Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: C(=O)([O-])[O-].[K+].[K+].[CH2:7]([C:10]1[NH:11][C:12](=[O:28])[C:13](=[C:15]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[N:14]=1)[CH2:8][CH3:9].Br[CH2:30][C:31]1[CH:36]=[CH:35][C:34]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=2[CH:43]2[N:47]([CH3:48])[N:46]([C:49]3[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=3)[N:45]([C:55]3[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=3)[N:44]2[C:61]2[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=2)=[CH:33][CH:32]=1>CN(C)C=O.C(Cl)Cl>[C:22]1([C:15]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[C:13]2[N:14]=[C:10]([CH2:7][CH2:8][CH3:9])[N:11]([CH2:30][C:31]3[CH:32]=[CH:33][C:34]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=4[CH:43]4[N:47]([CH3:48])[N:46]([C:49]5[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=5)[N:45]([C:55]5[CH:56]=[CH:57][CH:58]=[CH:59][CH:60]=5)[N:44]4[C:61]4[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=4)=[CH:35][CH:36]=3)[C:12]2=[O:28])[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1
Reactant: CCCC1=NC(=C(c2ccccc2)c2ccccc2)C(=O)N1
Reactant: CN1C(c2ccccc2-c2ccc(CBr)cc2)N(c2ccccc2)N(c2ccccc2)N1c1ccccc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: ClCCl
Solvent: CN(C)C=O
Product: CCCC1=NC(=C(c2ccccc2)c2ccccc2)C(=O)N1Cc1ccc(-c2ccccc2C2N(C)N(c3ccccc3)N(c3ccccc3)N2c2ccccc2)cc1
Temperature: 25 °C
Reaction time: 48 h
Yield: 43.2 %

Procedure:
A mixture of potassium carbonate (83 mg, 2 eq.), 2-propyl-4-(diphenylmethylene)-1H-imidazol-5(4H)-one (90 mg, 0.3 mmol), and 4'-bromomethyl-2-(triphenyl methyl tetrazol-5-yl)biphenyl (0.21 g, 1.2 eq.) in dimethyl formamide (10 mL) was allowed to stir at room temperature for 2 days. The solvent was in vacuo, the residue was dissolved in CH2Cl2 and washed with water and brine. The organic layer was dried over MgSO4 and concentrated. The crude mixture was chromatographed over silica gel eluting with ethyl acetate-hexane (1:4) to give 3,5-dihydro-5-(diphenylmethylene)-2-propyl-3-[(2'-(triphenyl methyl tetrazol-5-yl)(1,1'-biphenyl)-4-yl)methyl]-4H-imidazol-4-one (100 mg). M.S. m/e 767 (M+ +H) NMR (CDCl3 /TMS) δ0.90 (m, 3H, CH3), 1.65 (m, 2H, CH2), 2.38 (m, 2H, CH2), 4.62 (s, 2H, CH2), 6.88-7.50 (m, 30H, Harom), 7.61 (m, 2H, Harom), 7.90 (d, 1H, Harom). The above compound was detritylated following the procedure described in Example 2C, to give 61 mg of the desired product. M.S. m/e 524 (M+ +H) NMR (CDCl3 /TMS) d 1.01 (t, 3H, CH3), 1.78 (m, 2H, CH2), 2.49 (t, 2H, CH2), 4.75 (s, 2H, CH2), 7.12-7.41 (m, 15H, Harom), 7.58 (m,2H, Harom), 8.10 (d, 1H, Harom).
Reaction SMILES: ClCCl.[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([S:11]([CH:14]([C:24]2[CH:29]=[C:28]([F:30])[CH:27]=[CH:26][C:25]=2[F:31])[CH2:15][CH2:16][C:17]([O:19]C(C)(C)C)=[O:18])(=[O:13])=[O:12])=[CH:7][CH:6]=1.FC(F)(F)C(O)=O>C(OCC)(=O)C>[Cl:4][C:5]1[CH:6]=[CH:7][C:8]([S:11]([CH:14]([C:24]2[CH:29]=[C:28]([F:30])[CH:27]=[CH:26][C:25]=2[F:31])[CH2:15][CH2:16][C:17]([OH:19])=[O:18])(=[O:13])=[O:12])=[CH:9][CH:10]=1
Reactant: CC(C)(C)OC(=O)CCC(c1cc(F)ccc1F)S(=O)(=O)c1ccc(Cl)cc1
Solvent: CCOC(C)=O
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: O=C(O)CCC(c1cc(F)ccc1F)S(=O)(=O)c1ccc(Cl)cc1
Temperature: 25 °C
Reaction time: 4 h
Yield: 47.7 %

Procedure:
To a dichloromethane solution (10 ml) of t-butyl 4-[(4-chlorophenyl)sulfonyl]-4-(2,5-difluorophenyl)butyrate (1.25 g, 3.33 mmol) was added trifluoroacetic acid (5 ml). The resulting mixture was stirred at room temperature for 4 hours. The solid obtained by concentrating the reaction mixture was recrystallized from ethyl acetate, whereby the title compound (595 mg, 1.59 mmol, 48%) was obtained as colorless needle crystals.
Reaction SMILES: [CH:1]([Si:4]([O:11][C:12]1[CH:17]=[C:16]([CH3:18])[C:15](Br)=[C:14]([CH3:20])[CH:13]=1)([CH:8]([CH3:10])[CH3:9])[CH:5]([CH3:7])[CH3:6])([CH3:3])[CH3:2].C([Li])CCC.[CH2:26]([O:33][C:34]1[CH:41]=[CH:40][C:37]([CH:38]=[O:39])=[CH:36][C:35]=1[S:42]([C:45]1[CH:50]=[CH:49][C:48]([F:51])=[CH:47][CH:46]=1)(=[O:44])=[O:43])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[Cl-].[NH4+]>O1CCCC1>[CH2:26]([O:33][C:34]1[CH:41]=[CH:40][C:37]([CH:38]([C:15]2[C:16]([CH3:18])=[CH:17][C:12]([O:11][Si:4]([CH:8]([CH3:10])[CH3:9])([CH:5]([CH3:7])[CH3:6])[CH:1]([CH3:3])[CH3:2])=[CH:13][C:14]=2[CH3:20])[OH:39])=[CH:36][C:35]=1[S:42]([C:45]1[CH:46]=[CH:47][C:48]([F:51])=[CH:49][CH:50]=1)(=[O:44])=[O:43])[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1
Reactant: Cc1cc(O[Si](C(C)C)(C(C)C)C(C)C)cc(C)c1Br
Reactant: O=Cc1ccc(OCc2ccccc2)c(S(=O)(=O)c2ccc(F)cc2)c1
Agent: [Cl-]
Agent: [Li]CCCC
Agent: [NH4+]
Solvent: C1CCOC1
Product: Cc1cc(O[Si](C(C)C)(C(C)C)C(C)C)cc(C)c1C(O)c1ccc(OCc2ccccc2)c(S(=O)(=O)c2ccc(F)cc2)c1
Reaction time: 1 h

Procedure:
810 mg (2.27 mmol) of 4-bromo-3,5-dimethylphenyl triisopropylsilyl ether (Example VII) are dissolved in 10 ml of tetrahydrofuran. At −78° C., 147.3 mg (2.3 mmol) of butyllithium (2.4 molar in hexane) are added dropwise. At the same temperature, stirring is continued for one hour, and 600 mg (1.62 mmol) of 4-(benzyloxy)-3-[(4-fluorophenyl)sulphonyl]benzaldehyde (Example VI), dissolved in 4 ml of tetrahydrofuran, are then added dropwise. The mixture is stirred at −78° C. for one hour, and saturated ammonium chloride solution is then added. The mixture is extracted three times with ethyl acetate and the combined organic phases are dried with sodium sulphate and concentrated. This gives 580 mg (55% of theory) of {4-(benzyloxy)-3-[(4-fluorophenyl)sulphonyl]phenyl}{2,6-dimethyl-4-(triisopropylsilyl)oxy]phenyl}methanol.
Reaction SMILES: N[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[OH:8].[NH:9]([C:18](OC(C)(C)C)=O)[C@H:10]([C:15]([OH:17])=O)[C:11]([CH3:14])([CH3:13])[CH3:12]>>[C:11]([C:2]1[C:3]([OH:8])=[C:4]([CH:5]=[CH:6][CH:7]=1)[CH2:18][NH:9][C@@H:10]([C:11]([CH3:12])([CH3:13])[CH3:14])[C:15]([N:9]([CH3:18])[CH3:10])=[O:17])([CH3:14])([CH3:13])[CH3:12]
Reactant: CC(C)(C)OC(=O)N[C@H](C(=O)O)C(C)(C)C
Reactant: Nc1ccccc1O
Product: CN(C)C(=O)[C@@H](NCc1cccc(C(C)(C)C)c1O)C(C)(C)C

Procedure:
The title compound is prepared according to the representative synthesis of aminophenol 2g except for the following changes: 1) Initial amide formation carried out with Boc-Tle-OH instead of Boc-Val-OH. 2) The product from the reduction process is quenched with a saturated solution of aqueous NaHCO3 (formation of the HCl salt is omitted) and the desired product is purified by silica gel chromatography (9:1 hexanes:ethyl acetate to 6:1 hexanes:ethyl acetate to 4:1 hexanes:ethyl acetate) to afford 2h as a white solid. M.p.=96-98° C. IR (neat): 2948 (w, br), 1639 (s), 1460 (m), 1433 (m), 1352 (m), 1240 (m), 1135 (m), 878 (m), 782 (m), 751 (s) cm−1; 1H NMR (400 MHz, CDCl3): δ 10.87 (1H, br s), 7.19 (1H, d, J=7.3 Hz), 6.77 (1H, d, J=7.3 Hz), 6.70 (1H, t, J=7.5), 4.09 and 3.40 (2H, ABq, JAB=13.6 Hz), 3.31 (1H, d, J=11.3 Hz), 3.03 (3H, s), 2.89 (3H, s), 2.71 (1H, br s), 1.40 (9H, s), 0.96 (9H, s); 13C NMR (100 MHz, CDCl3): δ 173.3, 157.0, 137.2, 126.9, 126.3, 122.9, 118.5, 62.4, 51.3, 38.0, 35.8, 34.8, 34.7, 29.6, 27.0; HRMS Calcd for C19H33N2O2 [M+H]+: 321.25420. Found: 321.25442. [α]20D=−33 (c=0.93, CHCl3).
Reaction SMILES: C[O:2][C:3](=[O:22])[CH2:4][O:5][C:6]1[CH:11]=[CH:10][C:9]([C:12](=[O:21])[NH:13][C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)=[CH:8][N:7]=1.[OH-].[Na+].Cl>C1COCC1>[F:20][C:17]1[CH:16]=[CH:15][C:14]([NH:13][C:12]([C:9]2[CH:10]=[CH:11][C:6]([O:5][CH2:4][C:3]([OH:22])=[O:2])=[N:7][CH:8]=2)=[O:21])=[CH:19][CH:18]=1
Reactant: COC(=O)COc1ccc(C(=O)Nc2ccc(F)cc2)cn1
Agent: Cl
Agent: [Na+]
Agent: [OH-]
Solvent: C1CCOC1
Product: O=C(O)COc1ccc(C(=O)Nc2ccc(F)cc2)cn1
Yield: 871.5 %

Procedure:
To a solution of [5-(4-fluorophenylcarbamoyl)pyridin-2-yloxy]acetic acid methyl ester (0.052 g, 0.17 mmol) in THF (1.2 mL) was added an aqueous solution of sodium hydroxide (0.34 mL of a 1 M solution, 0.34 mmol). After 30 minutes the reaction was acidified to pH 3 with 6N HCl and the solvent removed in vacuo. The solids were washed with cold water and the volatiles removed to yield 0.43 g (82%) of the titled product as a white solid: 1H NMR (300 MHz, DMSO-d6) δ 10.29 (s, 1H), 8.67 (m, 1H), 8.20 (m, 1H), 7.71 (m, 2H), 7.17 (m, 2H), 7.00 (m, 1H), 4.88 (m, 2H); MS (EI) m/z 289.06 (M−H)−.
Reaction SMILES: [Br:1][C:2]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([OH:12])=[CH:6][C:3]=1[CH:4]=[O:5].C([O-])([O-])=O.[K+].[K+].C(#N)C.[CH2:22](Br)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1>O>[CH2:22]([O:12][C:7]1[C:8]([O:10][CH3:11])=[CH:9][C:2]([Br:1])=[C:3]([CH:6]=1)[CH:4]=[O:5])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1
Reactant: COc1cc(Br)c(C=O)cc1O
Reactant: BrCc1ccccc1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CC#N
Product: COc1cc(Br)c(C=O)cc1OCc1ccccc1
Temperature: 50 °C
Yield: 83 %

Procedure:
2-Bromo-5-hydroxy-4-methoxybenzaldehyde (25 g, 0.108 mol) and K2CO3 (30 g, 0.216 mol) were added to acetonitrile (250 mL) and flushed with Ar. Benzyl bromide (20 g, 0.12 mol) was added and the mixture was heated under Ar for 20 h at 50° C. After cooling, the mixture was poured into water (200 ml) and extracted with CH2Cl2 (300 mL). The CH2Cl2 was washed with water (3×100 mL), dried and concentrated. Recrystallization with isopropanol: water (3:1) gave 28.8 g (83%) of 2 as a light brown solid. 1H-NMR (400 MHz, CDCl3) dH 3.96 (3H, s, OCH3), 5.16 (2H, s, CH2Ph), 7.07-7.48 (7H, m, ArH+CH2Ph), 10.16 (1H, s, CHO).
Reaction SMILES: [C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[CH:16]([NH:17][C:18](=[O:29])[C:19]([C:23]3[N:24]=[C:25]([NH2:28])[S:26][CH:27]=3)=[N:20][O:21]C)[C:15](=[O:30])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[CH3:2].C(OCC1CS[C@@H]2C(NC(=O)C(C3N=C(N)SC=3)=NOC)C(=O)N2C=1C([O-])=O)(=O)C.[Na+].[C:62]([O:65][CH2:66][C:67]1[CH2:68][S:69][C@@H:70]2[CH:77]([NH:78][C:79](=[O:92])[C:80]([C:86]3[N:87]=[C:88]([NH2:91])[S:89][CH:90]=3)=[N:81][O:82][CH:83](C)[CH3:84])[C:76](=[O:93])[N:71]2[C:72]=1[C:73]([OH:75])=[O:74])(=[O:64])[CH3:63]>>[NH2:28][C:25]1[S:26][CH:27]=[C:23]([C:19](=[N:20][OH:21])[C:18]([NH:17][CH:16]2[C:15](=[O:30])[N:10]3[C:11]([C:12]([OH:14])=[O:13])=[C:6]([CH2:5][O:4][C:1](=[O:3])[CH3:2])[CH2:7][S:8][C@H:9]23)=[O:29])[N:24]=1.[C:62]([O:65][CH2:66][C:67]1[CH2:68][S:69][C@@H:70]2[CH:77]([NH:78][C:79](=[O:92])[C:80]([C:86]3[N:87]=[C:88]([NH2:91])[S:89][CH:90]=3)=[N:81][O:82][CH:83]=[CH2:84])[C:76](=[O:93])[N:71]2[C:72]=1[C:73]([OH:75])=[O:74])(=[O:64])[CH3:63]
Reactant: CON=C(C(=O)NC1C(=O)N2C(C(=O)O)=C(COC(C)=O)CS[C@H]12)c1csc(N)n1
Reactant: CC(=O)OCC1=C(C(=O)O)N2C(=O)C(NC(=O)C(=NOC(C)C)c3csc(N)n3)[C@H]2SC1
Agent: CON=C(C(=O)NC1C(=O)N2C(C(=O)[O-])=C(COC(C)=O)CS[C@H]12)c1csc(N)n1
Agent: [Na+]
Product: C=CON=C(C(=O)NC1C(=O)N2C(C(=O)O)=C(COC(C)=O)CS[C@H]12)c1csc(N)n1
Product: CC(=O)OCC1=C(C(=O)O)N2C(=O)C(NC(=O)C(=NO)c3csc(N)n3)[C@H]2SC1

Procedure:
Gelules were prepared with 250 mg of 3-acetoxymethyl-7-[2-(2-amino-4-thiazolyl)-2-methoxyimino-acetamido]-ceph-3-eme-4-carboxylic acid or sodium 3-acetoxymethyl-7-[2-(2-amino-4-thiazolyl)-2-methoxyimino-acetamido]-ceph-3-eme-4-carboxylate or 3-acetoxymethyl-7-[2-(2-amino-4-thiazolyl)-2-(1-methylethoxylimino)-acetamido]-ceph-3-eme-4-carboxylic acid or the syn isomer of 7-[2-(2-amino-4-thiazolyl)-2-hydroxyimino-acetamido]-3-acetoxymethyl-ceph-3-eme-4-carboxylic acid or the syn isomer of 3-acetoxymethyl-7-[2-(2-amino-4-thiazolyl)-2-vinyloxyimino-acetamido]-ceph-3-eme-4-carboxylic acid and sufficient excipient to obtain a final weight of 400 mg.
Reaction SMILES: [NH2:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([NH:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:5][CH:4]=1.[N:17]1[C:26]2[C:21](=[CH:22][C:23]([C:27](O)=[O:28])=[CH:24][CH:25]=2)[CH:20]=[CH:19][CH:18]=1.F[P-](F)(F)(F)(F)F.N1([P+](N(C)C)(N(C)C)N(C)C)C2C=CC=CC=2N=N1.C(N(CC)CC)C>CN(C)C=O.O>[CH2:10]([NH:9][C:6]1[CH:7]=[CH:8][C:3]([CH2:2][NH:1][C:27]([C:23]2[CH:22]=[C:21]3[C:26](=[CH:25][CH:24]=2)[N:17]=[CH:18][CH:19]=[CH:20]3)=[O:28])=[CH:4][CH:5]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1
Reactant: O=C(O)c1ccc2ncccc2c1
Reactant: NCc1ccc(NCc2ccccc2)cc1
Agent: CN(C)[P+](N(C)C)(N(C)C)n1nnc2ccccc21
Agent: F[P-](F)(F)(F)(F)F
Solvent: CN(C)C=O
Solvent: CCN(CC)CC
Solvent: O
Product: O=C(NCc1ccc(NCc2ccccc2)cc1)c1ccc2ncccc2c1
Temperature: 25 °C
Reaction time: 2 h
Yield: 82.9 %

Procedure:
The resulting (4-aminomethyl-phenyl)-benzylamine (162 mg, 0.763 mmol), quinoline-6-carboxylic acid (132 mg, 0.736 mmol), benzotriazol-1-yl-tris(dimethylamino)phosphonium hexafluorophosphate (506 mg, 1.14 mmol) and triethylamine (319 μl, 2.29 mmol) were dissolved in N,N-dimethylformamide (4.0 mL), and the solution was stirred for 2 hours at room temperature. Water was added to the reaction solution, which was then extracted with ethyl acetate, the organic layer was washed with water and brine and dried over anhydrous magnesium sulfate. The solvent was evaporated in vacuo, the residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1), and the title compound (224 mg, 0.610 mmol, 80%) was obtained as a white solid.
Reaction SMILES: O([C@H]1CC[C@H](C[NH:12][C:13](=[O:19])[CH2:14][CH2:15][C:16]([OH:18])=[O:17])CC1)[N+]([O-])=O.[O:20]([C@H:24]1[CH2:29][CH2:28][C@H:27](CN)[CH2:26][CH2:25]1)[N+:21]([O-:23])=[O:22].C1(=O)OC(=O)CC1>>[O:20]([C@H:24]1[CH2:25][CH2:26][C@H:27]([NH:12][C:13](=[O:19])[CH2:14][CH2:15][C:16]([OH:18])=[O:17])[CH2:28][CH2:29]1)[N+:21]([O-:23])=[O:22]
Reactant: O=C(O)CCC(=O)NC[C@H]1CC[C@H](O[N+](=O)[O-])CC1
Reactant: NC[C@H]1CC[C@H](O[N+](=O)[O-])CC1
Agent: O=C1CCC(=O)O1
Product: O=C(O)CCC(=O)N[C@H]1CC[C@H](O[N+](=O)[O-])CC1

Procedure:
N-(trans-4-nitroxycyclohexylmethyl)-succinic acid monoamide from trans-4-nitroxycyclohexylmethylamine and succinic acid anhydride melting point: 79°-81° C. (ether), yield: 80%.
Reaction SMILES: C([C:5]1[CH:10]=[CH:9][C:8](C)=[C:7]([OH:12])[C:6]=1[CH2:13][CH2:14][CH2:15][CH3:16])CCC.[C:17](O)(=[O:20])[CH:18]=[CH2:19].[Cl-].C[NH+](C)C>C1(C)C=CC=CC=1>[CH:16]1[CH:15]=[C:14]([CH2:13][C:6]2[C:7]([OH:12])=[CH:8][CH:9]=[CH:10][CH:5]=2)[C:17]([OH:20])=[CH:18][CH:19]=1
Reactant: CCCCc1ccc(C)c(O)c1CCCC
Reactant: C=CC(=O)O
Agent: C[NH+](C)C
Agent: [Cl-]
Solvent: Cc1ccccc1
Product: Oc1ccccc1Cc1ccccc1O
Temperature: 98 °C
Reaction time: 50 h

Procedure:
Bisphenol F epoxy resin (Nihon Kayaku Co., Ltd. RE-404P, epoxy equivalent 160 g/eq., amount of hydrolysis 30 ppm) was dissolved in toluene, and added dibutylhydroxy toluene as the polymerization inhibitor therein, then temperature was risen up to 60° C. Thereafter, acrylic acid in 100% equivalent amount to epoxy group was added, further temperature was risen up to 80° C. Then trimethylammonium chloride as the reaction catalyst was added thereto, followed by stirring at 98° C. for about 50 hours. The resultant reaction mixture was washed with water, and toluene was distilled out to obtain epoxy acrylate of bisphenol F (Epoxyacrylate C).
Reaction SMILES: [CH3:1][C:2]1[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][C:3]=1[O:4][CH2:5][C:6]1[CH:17]=[CH:16][CH:15]=[CH:14][C:7]=1[C:8]([C:12]#N)=[N:9][O:10][CH3:11].[OH-:23].[K+].C(O)CCC.Cl.[OH2:31]>>[CH3:1][C:2]1[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][C:3]=1[O:4][CH2:5][C:6]1[CH:17]=[CH:16][CH:15]=[CH:14][C:7]=1[C:8](=[N:9][O:10][CH3:11])[C:12]([OH:31])=[O:23]
Reactant: [OH-]
Reactant: O
Reactant: CON=C(C#N)c1ccccc1COc1cc(C)ccc1C
Agent: Cl
Agent: [K+]
Solvent: CCCCO
Product: CON=C(C(=O)O)c1ccccc1COc1cc(C)ccc1C
Yield: 95.5 %

Procedure:
To 2-(2,5-dimethylphenoxymethyl)-α-methoxyiminobenzyl cyanide (E/Z=13/87)(2.94 g, 10 mmol) were added 96.7% potassium hydroxide (1.16 g, 20 mmol), butanol (20 ml) and water (2 ml). The mixture was stirred under reflux for 13 hours. After completion of the reaction, 1N aqueous hydrochloric acid solution (150 ml) was added. The mixture was extracted with toluene (150 ml), washed with water (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude 2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetic acid (2.99 g, Yield 95.5%, Z=at least 99%).
Reaction SMILES: C([O:8][C:9]1[CH:36]=[C:35]([NH:37][CH3:38])[CH:34]=[CH:33][C:10]=1[C:11]([NH:13][C:14]1[CH:26]=[C:25]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH:24]=[CH:23][C:15]=1[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[O:12])C1C=CC=CC=1.O1CCOCC1>CO.C(OCC)(=O)C.[C].[Pd]>[OH:8][C:9]1[CH:36]=[C:35]([NH:37][CH3:38])[CH:34]=[CH:33][C:10]=1[C:11]([NH:13][C:14]1[CH:26]=[C:25]([C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH:24]=[CH:23][C:15]=1[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[O:12]
Reactant: CNc1ccc(C(=O)Nc2cc(-c3ccccc3)ccc2C(=O)OC(C)(C)C)c(OCc2ccccc2)c1
Agent: [Pd]
Solvent: CO
Solvent: CCOC(C)=O
Solvent: C1COCCO1
Product: CNc1ccc(C(=O)Nc2cc(-c3ccccc3)ccc2C(=O)OC(C)(C)C)c(O)c1
Temperature: 25 °C
Reaction time: 2 h
Yield: 61.9 %

Procedure:
To a solution mixture of tert-butyl 2-(2-(benzyloxy)-4-(methylamino)benzamido)-4-phenylbenzoate (0.053 g) in methanol (1.5 mL), ethyl acetate (3 mL), and dioxane (4.5 mL), 10% palladium-carbon (27 mg) was added, followed by stirring under a hydrogen atmosphere at room temperature for 2 hours. The insoluble substance was removed by filtration, and the solvent was evaporated under reduced pressure. Diisopropyl ether was added to the obtained residue, and then the solid substance was collected by filtration to obtain 0.027 g of tert-butyl 2-(2-hydroxy-4-(methylamino)benzamido)-4-phenylbenzoate as a white solid.
Reaction SMILES: [C:1]([OH:20])(=[O:19])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[CH:21]#[C:22][CH3:23].C=C=C.CCC>C([O-])(=O)C.[Zn+2].C([O-])(=O)C>[C:1]([O:20][C:22]([CH3:23])=[CH2:21])(=[O:19])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]
Reactant: C#CC
Reactant: CCCCCCCCCCCCCCCCCC(=O)O
Agent: C=C=C
Agent: CC(=O)[O-]
Agent: [Zn+2]
Solvent: CCC
Product: C=C(C)OC(=O)CCCCCCCCCCCCCCCCC
Temperature: 120 °C

Procedure:
The zeolite was prepared in a conventional way using a 1N aqueous zinc acetate solution and drying the partially exchanged zeolite for about 16 hours at about 150° C. The dried zeolite contained about 4.0% zinc. Fifteen grams of the loaded zeolite plus 100 g (0.36 moles) of melted stearic acid were sealed in a 1-liter pressure vessel equipped with a magnetic stirrer, a gas inlet tube and a thermocouple, and the air within replaced by nitrogen. Approximately 80 ml of a liquified gas, the composition of which is about 60% of a 50--50 mixture of propyne and allene and about 40% propane, containing approximately 0.5 mole methyl acetylene in a pressure burette was pushed into the pressure vessel using pressurized nitrogen gas. An electric heater was used to heat the vigorously stirred mixture for 10 minutes at 120° C. at a pressure of about 400 pounds per square inch at which time the pressure vessel and its contents were rapidly cooled and the pressure in the vessel discharged to atmospheric pressure. Infrared analysis of the pale ivory colored solid gave the same spectra as that of a reference sample of isopropenyl stearate.
Reaction SMILES: Br[C:2]1[NH:3][C:4]2[C:9]([C:10]=1[CH:11]1[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1)=[CH:8][CH:7]=[C:6]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH:5]=2.[C:24]1(B(O)O)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>COCCOC.CCO.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>[CH:11]1([C:10]2[C:9]3[C:4](=[CH:5][C:6]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[CH:7][CH:8]=3)[NH:3][C:2]=2[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1
Reactant: OB(O)c1ccccc1
Reactant: CC(C)(C)OC(=O)c1ccc2c(C3CCCCC3)c(Br)[nH]c2c1
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: CCO
Solvent: CCOC(C)=O
Solvent: COCCOC
Product: CC(C)(C)OC(=O)c1ccc2c(C3CCCCC3)c(-c3ccccc3)[nH]c2c1
Temperature: 80 °C
Reaction time: 1 h
Yield: 90 %

Procedure:
To a solution of tert-butyl 2-bromo-3-cyclohexyl-1H-indole-6-carboxylate (from Step 2) in DME and EtOH (0.2 M, 3:1, v/v) was added phenyl-boronic acid (1.2 eq.) followed by 2 M aqueous Na2CO3 (8.5 eq.). The mixture was degassed with argon, then Pd(PPh3)4 (0.1 eq.) was added and the mixture stirred under argon at 80° C. for 1 h. After cooling to RT, EtOAc was added and the organic layer washed with HCl solution (1N, ×2) and brine. The organic layer was dried over Na2SO4 and evaporated and the residue purified by silica gel chromatography (Flashmaster Personal, PE:EtOAc, 20:1) to give the title compound (90%). 1H NMR (400 MHz, DMSO-d6, 300 K) δ 1.21-1.48 (m, 3H), 1.56 (s, 9H), 1.65-1.80 (m, 5H), 1.90-2.05 (m, 2H), 2.79-2.95 (m, 1H), 7.50-7.57 (m, 6H), 7.40-7.50 (m, 1H), 7.79 (d, J 7.6, 1H), 7.94 (s, 1H); MS (ES+) m/z 376 (M+H)+.
Reaction SMILES: [CH3:1][NH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]O.[OH-:15].[Na+].[C:17](Cl)(=[O:20])[CH:18]=[CH2:19]>ClCCl.O>[OH:15][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][N:2]([CH3:1])[C:17](=[O:20])[CH:18]=[CH2:19]
Reactant: CNCCCCCCCCCCCO
Reactant: C=CC(=O)Cl
Reactant: [OH-]
Agent: [Na+]
Solvent: ClCCl
Solvent: O
Product: C=CC(=O)N(C)CCCCCCCCCCCO
Temperature: -5 °C
Reaction time: 16 h
Yield: 81 %

Procedure:
11-methylamino undecan-1-ol (10.07 g, 50.0 mmol) was dissolved in dichloromethane (30 ml). A solution of sodium hydroxide (2.40 g, 60.0 mmol) in water (30 ml) was added. The mixture was cooled to −5° C. and a solution of acrylic acid chloride (4.75 g, 52.5 mmol) and BHT (10 mg) in dichloromethane (30 ml) was added dropwise. Once the addition had ended the reaction mixture was stirred for 2 h at −5° C. and for a further 16 h at RT. Organic and aqueous phases were separated. The aqueous phase was saturated with NaCl and extracted with dichloromethane (2×50 ml). The combined organic phases were dried over Na2SO4, filtered and concentrated on the rotary evaporator. The crude product was purified by means of column chromatography (SiO2/ethyl acetate). 10.38 g (40.6 mmol; 81% yield) of a yellowish liquid was obtained.
Reaction SMILES: [CH2:1]([N:8]1[CH2:13][CH2:12][C:11]2([C:26]3[CH:25]=[CH:24][CH:23]=[C:22]([O:27][CH3:28])[C:21]=3[S:20][C:19]3[C:14]2=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH2:10][CH2:9]1)C1C=CC=CC=1.[N:29]#CBr>C(Cl)Cl>[C:1]([N:8]1[CH2:13][CH2:12][C:11]2([C:26]3[CH:25]=[CH:24][CH:23]=[C:22]([O:27][CH3:28])[C:21]=3[S:20][C:19]3[C:14]2=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH2:10][CH2:9]1)#[N:29]
Reactant: COc1cccc2c1Sc1ccccc1C21CCN(Cc2ccccc2)CC1
Reactant: N#CBr
Solvent: ClCCl
Product: COc1cccc2c1Sc1ccccc1C21CCN(C#N)CC1

Procedure:
A solution of 1'-benzyl-4-methoxythioxanthene-9-spiro-4'-piperidine (15.48 g.) and cyanogen bromide (4.68 g.) in methylene chloride (155 ml.) is stirred at ambient temperature overnight. The solvent is evaporated in vacuo, the residual gum dissolved in toluene and subjected to chromatography on magnesium silicate (200 g.), eluting consecutively with petroleum ether (b.p. 60°-80° C.) (5 × 200 ml.), toluene (5 × 200 ml.) and chloroform (5 × 200 ml.). The combined chloroform fractions are evaporated in vacuo and the residual gum is triturated with ice-cold ether to give 1'-cyano-4-methoxythioxanthene-9-spiro-4'-piperidine, m.p. 145°-146° C. on recrystallisation from toluene/ether 1/2.5.