Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][CH:2]([S:4](Cl)(=[O:6])=[O:5])[CH3:3].[NH2:8][C:9]1[CH:10]=[CH:11][C:12]([O:26][CH2:27][CH3:28])=[C:13]([C:15]2[NH:16][C:17](=[O:25])[C:18]3[N:24]=[CH:23][CH:22]=[CH:21][C:19]=3[N:20]=2)[CH:14]=1>>[CH2:27]([O:26][C:12]1[CH:11]=[CH:10][C:9]([NH:8][S:4]([CH:2]([CH3:3])[CH3:1])(=[O:6])=[O:5])=[CH:14][C:13]=1[C:15]1[NH:16][C:17](=[O:25])[C:18]2[N:24]=[CH:23][CH:22]=[CH:21][C:19]=2[N:20]=1)[CH3:28]
Reactant: CC(C)S(=O)(=O)Cl
Reactant: CCOc1ccc(N)cc1-c1nc2cccnc2c(=O)[nH]1
Product: CCOc1ccc(NS(=O)(=O)C(C)C)cc1-c1nc2cccnc2c(=O)[nH]1

Procedure:
The title compound was prepared using 2-propyl-sulphonyl chloride and 2-(5-amino-2-ethoxyphenyl)-pyrido[3,2-d]pyrimidin-4(3H)-one (Example 20), following the procedure of Example 12, and was obtained as a hydrated solid (59%), m.p. 211°-213° C. Found: C,54.98; H,5.07; N;14.21. C18H20N4O4S;0.25 H2O requires C,55.02; H,5.26; N,14.26%.
Reaction SMILES: [Cl:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[C:7]([O:12][C:13]3[CH:18]=[CH:17][C:16]([OH:19])=[CH:15][CH:14]=3)[N:8]=[CH:9]2)=[CH:4][CH:3]=1.Br[CH:21]([CH3:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23].C(=O)([O-])[O-].[K+].[K+].ClCCl>C(C(C)=O)C>[Cl:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[C:7]([O:12][C:13]3[CH:14]=[CH:15][C:16]([O:19][CH:21]([CH3:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:17][CH:18]=3)[N:8]=[CH:9]2)=[CH:4][CH:3]=1
Reactant: CCOC(=O)C(C)Br
Reactant: Oc1ccc(Oc2cc3ccc(Cl)cc3cn2)cc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: ClCCl
Solvent: CCC(C)=O
Product: CCOC(=O)C(C)Oc1ccc(Oc2cc3ccc(Cl)cc3cn2)cc1
Yield: 86.3 %

Procedure:
4-[(7-chloroisoquinolin-3-yl)oxy]phenol (2.82 g) and ethyl 2-bromopropionate (2.07 g) in the presence of anhydrous potassium carbonate (1.58 g) were refluxed in methyl ethyl ketone (50 ml) for 4 hrs. The mixture was cooled, poured into dichloromethane, washed with water, dried (MgSO4) and evaporated. Purification by column chromatography over silica gel (eluant dichloromethane) gave ethyl 2-{4-[(7-chloroisoquinolin-3-yl)oxy]phenoxy}propionate (3.33 g) as a brown oil.
Reaction SMILES: [OH-:1].[Na+].O.[C:4]([NH:8][S:9]([C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([C:18]2[N:26]3[C:21]([CH:22]=[N:23][C:24](S(C)(=O)=O)=[N:25]3)=[CH:20][CH:19]=2)[CH:13]=1)(=[O:11])=[O:10])([CH3:7])([CH3:6])[CH3:5]>C(O)(=O)C>[C:4]([NH:8][S:9]([C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([C:18]2[N:26]3[C:21]([CH:22]=[N:23][C:24]([OH:1])=[N:25]3)=[CH:20][CH:19]=2)[CH:13]=1)(=[O:11])=[O:10])([CH3:7])([CH3:6])[CH3:5]
Reactant: [OH-]
Reactant: CC(C)(C)NS(=O)(=O)c1cccc(-c2ccc3cnc(S(C)(=O)=O)nn23)c1
Agent: [Na+]
Solvent: O
Solvent: CC(=O)O
Product: CC(C)(C)NS(=O)(=O)c1cccc(-c2ccc3cnc(O)nn23)c1
Temperature: 120 °C
Reaction time: 0.5 h
Yield: 70 %

Procedure:
10 M sodium hydroxide in water (2.74 mL, 52.4 mmol) was heated at 100° C. N-tert-butyl-3-(2-methanesulfonyl-pyrrolo[2,1-f][1,2,4]triazin-7-yl)-benzenesulfonamide (780 mg, 1.91 mmol) was added portion wise over 10 minutes. The reaction mixture was heated at 120° C. for 60 minutes and then cooled to room temperature. Glacial acetic acid was added to adjust the pH to 4 and the mixture was stirred at room temperature for 30 minutes. The solid was filtered and washed sequentially with water (75 mL) and Et2O (50 mL) to obtain N-tert-butyl-3-(2-hydroxy-pyrrolo[2,1-f][1,2,4]triazin-7-yl)-benzenesulfonamide as a red-orange solid (460 mg, 70%). LCMS (m/e) 347 (M+H); 1H-NMR (d6-DMSO, 400 MHz) δ 9.00 (s, 1H), 8.68 (s, 1H), 8.47 (d, 1H, J=8.0 Hz), 7.78 (d, 1H, J=7.7 Hz), 7.71-7.64 (m, 1H), 7.59 (s, 1H), 7.30 (d, 1H, J=4.8 Hz), 7.01 (d, 1H, J=4.8 Hz), 1.91 (s, 1H), 1.13 (s, 9H).
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4]([O:9][CH2:10][C:11]2[C:16]([F:17])=[CH:15][CH:14]=[CH:13][C:12]=2[F:18])[C:5]([NH2:8])=[N:6][CH:7]=1.Cl[CH:20]([C:26]([CH3:28])=O)[C:21]([O:23][CH2:24][CH3:25])=[O:22]>C(O)C>[Cl:1][C:2]1[CH:3]=[C:4]([O:9][CH2:10][C:11]2[C:12]([F:18])=[CH:13][CH:14]=[CH:15][C:16]=2[F:17])[C:5]2[N:6]([C:20]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[C:26]([CH3:28])[N:8]=2)[CH:7]=1
Reactant: Nc1ncc(Cl)cc1OCc1c(F)cccc1F
Reactant: CCOC(=O)C(Cl)C(C)=O
Solvent: CCO
Product: CCOC(=O)c1c(C)nc2c(OCc3c(F)cccc3F)cc(Cl)cn12

Procedure:
40 g of 5-chloro-3-[(2,6-difluorobenzyl)oxy]pyridine-2-amine (Example 14A; 147.8 mmol; 1 equivalent) were initially charged in 800 ml of ethanol, 30 g of powdered molecular sieve 3 Å and 128 g of ethyl 2-chloroacetoacetate (739 mmol, 5 equivalents) were added and the mixture was heated at reflux overnight. The reaction mixture was concentrated and the residue was taken up in ethyl acetate and filtered. The ethyl acetate phase was washed with water, dried, filtered and concentrated. This gave 44 g (78% of theory) of the title compound.
Reaction SMILES: C[Si](C)(C)CC[O:5][C:6]([C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:11]=[CH:10][C:9]=1[NH:18][C:19]([O:21][CH2:22][C:23]1[O:24][C:25]2[CH:31]=[CH:30][C:29]([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[CH:28][C:26]=2[CH:27]=1)=[O:20])=[O:7].[F-].C([N+](CCCC)(CCCC)CCCC)CCC.O>CN(C=O)C>[C:32]1([C:29]2[CH:30]=[CH:31][C:25]3[O:24][C:23]([CH2:22][O:21][C:19]([NH:18][C:9]4[CH:10]=[CH:11][C:12]5[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=5)[C:8]=4[C:6]([OH:7])=[O:5])=[O:20])=[CH:27][C:26]=3[CH:28]=2)[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1
Reactant: C[Si](C)(C)CCOC(=O)c1c(NC(=O)OCc2cc3cc(-c4ccccc4)ccc3o2)ccc2ccccc12
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: [F-]
Solvent: O
Solvent: CN(C)C=O
Product: O=C(Nc1ccc2ccccc2c1C(=O)O)OCc1cc2cc(-c3ccccc3)ccc2o1
Temperature: 2.5 °C
Reaction time: 1.5 h
Yield: 47.9 %

Procedure:
To a solution of 2-(5-phenyl-benzofuran-2-ylmethoxycarbonylamino)-naphthalene-1-carboxylic acid 2-trimethylsilanyl-ethyl ester (574 mg, 1.07 mmol) in DMF (5 mL) was added 1.0M tetra-n-butylammonium fluoride (1.1 mL, 1.07 mmol) under a nitrogen atmosphere. The mixture was stirred for 1.5 h. Water was added and the mixture was extracted, washed with water and brine, dried and concentrated to ca. 3 mL. The suspension was cooled at 0-5° C. for 40 min and filtered. Recrystallization of the obtained white solid gave 224 mg of 2-(5-phenyl-benzofuran-2-ylmethoxycarbonylamino)-naphthalene-1-carboxylic acid, 201, mp: 174.5-177.2° C.
Reaction SMILES: [Na].Cl[CH2:3][C:4]1[S:8][CH:7]=[N:6][CH:5]=1.[C:9]([NH:12][CH:13]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:14]([O:16][CH2:17][CH3:18])=[O:15])(=[O:11])[CH3:10]>C(O)C>[C:9]([NH:12][C:13]([CH2:3][C:4]1[S:8][CH:7]=[N:6][CH:5]=1)([C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:14]([O:16][CH2:17][CH3:18])=[O:15])(=[O:11])[CH3:10]
Reactant: ClCc1cncs1
Reactant: CCOC(=O)C(NC(C)=O)C(=O)OCC
Agent: [Na]
Solvent: CCO
Product: CCOC(=O)C(Cc1cncs1)(NC(C)=O)C(=O)OCC
Temperature: 75 °C
Reaction time: 0.25 h

Procedure:
after dissolving 1.24 g of sodium in 20 cm3 of ethanol, 10.86 cm3 of diethyl acetamidomalonate are added, followed by heating at a temperature in the region of 75° C. After 15 minutes, a solution of 5-chloromethylthiazole in 20 cm3 of ethanol is added, followed by heating for 2 hours at a temperature in the region of 75° C. The reaction medium is evaporated under reduced pressure (1 kPa) at a temperature in the region of 40° C. The residue is chromatographed under an argon pressure of 60 kPa on a column of silica gel (particle size 60-200μ; diameter 6.5 cm; height 40 cm), eluting with a dichloromethane/methanol mixture (99/1 by volume), a dichloromethane/methanol mixture (98/02 by volume) and then a dichloromethane/methanol mixture (95/5 by volume). The fractions containing the expected product are combined and then concentrated under the above conditions. 3.3 g of diethyl 2-acetylamino-2-(5-thiazolylmethyl)malonate are obtained in the form of an orange-colored solid [1H NMR spectrum (300 MHz, (CD3)2SO-d6, δ in ppm): 1.18 (t, J=7.5 Hz: 6H); 2.00 (s: 3H); 3.75 (s: 2H); 4.17 (q, J=7.5 Hz: 4H); 7.61 (s: 1H); 8.37 (broad s: 1H); 9.00 (s: 1H)].
Reaction SMILES: F[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[OH-].[K+].S(=O)(=O)(O)[OH:15].[F-].[Si](O)(O)(O)O.[OH-].[Ca+2].[OH-]>O>[F:8][C:6]1[CH:5]=[CH:4][C:3]([N+:9]([O-:11])=[O:10])=[C:2]([OH:15])[CH:7]=1
Reactant: O=S(=O)(O)O
Reactant: O=[N+]([O-])c1ccc(F)cc1F
Agent: O[Si](O)(O)O
Agent: [Ca+2]
Agent: [F-]
Solvent: O
Product: O=[N+]([O-])c1ccc(F)cc1O
Temperature: 60 °C
Yield: 78 %

Procedure:
In this example, the stirrer described in Example 1 was introduced via an axial face seal into an otherwise commercially available PTFE reactor, the axial face seal being made of α-silicon carbide. Instead of Asplit FN, Asplit CN and, as the shaft material, CFP (carbon fiber-reinforced plastic based on phenolic resin) were employed. 119.4 g (0.75 mol) of 2,4-difluoronitro-benzene were initially introduced into the PTFE reactor, 104.8 g (1.566 mol) of potassium hydroxide (85% strength) in 300 g of water were added dropwise at 55° C. in the course of 4 hours, and the temperature was then increased to 60° C. Specimens (stainless steel V4A) of material No. 1.4571 were positioned in the liquid and in the vapor space. After the end of the reaction, 96% strength sulfuric acid was added until pH 2.3 was reached and, as a fluoride-trapping agent, 40 g of highly disperse silicic acid (Aerosil®) and 38.0 g of calcium hydroxide were added, a pH of 4.2 being established. Introduction of steam was started, after which 5-fluoro-2-nitrophenol was distilled off with the steam. During the steam distillation, the pH was reduced to 1.5 in the course of 1.5 hours by means of 96% strength sulfuric acid, and was then kept at this value. The distillate was cooled to 10° C. and then filtered. 91.9 g (0.58 mol, 78%) of 5-fluoro-2-nitrophenol were obtained as a yellow solid. After the experiment had been repeated several times, the stirrer proved to be unchanged. Specimens of materials 1.4462 and 1.4539 showed uniform attack (integral rates of removal of material of between 1 and 6 mm/a) and partial pitting corrosion and stress corrosion cracking after an exposure time of only 50 hours.
Reaction SMILES: [CH2:1]([O:5][C:6]1[C:7]([CH:11]2[CH:16]3[CH2:17][CH2:18][N:13]([CH2:14][CH2:15]3)[CH2:12]2)=[N:8][NH:9][CH:10]=1)[CH2:2][CH2:3]C.C(O)CC.IC1C(C2C3CCN(CC3)C2)=NN(COCC[Si](C)(C)C)C=1.CCO>CCO.C(OCC)(=O)C.C(N(CC)CC)C.CCO.C(N(CC)CC)C>[CH2:1]([O:5][C:6]1[C:7]([CH:11]2[CH:16]3[CH2:17][CH2:18][N:13]([CH2:14][CH2:15]3)[CH2:12]2)=[N:8][NH:9][CH:10]=1)[CH2:2][CH3:3]
Reactant: CCCCOc1c[nH]nc1C1CN2CCC1CC2
Agent: C[Si](C)(C)CCOCn1cc(I)c(C2CN3CCC2CC3)n1
Solvent: CCCO
Solvent: CCOC(C)=O
Solvent: CCN(CC)CC
Product: CCCOc1c[nH]nc1C1CN2CCC1CC2

Procedure:
Compound 52B was prepared following the procedure as described for the synthesis of compound 52A (see Scheme 10) using propanol and 3-[4-iodo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazol-3-yl]-1-azabicyclo[2.2.2]octane (50). Work-up and flash chromatography (gradient EtOH to EtOH/triethylamine 300/1) followed by a second flash chromatography (EtOH/ethyl acetate/triethylamine 25/75/1) afforded compound 51B as an oil (14%). LCMS (method B): Rt: 7.15 min, ([M+H]+=366). Compound 51A was subsequently deprotected (TBAF/THF) and purified by flash chromatography (gradient EtOH to EtOH/triethylamine 97/3), followed by a preperative TLC purification (CH3CN/H2O) to afford the title compound 52B as an oil. (51%). LCMS (method A); Rt: 0.91 min, ([M+H]+=236). 1H-NMR (600 MHz, D6DMSO): δ 7.34 (s, 1H), 3.74 (t, J=7 Hz, 2H), 3.24-3.19 (m, 1H), 3.03-2.96 (m, 1H), 2.92-2.87 (m, 1H), 2.86-2.74 (m, 3H), 2.69-2.62 (m, 1H), 1.88-1.84 (m, 1H), 1.67-1.55 (m, 5H), 1.26-1.20 (m, 1H), 0.92 (t, J=7 Hz, 3H).
Reaction SMILES: [CH3:1]I.[OH:3][CH2:4][CH2:5][N:6]1[C:10](=[O:11])[CH:9]([CH3:12])[S:8][CH:7]1[C:13]1[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=1.[H-].[Na+].[Na+].[Cl-]>CN(C)C=O>[CH3:1][O:3][CH2:4][CH2:5][N:6]1[C:10](=[O:11])[CH:9]([CH3:12])[S:8][CH:7]1[C:13]1[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=1
Reactant: CI
Reactant: CC1SC(c2cccnc2)N(CCO)C1=O
Agent: [Cl-]
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: COCCN1C(=O)C(C)SC1c1cccnc1
Yield: 48.1 %

Procedure:
Methyl iodide (0.72 g, 5.0 mmol) was added to a solution of 3-(2-hydroxyethyl)-5-methyl-2-(3-pyridyl)thiazolidin-4-one (1 g, 4.2 mmol) in dry dimethylformamide (5 ml), and 40% sodium hydride (176 mg, 4.4 mmol) was added portionwise to the mixture under ice-cooling. Then, the mixture was kept cooling for 1 hour. The resulting mixture was poured into aqueous NaCl, and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous Na2SO4, and filtered. The filtrate was concentrated and subjected to medium-pressure chromatography (hexane-acetone), giving 3-(2-methoxyethyl)-5-methyl-2-(3-pyridyl)thiazolidin-4-one (0.51 g, 48% yield).
Reaction SMILES: [CH3:1][C:2]1[CH:3]=[C:4]([CH:17]=[C:18]([CH3:20])[CH:19]=1)[O:5][C:6]1[C:7]([CH:15]=[O:16])=[C:8]([CH3:14])[NH:9][C:10](=[O:13])[C:11]=1[I:12].[BH4-].[Na+].O.C(=O)([O-])[O-].[K+].[K+]>CO>[CH3:20][C:18]1[CH:17]=[C:4]([CH:3]=[C:2]([CH3:1])[CH:19]=1)[O:5][C:6]1[C:7]([CH2:15][OH:16])=[C:8]([CH3:14])[NH:9][C:10](=[O:13])[C:11]=1[I:12]
Reactant: Cc1cc(C)cc(Oc2c(C=O)c(C)[nH]c(=O)c2I)c1
Agent: O=C([O-])[O-]
Agent: [BH4-]
Agent: [K+]
Solvent: CO
Solvent: O
Product: Cc1cc(C)cc(Oc2c(CO)c(C)[nH]c(=O)c2I)c1
Temperature: 25 °C
Reaction time: 1 h
Yield: 97.9 %

Procedure:
To a stirred solution of compound 269 (500 mg; 1.3 mmol) in methanol (50 ml) was added NaBH4 (350 mg; 9.2 mmol) in small portions for a period of 10 min. After 1 hour on stirring at room temperature, water (20 ml) and a solution 10% potassium carbonate (30 ml) were added. The mixture was extracted with ethyl acetate (3×60 ml) and the organic layer was washed with brine, dried over magnesium sulfate and the solvent was removed under reduced pressure giving colorless microcrystals which correspond to the titled compound (490 mg; 97%) m.p.=248–250° C.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[O:11][CH2:10][C:9](=O)[CH2:8][C:7]=2[CH:13]=1.[CH2:14]([NH:17][CH2:18][CH2:19][CH3:20])[CH2:15][CH3:16].FC(F)(F)C(O)=O>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[O:11][CH2:10][CH:9]([N:17]([CH2:18][CH2:19][CH3:20])[CH2:14][CH2:15][CH3:16])[CH2:8][C:7]=2[CH:13]=1
Reactant: COc1ccc2c(c1)CC(=O)CO2
Reactant: CCCNCCC
Solvent: Cc1ccccc1
Solvent: O=C(O)C(F)(F)F
Product: CCCN(CCC)C1COc2ccc(OC)cc2C1

Procedure:
A mixture of 11.58 g of 6-methoxy-3,4-dihydro-2H-[1]-benzopyran-3-one, 26 g of dipropylamine, 0.3 ml of trifluoroacetic acid and 160 ml of toluene is refluxed in a Dean-Stark apparatus for 2 hours. The solution concentrated in vacuo and the residue is added to a solution of 8 g of sodium cyanoborohydride in 160 ml of ethanol and 40 ml of acetic acid. After 15 minutes at room temperature most of the solvent is removed in vacuo. The residue is dissolved in 6N hydrochloric acid and washed with ether. The aqueous layer is made basic and the product is extracted with ether. The aqueous layer is made basic and the product is extracted with ether. The ether layer is dried over magnesium sulfate and the solvent is removed in vacuo, to afford 6-methoxy-3,4-dihydro-N,N-di-propyl-2H-[1]-benzopyran-3-amine. The fumaric acid salt melts at 107°-113°.
Reaction SMILES: [CH3:1][C:2]([O:4][CH2:5][C@H:6]1[O:11][C@H:10](Br)[C@H:9]([O:13][C:14]([CH3:16])=[O:15])[C@@H:8]([O:17][C:18]([CH3:20])=[O:19])[C@@H:7]1[O:21][C:22]([CH3:24])=[O:23])=[O:3].[CH3:25][O:26][C:27]1[CH:32]=[C:31]([O:33][CH3:34])[CH:30]=[C:29](/[CH:35]=[CH:36]/[C:37]2[CH:38]=[CH:39][C:40]([OH:43])=[CH:41][CH:42]=2)[CH:28]=1.C(OCC)(=O)C>[Br-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(Cl)(Cl)Cl.[OH-].[Na+]>[C:22]([O:21][CH:7]1[CH:8]([O:17][C:18](=[O:19])[CH3:20])[CH:9]([O:13][C:14](=[O:15])[CH3:16])[CH:10]([O:43][C:40]2[CH:39]=[CH:38][C:37](/[CH:36]=[CH:35]/[C:29]3[CH:30]=[C:31]([O:33][CH3:34])[CH:32]=[C:27]([O:26][CH3:25])[CH:28]=3)=[CH:42][CH:41]=2)[O:11][CH:6]1[CH2:5][O:4][C:2](=[O:3])[CH3:1])(=[O:23])[CH3:24]
Reactant: COc1cc(/C=C/c2ccc(O)cc2)cc(OC)c1
Reactant: CC(=O)OC[C@H]1O[C@H](Br)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
Agent: CC[N+](CC)(CC)Cc1ccccc1
Agent: [Br-]
Agent: [Na+]
Solvent: ClC(Cl)Cl
Solvent: CCOC(C)=O
Product: COc1cc(/C=C/c2ccc(OC3OC(COC(C)=O)C(OC(C)=O)C(OC(C)=O)C3OC(C)=O)cc2)cc(OC)c1
Temperature: 60 °C
Reaction time: 5 h

Procedure:
To a solution of acetobromo-α-D-glucose (48 mg, 0.11 mM) and benzyltriethylammonium bromide (13 mg, 0.04 mM) in chloroform was added a solution of pterostilbene (30 mg, 0.11 mM)) in 1.25 M (2.5 mL) of NaOH. The mixture was stirred at 60° C. for 5 h and after a second addition of 10 mg of acetobromo-α-D-glucose and 1.0 mL of NaOH) the mixture was stirred at 60° C. for additional 5 h. Ethyl acetate was added and the organic phase was washed with water. The crude mixture was purified using flash chromatography eluting with ethyl acetate/hexanes (3:2) and afforded (E)-2-(acetoxy-methyl)-6-(4-(3,5-dimethoxystyryl)phenoxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate.
Reaction SMILES: CS(O[C@H:6]1[C:30]2[C@:25]([CH3:32])([CH2:26][CH2:27][C:28](=[O:31])[CH:29]=2)[C@@H:24]2[C@H:8]([C@H:9]3[C@:21]([CH3:33])([CH2:22][CH2:23]2)[C@@H:12]([C@H:13]([CH3:20])[CH2:14][CH2:15][CH2:16][CH:17]([CH3:19])[CH3:18])[CH2:11][CH2:10]3)[C@H:7]1OS(C)(=O)=O)(=O)=O.[N-:39]=[N+:40]=[N-:41].[Na+].C(O)(=O)C>CO>[N:39]([C:6]1[C:30]2[C@:25]([CH3:32])([CH2:26][CH2:27][C:28](=[O:31])[CH:29]=2)[C@@H:24]2[C@H:8]([C@H:9]3[C@:21]([CH3:33])([CH2:22][CH2:23]2)[C@@H:12]([C@H:13]([CH3:20])[CH2:14][CH2:15][CH2:16][CH:17]([CH3:19])[CH3:18])[CH2:11][CH2:10]3)[CH:7]=1)=[N+:40]=[N-:41]
Reactant: [N-]=[N+]=[N-]
Reactant: CC(C)CCC[C@@H](C)[C@H]1CC[C@H]2[C@@H]3[C@@H](OS(C)(=O)=O)[C@@H](OS(C)(=O)=O)C4=CC(=O)CC[C@]4(C)[C@H]3CC[C@]12C
Agent: [Na+]
Solvent: CC(=O)O
Solvent: CO
Product: CC(C)CCC[C@@H](C)[C@H]1CC[C@H]2[C@@H]3C=C(N=[N+]=[N-])C4=CC(=O)CC[C@]4(C)[C@H]3CC[C@]12C

Procedure:
In a manner similar to that described in Example 6C, treat 6β,7β-dimethanesulfonyloxy-4-cholestene-3-one with sodium azide in aqueous methanol in the presence of acetic acid. Isolate and purify the resultant product in a manner similar to that described to obtain 6-azido-4,6-cholestadiene-3-one.
Reaction SMILES: [OH:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[N+:11]([O-:13])=[O:12])C(O)=O.C1C=CC2N(O)N=NC=2C=1.CC(C)N=C=NC(C)C>>[N+:11]([C:10]1[CH:9]=[CH:8][CH:4]=[CH:3][C:2]=1[OH:1])([O-:13])=[O:12]
Reactant: O=C(O)c1ccc([N+](=O)[O-])c(O)c1
Agent: CC(C)N=C=NC(C)C
Agent: On1nnc2ccccc21
Product: O=[N+]([O-])c1ccccc1O

Procedure:
This material was prepared from 3-hydroxy-4-nitrobenzoic acid (1b) (1 g, 5.46 mmol), HOBt (1 g, 7.4 mmol), DIC (1,3-diisopropylcarbodiimide, 1 mL, 6.4 mmol), and an amino polystyrene resin (1 g, 1.2 mmol) using a procedure similar to polystyrene resin (PS-2a).
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[SH:8].[OH:9][C:10]1[CH:18]=[CH:17][C:13]([C:14](O)=O)=[CH:12][CH:11]=1.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.CS(O)(=O)=O>C(=O)(O)[O-].[Na+]>[OH:9][C:10]1[CH:18]=[CH:17][C:13]([C:14]2[S:8][C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=3[N:1]=2)=[CH:12][CH:11]=1
Reactant: O=C(O)c1ccc(O)cc1
Reactant: Nc1ccccc1S
Agent: CS(=O)(=O)O
Agent: O=C([O-])O
Agent: O=P12OP3(=O)OP(=O)(O1)OP(=O)(O2)O3
Product: Oc1ccc(-c2nc3ccccc3s2)cc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 104.2 %

Procedure:
A mixture of 3.7 g 2-aminothiophenol, 4.2 g 4-hydroxybenzoic acid, 4.5 g phosphorus pentoxide and 45 g methanesulfonic acid was stirred for one hour at room temperature and then heated at 90° C. for 10 hours. The reaction mixture was poured slowly into 750 ml 5% sodium bicarbonate solution. The solid which precipitated was collected and dried to give 7.0 g 2-(4-hydroxyphenyl)-benzothiazole.
Reaction SMILES: [Cl:1][C:2]1[C:3]2[C:10]3[CH2:11][CH2:12][CH:13]([C:15]([OH:17])=O)[CH2:14][C:9]=3[S:8][C:4]=2[N:5]=[CH:6][N:7]=1.[CH2:18]([NH:22][CH2:23][C:24]#[N:25])[CH2:19][CH2:20][CH3:21]>>[CH2:18]([N:22]([CH2:23][C:24]#[N:25])[C:15]([CH:13]1[CH2:12][CH2:11][C:10]2[C:3]3[C:2]([Cl:1])=[N:7][CH:6]=[N:5][C:4]=3[S:8][C:9]=2[CH2:14]1)=[O:17])[CH2:19][CH2:20][CH3:21]
Reactant: CCCCNCC#N
Reactant: O=C(O)C1CCc2c(sc3ncnc(Cl)c23)C1
Product: CCCCN(CC#N)C(=O)C1CCc2c(sc3ncnc(Cl)c23)C1

Procedure:
300 mg (1.12 mmol) (RS)-4-chloro-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]pyrimidine-7-carboxylic acid (prepared according to intermediate example 31b) were transformed in analogy to example 3 using (butylamino)acetonitrile to give after working up and purification 280 mg (69%) of the title compound.
Reaction SMILES: C(N(C(C)C)CC)(C)C.[CH3:10][S:11](Cl)(=[O:13])=[O:12].[OH:15][CH2:16][CH2:17][O:18][CH:19]([C:28]1[NH:29][CH:30]=[N:31][CH:32]=1)[C:20]1[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][CH:21]=1.O>ClCCl>[CH3:10][S:11]([O:15][CH2:16][CH2:17][O:18][CH:19]([C:20]1[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][CH:21]=1)[C:28]1[NH:29][CH:30]=[N:31][CH:32]=1)(=[O:13])=[O:12]
Reactant: N#Cc1ccc(C(OCCO)c2cnc[nH]2)cc1
Reactant: CS(=O)(=O)Cl
Solvent: CCN(C(C)C)C(C)C
Solvent: O
Solvent: ClCCl
Product: CS(=O)(=O)OCCOC(c1ccc(C#N)cc1)c1cnc[nH]1
Temperature: 0 °C
Reaction time: 3 h

Procedure:
1.44 mmol of diisopropylethylamine and 1.20 mmol of methanesulphonyl chloride are added to a solution of 1.20 mmol of 4-[(2-hydroxyethoxy)-(3H-imidazol-4-yl)methyl]benzonitrile in 10 ml of dichloromethane at 0° C. The reaction mixture is stirred at 0° C. for 3 hours, tipped into water and extracted with dichloromethane. The combined organic phases are washed with brine, dried over sodium sulphate and evaporated. The crude title compound is used without further purification in the next stage.
Reaction SMILES: [C:1]1(C2C=[N+](CCC)C=CC=2C2C=C[NH+]=CC=2)[CH:6]=CC=C[CH:2]=1.[C:22]1(=[O:28])[O:27][CH:25](C)[CH2:24][O:23]1>CC1C=CC(O)=C(N2N=C3C(C=CC=C3)=N2)C=1.CN1C2C(=CC=CC=2)N(C)C2C=CC=CC1=2>[CH3:6][C:1]([C:22]([O:23][CH2:24][CH2:25][OH:27])=[O:28])=[CH2:2]
Reactant: CC1COC(=O)O1
Reactant: CCC[n+]1ccc(-c2cc[nH+]cc2)c(-c2ccccc2)c1
Agent: CN1c2ccccc2N(C)c2ccccc21
Agent: Cc1ccc(O)c(-n2nc3ccccc3n2)c1
Product: C=C(C)C(=O)OCCO

Procedure:
The pre-polymer solution of Example 13 A was diluted to 7% by weight polymer with propylene carbonate. The pre-polymer solution was made 30 millimolar in Tinuvin p, 17 millimolar in 1,1′-d-(3-phenyl(n-propyl)-4,4′ bipyridinium and 14 millimolar in 5,10-dihydro-5,10-dimethlphenazine simply by dissolving appropriate amounts of these materials in the pre-polymer solution. This solution was degassed by vacuum and flushed with nitrogen. Sufficient tolylene 2,4-diisocyanate (available from Aldrich Chemical Company, Inc. Milwaukee, Wis.) crosslinker was added to crosslink approximately 50 percent of the theoretical hydroxyl position. This solution was thoroughly mixed to ensure that the crosslinker was evenly distributed throughout the fluid.