-2-propenyl]amino]benzoic acid (259 mg, 71%) as a colourless crystalline solid; mp 190-193° C.; δH (400 MHz, DMSO-d6) 6.96 (d, J=15.6 Hz, 1H, CH═CHCO), 7.18 (t, J3,4=J4,5=8.0 Hz, 1H, H4), 7.27 (t, J=73 Hz, 2H, OCHF2), 7.38 (d, J5′,6′=8.0 Hz, 1H, H5′), 7.61 (d, J=15.6 Hz, 1H, CH═CHCO), 7.62 (t, J4,5=J5,6=8.0 Hz, 1H, H5), 7.78 (d, J2′,6=1.6 Hz, 1H, H2′), 7.68 (dd, J5′,6′=8.0, J2′,6′=1.6 Hz, 1H, H6′), 8.00 (d, J3,4=8.0 Hz, 1H, H3), 8.69 (d, J5,6=8.0 Hz, 1H, H6), 11.35 (s, 1H, NH), 13.56 (br s, 1H, CO2H); δC (100 MHz, DMSO-d6) 116.3 (t, J=258 Hz), 116.5 (t, J=258 Hz), 117.0, 120.1, 120.5, 120.8, 123.0, 123.8, 126.7, 131.1, 132.8, 133.9, 139.3, 140.7, 141.9, 142.7, 163.5, 169.4; HRMS (ESI) calculated for C18H13F4NO5 [M−H]− 398.0646, found 398.0652; νmax 1034, 1217, 1513, 1604, 1683, 2892, 3466 cm−1.
Reaction SMILES: [CH3:1][C:2]([OH:6])([CH3:5])[C:3]#[CH:4].C1(C)C=CC(S(O)(=O)=O)=CC=1.[O:18]1[CH:23]=[CH:22][CH2:21][CH2:20][CH2:19]1>>[O:18]1[CH2:23][CH2:22][CH2:21][CH2:20][CH:19]1[O:6][C:2]([CH3:5])([CH3:1])[C:3]#[CH:4]
Reactant: C1=COCCC1
Reactant: C#CC(C)(C)O
Agent: Cc1ccc(S(=O)(=O)O)cc1
Product: C#CC(C)(C)OC1CCCCO1
Temperature: 25 °C
Reaction time: 40 h

Procedure:
3-Methyl-1-butyn-3-ol (25 ml, 21.7 g), dihydropyran (50 ml) and p-toluenesulphonic acid (5 mg) were mixed together at 0° C. for 1 hr, and then stirred at room temperature for a further 40 hr. The mixture was concentrated and the reside added to 5% aqueous NaHCO3 and extracted with benzene. The organic solution was dried to give after distillation 37.3 g (86%) of the title ether. b.p. 47° C./0.8 mm Hg (lit. 30°-33° C./ 0.5 mm50 ; 57° C./3.5mm170); 1Hnmr δ 5.6 (m, THP C-2'H), 2.45 (s. C-1H), 1.51 (s, CH3), 1.48 (s, CH3); IR (thin film) 3350 s), 2950 (s), 2900 (sh), 112S (s), 1070 (s), 1030 (s), cm-1.