Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [C:1]([O:5][C:6](=[O:23])[NH:7][CH:8]([C:15]1[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([Cl:22])[CH:16]=1)[C:9](=[O:14])N(OC)C)([CH3:4])([CH3:3])[CH3:2].[Br:24][C:25]1[CH:26]=[CH:27][C:28](I)=[C:29]([CH3:31])[CH:30]=1>>[C:1]([O:5][C:6](=[O:23])[NH:7][CH:8]([C:15]1[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([Cl:22])[CH:16]=1)[C:9]([C:28]1[CH:27]=[CH:26][C:25]([Br:24])=[CH:30][C:29]=1[CH3:31])=[O:14])([CH3:2])([CH3:3])[CH3:4]
Reactant: CON(C)C(=O)C(NC(=O)OC(C)(C)C)c1ccc(Cl)c(Cl)c1
Reactant: Cc1cc(Br)ccc1I
Product: Cc1cc(Br)ccc1C(=O)C(NC(=O)OC(C)(C)C)c1ccc(Cl)c(Cl)c1

Procedure:
The title compound was prepared from rac-[(3,4-dichloro-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 9) and 5-bromo-2-iodotoluene in analogy to Example 1a): MS (ISP): 473.9 (M+H)+ and 373.9 ((M-Boc)+H)+.
Reaction SMILES: [C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH2:22][CH2:23][CH2:24][CH3:25])=[CH:17][CH:16]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:26][O:27][C:28]1[CH:29]=[C:30]([C:38]2[CH:39]=[C:40]([CH:43]=[CH:44][CH:45]=2)[CH2:41]Cl)[CH:31]=[C:32]([O:36][CH3:37])[C:33]=1[O:34][CH3:35]>>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([N:14]([C:15]2[CH:20]=[CH:19][C:18]([O:21][CH2:22][CH2:23][CH2:24][CH3:25])=[CH:17][CH:16]=2)[CH2:41][C:40]2[CH:43]=[CH:44][CH:45]=[C:38]([C:30]3[CH:31]=[C:32]([O:36][CH3:37])[C:33]([O:34][CH3:35])=[C:28]([O:27][CH3:26])[CH:29]=3)[CH:39]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]
Reactant: CCCCOc1ccc(NC2CCN(C(=O)OC(C)(C)C)CC2)cc1
Reactant: COc1cc(-c2cccc(CCl)c2)cc(OC)c1OC
Product: CCCCOc1ccc(N(Cc2cccc(-c3cc(OC)c(OC)c(OC)c3)c2)C2CCN(C(=O)OC(C)(C)C)CC2)cc1

Procedure:
1-(tert-Butoxycarbonyl)-4-[(4-butoxyphenyl)amino]piperidine (697 mg) and 3-(3,4,5-trimethoxyphenyl)benzyl chloride (586 mg) was treated in the same manner as described in Example 9 to give light yellow amorphous of the title compound.
Reaction SMILES: I[C:2]1[C:10]2[C:5](=[N:6][CH:7]=[N:8][C:9]=2[NH2:11])[N:4]([C@H:12]2[CH2:17][CH2:16][C@@H:15]([N:18]3[CH2:23][CH2:22][N:21]([CH3:24])[CH2:20][CH2:19]3)[CH2:14][CH2:13]2)[N:3]=1.[CH2:25]([O:32][C:33]1[CH:38]=[CH:37][C:36](B(O)O)=[CH:35][CH:34]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:25]([O:32][C:33]1[CH:38]=[CH:37][C:36]([C:2]2[C:10]3[C:5](=[N:6][CH:7]=[N:8][C:9]=3[NH2:11])[N:4]([C@H:12]3[CH2:17][CH2:16][C@@H:15]([N:18]4[CH2:23][CH2:22][N:21]([CH3:24])[CH2:20][CH2:19]4)[CH2:14][CH2:13]3)[N:3]=2)=[CH:35][CH:34]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1
Reactant: OB(O)c1ccc(OCc2ccccc2)cc1
Reactant: CN1CCN([C@H]2CC[C@@H](n3nc(I)c4c(N)ncnc43)CC2)CC1
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: O
Solvent: COCCOC
Product: CN1CCN([C@H]2CC[C@@H](n3nc(-c4ccc(OCc5ccccc5)cc4)c4c(N)ncnc43)CC2)CC1
Temperature: 85 °C
Yield: 76.6 %

Procedure:
A mixture of cis-3-iodo-1-[4-(4-methylpiperazino)cyclohexyl]-1H-pyrazolo[3,4-d]pyrimidin-4-amine (3.41 g, 7.74 mmol) in ethylene glycol dimethyl ether (50 mL) was treated with 4-(benzyloxy)phenylboronic acid (1.94 g, 8.51 mmol), tetrakis(triphenylphosphine)palladium (0.537 g, 0.464 mmol), and a solution of sodium carbonate (1.97 g, 18.58 mmol) in water (25 mL). The reaction mixture was stirred over night at 85° C. under a nitrogen atmosphere. The organic solvent was removed under reduced pressure. Ethyl acetate (300 mL) was added to the aqueous layer. The layers were partitioned, and the aqueous layer was extracted with ethyl acetate (200 mL). The combined organic layers were washed with water and brine (1 L each), dried over magnesium sulfate, filtered and evaporated under reduced pressure. Ethyl acetate was added to the solid. A significant amount of the solid was not soluble in ethyl acetate, and was subsequently filtered to give 2.95 g (77%) of cis-3-[4-(benzyloxy)phenyl]-1-[4-(4-methylpiperazino)cyclohexyl]-1H-pyrazolo[3,4-d]pyrimidin-4-amine. 1H NMR (DMSO-d6, 400 MHz) δ 8.217 (s, 1H), 7.592-7.570 (m, 2H), 7.504-7.483 (m, 2H), 7.440-7.369 (m, 3H), 7.206-7.184 (m, 2H), 5.186 (s, 2H), 4.802-4.755 (m, 1H), 2.497-2.354 (m, 7H), 2.256-2.228 (m, 4H), 2.151 (s, 3H), 2.076-1.989 (m, 2H), 1.694-1.673 (m, 2H), 1.607-1.545 (m, 2H); HPLC Waters 2690 Alliance HPLC (Symmetry Shield RP18 3.5 μm, 2.1×50 mm; 5%-95% acetonitrile-0.1 M ammonium acetate over 15 min, 0.5 mL/min) Rt 5.128 min (100%).
Reaction SMILES: Cl[C:2]1[N:3]=[CH:4][C:5]2[N:11]([CH3:12])[C:10](=[O:13])[C:9]([F:15])([F:14])[CH2:8][N:7]([CH:16]3[CH2:20][CH2:19][CH2:18][CH2:17]3)[C:6]=2[N:21]=1.[NH2:22][C:23]1[CH:38]=[CH:37][C:26]([C:27]([NH:29][CH:30]2[CH2:35][CH2:34][N:33]([CH3:36])[CH2:32][CH2:31]2)=[O:28])=[CH:25][C:24]=1[O:39][CH:40]([CH3:42])[CH3:41].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(O)(C)C>ClCCl.C(=O)([O-])[O-].[Na+].[Na+]>[CH:16]1([N:7]2[CH2:8][C:9]([F:15])([F:14])[C:10](=[O:13])[N:11]([CH3:12])[C:5]3[CH:4]=[N:3][C:2]([NH:22][C:23]4[CH:38]=[CH:37][C:26]([C:27]([NH:29][CH:30]5[CH2:31][CH2:32][N:33]([CH3:36])[CH2:34][CH2:35]5)=[O:28])=[CH:25][C:24]=4[O:39][CH:40]([CH3:42])[CH3:41])=[N:21][C:6]2=3)[CH2:20][CH2:19][CH2:18][CH2:17]1
Reactant: CC(C)Oc1cc(C(=O)NC2CCN(C)CC2)ccc1N
Reactant: CN1C(=O)C(F)(F)CN(C2CCCC2)c2nc(Cl)ncc21
Agent: Cc1ccc(S(=O)(=O)O)cc1
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: CC(C)O
Solvent: O
Solvent: ClCCl
Product: CC(C)Oc1cc(C(=O)NC2CCN(C)CC2)ccc1Nc1ncc2c(n1)N(C1CCCC1)CC(F)(F)C(=O)N2C
Yield: 71.1 %

Procedure:
A mixture of 0.10 g (0.32 mmole) of 2-chloro-9-cyclopentyl-7,7-difluoro-5-methyl-5,7,8,9-tetrahydro-pyrimido[4,5-b][1,4]diazepin-6-one (VII-20), 0.11 g (0.38 mmole) of 4-amino-3-isopropoxy-N-(1-methyl-piperidin-4-yl)-benzamide, 0.090 g (0.48 mmole) of p-toluenesulfonic acid monohydrate and 4 mL of isopropanol was heated in a pressure tube at 140 degrees overnight, then cooled and diluted with dichloromethane and saturated sodium carbonate. The mixture was extracted twice with dichloromethane. The combined organic layers were washed three times with sodium carbonate, three times with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Purification by silica gel chromatography, eluting with dichloromethane-methanol (gradient, 100:0-60:40) gave 0.13 g of 4-(9-cyclopentyl-7,7-difluoro-5-methyl-6-oxo-6,7,8,9-tetrahydro-5H-pyrimido[4,5-b][1,4]diazepin-2-ylamino)-3-isopropoxy-N-(1-methyl-piperidin-4-yl)-benzamide (I-180) as a white solid.
Reaction SMILES: C(OC([NH:11][C:12]([C@H:14]1[C@@H:17]([C:18]([NH2:20])=[O:19])[CH2:16][NH:15]1)=[O:13])=O)C1C=CC=CC=1.[H][H]>CO>[NH:15]1[CH2:16][C@H:17]([C:18]([NH2:20])=[O:19])[C@@H:14]1[C:12]([NH2:11])=[O:13]
Reactant: NC(=O)[C@H]1CN[C@H]1C(=O)NC(=O)OCc1ccccc1
Reactant: [H][H]
Solvent: CO
Product: NC(=O)[C@H]1CN[C@H]1C(N)=O

Procedure:
A solution of cis-N-(benzyloxycarbonyl)azetidine-2,3dicarboxylic acid and, e.g., ammonia are reacted with [(CH3)2N]3PCl2 to form the cis-N-(benzyloxycarbonyl)azetidine-2,3-dicarboxamide (XI), as set forth by Appel et al., Chem. Ber. 116, 2037-2040 (1983). XI, 10% pd/C and methanol are hydrogenated in a Parr shaker under 3 atm of hydrogen, for 4 hours. The catalyst is filtered off and thoroughly washed. The solution is evaporated to dryness and dried in vacuo to arrive at cis-azetidine-2,3-dicarboxamide.
Reaction SMILES: C([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9](C=O)=[CH:8][C:7]([O:15][CH3:16])=[CH:6]2)C.Cl[C:18]1C=CC=C(C(OO)=O)[CH:19]=1.S([O-])([O-])(=[O:30])=S.[Na+].[Na+]>ClCCl>[CH2:18]([C:12]1[CH:11]=[C:10]2[C:5](=[CH:4][CH:3]=1)[C:6]([OH:30])=[C:7]([O:15][CH3:16])[CH:8]=[CH:9]2)[CH3:19]
Reactant: O=S([O-])([O-])=S
Reactant: O=C(OO)c1cccc(Cl)c1
Reactant: CCc1ccc2c(C=O)cc(OC)cc2c1
Agent: [Na+]
Solvent: ClCCl
Product: CCc1ccc2c(O)c(OC)ccc2c1
Temperature: 0 °C
Reaction time: 0.33 h

Procedure:
4.4 g of 6-ethyl-3-methoxy-1-naphthalene carbaldehyde and 4.9 g of 80-85% m-chloroperbenzoic acid were dissolved in 40 ml of dichloromethane and then refluxed under heating for 30 min. The solution was cooled to 0° C. and after adding an aqueous saturated solution of sodium thiosulfate and stirring for 20 min, insoluble matters were removed by filtration and then the filtrate was extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and then dried over anhydrous magnesium sulfate.
Reaction SMILES: FC(F)(F)[C:3](O)=[O:4].[NH2:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([NH:16][S:17]([CH3:20])(=[O:19])=[O:18])=[CH:12][C:11]=1OC.[C:23]([C:27]1[CH:37]=[CH:36][C:30]([O:31][CH2:32][C:33]([OH:35])=O)=[CH:29][CH:28]=1)([CH3:26])([CH3:25])[CH3:24].Cl.C(N=C=NCCCN(C)C)C.C(N(CC)CC)C>CN(C)C1C=CN=CC=1.CN(C)C=O>[C:23]([C:27]1[CH:28]=[CH:29][C:30]([O:31][CH2:32][C:33]([NH:8][CH2:9][C:10]2[CH:11]=[CH:12][C:13]([NH:16][S:17]([CH3:20])(=[O:18])=[O:19])=[C:14]([O:4][CH3:3])[CH:15]=2)=[O:35])=[CH:36][CH:37]=1)([CH3:24])([CH3:25])[CH3:26]
Reactant: O=C(O)C(F)(F)F
Reactant: COc1cc(NS(C)(=O)=O)ccc1CN
Reactant: CC(C)(C)c1ccc(OCC(=O)O)cc1
Agent: CCN=C=NCCCN(C)C
Agent: CN(C)c1ccncc1
Agent: Cl
Solvent: CCN(CC)CC
Solvent: CN(C)C=O
Product: COc1cc(CNC(=O)COc2ccc(C(C)(C)C)cc2)ccc1NS(C)(=O)=O
Yield: 43 %

Procedure:
A mixture of N-[4-(aminomethyl)-3-methoxyphenyl]methanesulfonamide trifluoroacetic acid (1.24 g, 3.6 mmol), (4-tert-butylphenoxy)acetic acid (625 mg, 3.0 mmol), 1-ethyl-3-(3′-dimethylaminopropyl) carbodiimide hydrogen chloride (EDC) (1.04 g, 5.4 mmol), triethylamine (1.21 g, 2.0 mmol) and 4-(dimethylamino)pyridine (DMAP) (110 mg, 0.9 mmol) in N,N-dimethylformamide (DMF) (30 ml) was treated in the same procedure described in Example 2(b) to give 543 mg (43% yield) of the title compound as a white amorphous solid.
Reaction SMILES: C(Cl)(=O)C(Cl)=O.[CH2:7]([O:14][C:15]1[CH:23]=[C:22]([CH3:24])[CH:21]=[CH:20][C:16]=1[C:17](O)=[O:18])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1>ClCCl.CN(C=O)C>[CH2:7]([O:14][C:15]1[CH:23]=[C:22]([CH3:24])[CH:21]=[CH:20][C:16]=1[CH:17]=[O:18])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1
Reactant: Cc1ccc(C(=O)O)c(OCc2ccccc2)c1
Agent: O=C(Cl)C(=O)Cl
Solvent: ClCCl
Solvent: CN(C)C=O
Product: Cc1ccc(C=O)c(OCc2ccccc2)c1
Temperature: -78 °C
Reaction time: 2 h
Yield: 44.3 %

Procedure:
Oxalyl chloride (3.6 ml) was added to a solution of 2-benzyloxy-4-methylbenzoic acid (9.02 g) in dichloromethane (20 ml), one drop of DMF was added and the mixture was stirred for 2 hours then evaporated to dryness. The residue was dissolved in diglyme (70 ml) and cooled to -78° C. under argon. Lithium-tri-t-butoxyaluminohydride (78 ml of 0.5M solution in diglyme) was added at such a rate that the temperature did not exceed -60° C. The mixture was stirred below this temperature for 2 hours and was then poured carefully onto ice and acidified with concentrated HCl. The mixture was extracted with diethylether (3×150 ml) and the gum obtained on work up was subjected to chromatography on silica eluted with dichloromethane to give 2-benzyloxy-4-methylbenzaldehyde (3.73 g).
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][N:5]2[C:8]3[CH:14]=[CH:13][CH:12]=[CH:11][C:9]=3[N:10]=[C:4]2[N:3]=1.[CH2:15]([OH:20])[CH2:16][CH2:17][C:18]#[CH:19].CCN(C(C)C)C(C)C>O1CCOCC1.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N:3]1[C:4]2[N:5]([C:8]3[CH:14]=[CH:13][CH:12]=[CH:11][C:9]=3[N:10]=2)[CH:6]=[CH:7][C:2]=1[C:19]#[C:18][CH2:17][CH2:16][CH2:15][OH:20]
Reactant: C#CCCCO
Reactant: Brc1ccn2c(n1)nc1ccccc12
Agent: c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Solvent: C1COCCO1
Solvent: CCN(C(C)C)C(C)C
Solvent: CCOC(C)=O
Product: OCCCC#Cc1ccn2c(n1)nc1ccccc12
Temperature: 120 °C
Yield: 55.7 %

Procedure:
A mixture of 2-bromobenzo[4,5]imidazo[1,2-a]pyrimidine (40 mg, 0.2 mmol), pent-4-yn-1-ol (22 mg, 0.26 mmol), tetrakis(triphenylphosphine)palladium (23 mg, 0.02 mmol), DIPEA (50 mg, 0.4 mmol) in 2 mL dioxane was heated at 120° C. for 20 min in a microwave reactor and then cooled to rt. It was diluted with EtOAc (20 mL) and washed with brine (30 mL) and water (2×30 mL) and concentrated. The residue was purified by silica chromatography (EtOAc in DCM, 10% to 100%) to afford 5-(benzo[4,5]imidazo[1,2-a]pyrimidin-2-yl)pent-4-yn-1-ol as a yellow solid (28 mg, 56%). 1H NMR (400 MHz, CDCl3): δ 8.68 (d, J=6.8, 1H), 8.03 (d, J=8.4 Hz, 1H), 7.86 (d, J=8.4 Hz, 1H), 7.57 (m, 1H), 7.42 (m, 1H), 6.95 (d, J=6.8 Hz, 1H), 3.85 (t, J=6 Hz, 2H), 2.82 (t, J=6.8 Hz, 2H), 1.93 (m, 2H); MS (ESI) m/z [M+H]+252.
Reaction SMILES: [C:1]1([CH:7]=[CH:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([OH:15])=[O:14])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:16][C:17]1[C:22]([CH3:23])=[CH:21][C:20]([CH3:24])=[CH:19][C:18]=1O.CS(O)(=O)=O.[OH2:31]>ClCCl>[OH:31][C:18]1[C:17]([CH3:16])=[C:22]([CH3:23])[CH:21]=[C:20]([CH3:24])[C:19]=1[CH:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([OH:15])=[O:14]
Reactant: Cc1cc(C)c(C)c(O)c1
Reactant: O
Reactant: O=C(O)CCCCC=Cc1ccccc1
Agent: CS(=O)(=O)O
Solvent: ClCCl
Product: Cc1cc(C)c(C(CCCCCC(=O)O)c2ccccc2)c(O)c1C
Temperature: 25 °C
Reaction time: 6 h
Yield: 85.2 %

Procedure:
7-Phenyl-6-heptenoic acid (10 g) and 2,3,5-trimethylphenol (8.3 g) were suspended in dichloromethane (80 ml). To the suspension was added dropwise methanesulfonic acid (9.4 g) at a temperature ranging from 17°-25° C. The mixture was stirred at 25° C. for 6 hours, to which was then added water (80 ml). The dichloromethane layer was separated and washed with water three times. Dichloromethane was distilled off under reduced pressure, and the residue was recrystallized from toluene (38 m;) to give 7-(2-hydroxy-3,4,6-trimethylphenyl)-7-phenylheptanoic acid (14.2g, 85.2%) as white crystals.
Reaction SMILES: C1([P:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:20]([O:27]C1C=C(CBr)C(OCCCCCCC)=CC=1CBr)CCCCCC.CN(C)[CH:48]=[O:49]>>[PH4+:7].[CH:48](=[O:49])[C:14]1[CH:15]=[CH:16][C:17]([CH:20]=[O:27])=[CH:18][CH:19]=1
Reactant: CN(C)C=O
Reactant: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Reactant: CCCCCCCOc1cc(CBr)c(OCCCCCCC)cc1CBr
Product: O=Cc1ccc(C=O)cc1
Product: [PH4+]

Procedure:
A phosphonium salt (A) was synthesized by the reaction of 2,5-diethyl-P-xylylene dibromide with triphenylphosphine in an N,N-dimethylformamide solvent, and a phosphonium salt (B) was synthesized by the reaction of 2,5-diheptyloxy-p-xylylene dibromide with triphenylphosphine in an N,N-dimethylformamide solvent. The obtained two phosphonium salts (A) (4.1 parts by weight) and (B) (1.0 part by weight) and terephthalaldehyde (0.8 parts by weight) were dissolved in ethyl alcohol. For a 3-hour polymerization, an ethyl alcohol solution containing 0.8 parts by weight of lithium ethoxide was added dropwise to an ethyl alcohol solution of the phosphonium salts and dialdehyde at room temperature. After allowed to stand alone at room temperature overnight, the reaction solution was subjected to fractionation by precipitation. The precipitate was then filtered out, washed with ethyl alcohol, and dissolved in chloroform, to which ethanol was added for re-precipitation. The obtained product was dried under reduced pressure to obtain 0.35 parts by weight of the end polymer. This is called a polymeric fluorescent substance 1. Set out below are the repeating unit in polymeric fluorescent substance 1 and its molar ratio calculated from the charge ratio of monomers.
Reaction SMILES: [Cl:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](Cl)=[O:7])=[CH:4][CH:3]=1.[CH2:11]([CH2:13][NH2:14])[OH:12].C(N(CC)CC)C.Cl>C(Cl)Cl>[OH:12][CH2:11][CH2:13][NH:14][C:6](=[O:7])[C:5]1[CH:9]=[CH:10][C:2]([Cl:1])=[CH:3][CH:4]=1
Reactant: O=C(Cl)c1ccc(Cl)cc1
Reactant: NCCO
Agent: Cl
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: O=C(NCCO)c1ccc(Cl)cc1
Yield: 77.6 %

Procedure:
2.6 ml (0.02 mol) of 4-chlorobenzoyl chloride are added dropwise at 0° to a solution of 1.2 ml (0.02 mol) of ethanolamine and 3 ml (about 0.02 mol) of triethylamine in 30 ml of methylene chloride. The mixture is then poured into dilute hydrochloric acid and extracted twice with methylene chloride. The methylene chloride extracts are dried over magnesium sulfate and concentrated. After purification on silica gel using chloroform and chloroform/methanol 9:1) as the eluting agent, there are obtained 3.1 g of N-(2-hydroxyethyl)-4-chlorobenzamide.
Reaction SMILES: [C:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH:7]=O)([OH:3])=[O:2].[NH2:12][C:13]1[C:18]([NH2:19])=[CH:17][C:16]([N+:20]([O-])=O)=[CH:15][N:14]=1.Cl[C:24]([O:26][CH:27]([CH3:29])[CH3:28])=[O:25].[OH-].[Na+]>CN1C(=O)CCC1.O>[CH:27]([O:26][C:24]([NH:20][C:16]1[CH:17]=[C:18]2[N:19]=[C:7]([C:6]3[CH:5]=[C:4]([CH:11]=[CH:10][CH:9]=3)[C:1]([OH:3])=[O:2])[NH:12][C:13]2=[N:14][CH:15]=1)=[O:25])([CH3:29])[CH3:28]
Reactant: CC(C)OC(=O)Cl
Reactant: Nc1cc([N+](=O)[O-])cnc1N
Reactant: O=Cc1cccc(C(=O)O)c1
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: CN1CCCC1=O
Product: CC(C)OC(=O)Nc1cnc2[nH]c(-c3cccc(C(=O)O)c3)nc2c1

Procedure:
was prepared starting from 3-carboxybenzaldehyde and 2,3-diamino-5-nitropyridine as described for 10-1. In the final step, after reacting with isopropyl chloroformate in NMP, the reaction mixture was treated with 100 mg sodium hydroxide and 1 ml water for 1 hr at room temperature. The crude product was precipitated by addition of 30 ml water and filtered off. It was further purified by dissolving in 50 ml aqueous sodium carbonate solution and washing with dichloromethane. The carbonate solution was acidified to pH 2-3 by addition acetic acid and HCl, and extracted with dichloromethane. The dichloromethane phase was evaporated to give 61 mg of the title product.
Reaction SMILES: [CH3:1][CH:2]([CH2:18][CH2:19][CH:20]=[C:21]([CH3:23])[CH3:22])[CH2:3][CH2:4][O:5][C:6](=[O:17])[CH2:7][CH2:8][CH:9]([OH:16])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].N1C=CC=CC=1.[CH2:30]([O:38][C:39](Cl)=[O:40])[CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.O>O1CCCC1>[CH3:1][CH:2]([CH2:18][CH2:19][CH:20]=[C:21]([CH3:23])[CH3:22])[CH2:3][CH2:4][O:5][C:6](=[O:17])[CH2:7][CH2:8][CH:9]([O:16][C:39]([O:38][CH2:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)=[O:40])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]
Reactant: O=C(Cl)OCCc1ccccc1
Reactant: CCCCCCC(O)CCC(=O)OCCC(C)CCC=C(C)C
Solvent: O
Solvent: c1ccncc1
Solvent: C1CCOC1
Product: CCCCCCC(CCC(=O)OCCC(C)CCC=C(C)C)OC(=O)OCCc1ccccc1
Reaction time: 16 h
Yield: 89.7 %

Procedure:
To a mixture of 3 g 4-hydroxy-decanoic acid 3,7-dimethyl-oct-6-enyl ester and 1.45 g pyridine in 7 ml tetrahydrofuran was slowly added a solution of 1.87 g chlorocarbonic acid phenethyl ester (Schiving et al., Bull. Soc. Chim. Fr. (4), 43, 1928, 858) in 7 ml tetrahydrofuran. The mixture was stirred for 16 hours. Water was added and the mixture extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate, 2N hydrochloric acid, water, dried over magnesium sulfate and evaporated to dryness. The residue was chromatographed on silica gel to give 3.91 g of a colorless liquid.
Reaction SMILES: [C:1]([O:4][CH2:5][CH:6]1[CH2:23][CH2:22][N:9]2[C:10]3[C:15]([C:16]([C:17](=O)[C:18](Cl)=[O:19])=[C:8]2[CH2:7]1)=[CH:14][CH:13]=[CH:12][CH:11]=3)(=[O:3])[CH3:2].Cl.[CH3:25][N:26]1[C:34]2[C:29](=[CH:30][CH:31]=[CH:32][CH:33]=2)[C:28]([CH2:35][C:36](=[NH:38])[OH:37])=[CH:27]1>>[C:1]([O:4][CH2:5][CH:6]1[CH2:23][CH2:22][N:9]2[C:10]3[C:15]([C:16]([C:17]4[C:18](=[O:19])[NH:38][C:36](=[O:37])[C:35]=4[C:28]4[C:29]5[C:34](=[CH:33][CH:32]=[CH:31][CH:30]=5)[N:26]([CH3:25])[CH:27]=4)=[C:8]2[CH2:7]1)=[CH:14][CH:13]=[CH:12][CH:11]=3)(=[O:3])[CH3:2]
Reactant: CC(=O)OCC1CCn2c(c(C(=O)C(=O)Cl)c3ccccc32)C1
Reactant: Cn1cc(CC(=N)O)c2ccccc21
Agent: Cl
Product: CC(=O)OCC1CCn2c(c(C3=C(c4cn(C)c5ccccc45)C(=O)NC3=O)c3ccccc32)C1

Procedure:
In a manner analogous to that described in Example 1, 333 mg (1 retool) of [8-(acetoxymethyl)-6,7,8,9-tetrahydropyrido[1,2-a]indol-10-yl]glyoxylyl chloride were treated with 266 mg (1 mmol) of isopopyl 1-methyl-3-indoleacetimidate hydrochloride in different solvents and at various temperatures to give 3-[8-(acetoxymethyl)-6,7,8,9-tetrahydropyrido[1,2-a]indol- 10-yl ]-4-(1-methyl-3-indolyl)- 1H-pyrrole-2,5-dione. The results obtained are compiled in Table I:
Reaction SMILES: [CH2:1]([O:11][C:12]1[CH:17]=[CH:16][C:15]([C:18](=O)[C:19]2[CH:24]=[CH:23][CH:22]=[C:21]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:20]=2)=[CH:14][C:13]=1[CH2:31][CH2:32][C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10].Cl.[NH2:39][OH:40].C(OCC)(=O)C>N1C=CC=CC=1>[CH2:28]([O:27][C:25]([C:21]1[CH:20]=[C:19]([C:18](=[N:39][OH:40])[C:15]2[CH:16]=[CH:17][C:12]([O:11][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10])=[C:13]([CH2:31][CH2:32][C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:14]=2)[CH:24]=[CH:23][CH:22]=1)=[O:26])[CH3:29]
Reactant: CCCCCCCCCCOc1ccc(C(=O)c2cccc(C(=O)OCC)c2)cc1CCC(=O)OCC
Reactant: NO
Agent: Cl
Solvent: c1ccncc1
Solvent: CCOC(C)=O
Product: CCCCCCCCCCOc1ccc(C(=NO)c2cccc(C(=O)OCC)c2)cc1CCC(=O)OCC
Temperature: 70 °C
Yield: 91.8 %

Procedure:
A mixture of 1.1 g of 2-(decyloxy)-5-[3-(ethyloxycarbonyl)benzoyl]benzenepropanoic acid, ethyl ester and 220 mg of hydroxylamine hydrochloride in 25 ml of pyridine was heated at 70° C. for approximately 18 hours. The reaction was allowed to cool to ambient temperature, ethyl acetate was added, and the solution was washed several times with 1N hydrochloric acid and water. The organic layer was dried over sodium sulfate and concentrated in vacuo to provide 1.04 g of the desired title product as an oil. NMR.
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([O:10][CH2:11][CH3:12])[CH:3]=1.C([Li])CCC.[O:18]1[C:22]2[CH:23]=[CH:24][C:25]([CH:27]=[O:28])=[CH:26][C:21]=2[O:20][CH2:19]1.C(O)(C)C>C1COCC1.O>[O:18]1[C:22]2[CH:23]=[CH:24][C:25]([CH:27]([C:2]3[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([O:10][CH2:11][CH3:12])[CH:3]=3)[OH:28])=[CH:26][C:21]=2[O:20][CH2:19]1
Reactant: CCOc1cc(Br)ccc1OC
Reactant: O=Cc1ccc2c(c1)OCO2
Agent: [Li]CCCC
Solvent: C1CCOC1
Solvent: CC(C)O
Solvent: O
Product: CCOc1cc(C(O)c2ccc3c(c2)OCO3)ccc1OC
Temperature: -78 °C
Reaction time: 0.33 h
Yield: 56 %

Procedure:
A stirred mixture of 4-bromo-2-ethoxy-1-methoxy-benzene (1.65 g, 7.1 mmol) and dry THF (15 mL) was cooled to −78° C., evacuated and refilled with nitrogen for 10 cycles. To this clear solution was slowly added n-butyllithium (2.9 mL, 7.1 mmol) and stirred for 20 min. Then a mixture of benzo[1,3]dioxole-5-carbaldehyde (0.98 g, 6.5 mmol) in dry THF (20 mL) was added and stirred for 1 hour at −78° C. The mixture was quenched with isopropanol (3.0 mL, 39 mmol) and added water (10 mL). The mixture was extracted with EtOAc (3×50 mL). The combined organic phases were washed with water (2×50 mL), dried over MgSO4 and concentrated to oil, which was purified by flash column chromatography (EtOAc/Hexane) to give benzo[1,3]dioxol-5-yl-(3-ethoxy-4-methoxy-phenyl)-methanol as an off-white solid (1.1 g, 56% yield): 1H NMR (CDCl3) δ 1.44 (t, J=7 Hz, 3H, CH2CH3), 2.11 (d, J=3 Hz, 1H, OH), 3.86 (s, 3H, OCH3), 4.07 (q, J=7 Hz, 2H, CH2CH3), 5.71 (d, J=3 Hz, 1H, CH), 5.93 (s, 2H, CH2), 6.74-6.91 (m, 6H, Ar). The product was used in the next step without further purification.