Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[CH2:12][C:13]([O:15][CH3:16])=[O:14].F[B-](F)(F)F.[CH3:22][Si:23]([C:26]#[CH:27])([CH3:25])[CH3:24].CN(C=O)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.CCN(CC)CC>[F:9][C:8]([F:11])([F:10])[C:5]1[CH:6]=[CH:7][C:2]([C:27]#[C:26][Si:23]([CH3:25])([CH3:24])[CH3:22])=[C:3]([CH2:12][C:13]([O:15][CH3:16])=[O:14])[CH:4]=1
Reactant: C#C[Si](C)(C)C
Reactant: COC(=O)Cc1cc(C(F)(F)F)ccc1Br
Agent: Cl[Pd](Cl)([P](c1ccccc1)(c1ccccc1)c1ccccc1)[P](c1ccccc1)(c1ccccc1)c1ccccc1
Agent: [Cu]I
Agent: F[B-](F)(F)F
Solvent: CN(C)C=O
Solvent: CCN(CC)CC
Product: COC(=O)Cc1cc(C(F)(F)F)ccc1C#C[Si](C)(C)C
Temperature: 80 °C
Reaction time: 16 h

Procedure:
A suspension of methyl 2-(2-bromo-5-(trifluoromethyl)phenyl)acetate (A103) (1.00 g, 3.36 mmol), PdCl2(PPh3)2 (0.118 g, 0.168 mmol), t-Bu3PH.BF4 (0.049 g, 0.17 mmol), CuI (0.032 g, 0.17 mmol) and trimethylsilylacetylene (0.951 mL, 6.73 mmol) in anhydrous degassed DMF (10 mL) and Et3N (10 mL) was stirred at 80° C. for 16 hours. The resulting mixture was adsorbed onto silica gel and purified by column chromatography (Biotage Isolera, SiO2 cartridge, 0-10% EtOAc in petroleum benzine 40-60° C.) to give the title compound A104 as an orange liquid (0.863 g, 82%); 1H NMR (400 MHz, CDCl3) δ 7.57 (d, J=8.0 Hz, 1H), 7.53 (d, J=0.5 Hz, 1H), 7.50-7.44 (m, 1H), 3.87 (s, 2H), 3.7s (s, 3H), 0.24 (s, 9H). LCMS: rt 6.931 min; m/z 315.1 [M+H]+.
Reaction SMILES: [C:1]([OH:10])(=[O:9])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH:7]=[CH2:8].[BrH:11]>C1(C)C=CC=CC=1>[Br:11][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:1]([OH:10])=[O:9]
Reactant: Br
Reactant: C=CCCCCCC(=O)O
Solvent: Cc1ccccc1
Product: O=C(O)CCCCCCCBr
Reaction time: 0.5 h
Yield: 89 %

Procedure:
A 500-ml four-necked flask equipped with hydrogen bromide inlet, thermometer, 7-octenoic acid inlet and oxygen inlet was charged with 10 g of 7-octenoic acid and 50 ml of toluene. After passing air at 20° C. with stirring at a rate of 10 liters per hour for 30 minutes, hydrogen bromide and a solution of 90 g of 7-octenoic acid in 250 ml of toluene were continuously fed with stirring at the rates of 120 ml/hr and 9 l/hr, respectively. After 3 hours of reaction, the reaction mixture was treated in the same manner as described above under (3) (i) to give 139 g (89% yield) of 8-bromocaprylic acid.
Reaction SMILES: CS(O[CH2:6][CH2:7][O:8][C:9]1[CH:18]=[CH:17][C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:10]=1)(=O)=O.[NH2:19][C:20]1[CH:30]=[CH:29][C:23]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[CH:22][CH:21]=1>CN(C)P(N(C)C)(N(C)C)=O.O>[CH:10]1[C:11]2[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:17]=[CH:18][C:9]=1[O:8][CH2:7][CH2:6][NH:19][C:20]1[CH:21]=[CH:22][C:23]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[CH:29][CH:30]=1
Reactant: CS(=O)(=O)OCCOc1ccc2ccccc2c1
Reactant: CCOC(=O)c1ccc(N)cc1
Solvent: CN(C)P(=O)(N(C)C)N(C)C
Solvent: O
Product: CCOC(=O)c1ccc(NCCOc2ccc3ccccc3c2)cc1

Procedure:
A mixture of 18.7 g of 2-(2-naphthyloxy)ethanol O-methanesulfonate and 23.6 g of ethyl p-aminobenzoate is heated in 300 ml of hexamethylphosphoramide at 110° C. for 16 hours. The mixture is cooled, diluted with water, and worked up as described in Example 3 to give the crystalline product. Recrystallization from ethanol gives crystals, mp 158°-162° C.
Reaction SMILES: [CH2:1]([O:3][C:4](=[O:17])/[CH:5]=[C:6](/[O:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:10]=1[Cl:16])\[CH3:7])[CH3:2].[Br:18]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[CH2:1]([O:3][C:4](=[O:17])/[CH:5]=[C:6](/[O:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:10]=1[Cl:16])\[CH2:7][Br:18])[CH3:2]
Reactant: CCOC(=O)/C=C(\C)Oc1cc(Cl)ccc1Cl
Reactant: O=C1CCC(=O)N1Br
Agent: O=C(OOC(=O)c1ccccc1)c1ccccc1
Solvent: ClC(Cl)(Cl)Cl
Product: CCOC(=O)/C=C(\CBr)Oc1cc(Cl)ccc1Cl
Yield: 42.4 %

Procedure:
To a stirred mixture of (E)-3-(2,5-dichloro-phenoxy)-but-2-enoic acid ethyl ester (3.25 g, 0.012 mol) in carbon tetrachloride (20 mL) under a nitrogen atmosphere was added N-bromosuccinimide (3.20 g, 0.018 mol) and benzoyl peroxide (290 mg, 0.001 mol). Nitrogen gas was bubbled through the mixture for 5 min, and the resulting mixture was heated to reflux for 4 h. The reaction mixture was then placed in the refrigerator overnight. The solids formed were removed by filtration and the filtrate concentrated in vacuo. The crude product obtained was purified using flash column chromatography (silica gel (100-200 mesh), ethyl acetate/hexanes) to afford (E)-4-bromo-3-(2,5-dichloro-phenoxy)-but-2-enoic acid ethyl ester (1.80 g, 43%) as a yellow oil.
Reaction SMILES: C(OP([CH2:9][C:10]1[N:11]=[CH:12][N:13]([C:15]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)([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)[CH:14]=1)(=O)OCC)C.CC([O-])(C)C.[K+].[CH3:40][C:41]([CH3:51])([CH3:50])[C:42]([C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)=O.C1CCCCC1>C1COCC1>[CH3:40][C:41]([CH3:51])([CH3:50])[C:42]([C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)=[CH:9][C:10]1[N:11]=[CH:12][N:13]([C:15]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:14]=1
Reactant: CCOP(=O)(Cc1cn(C(c2ccccc2)(c2ccccc2)c2ccccc2)cn1)OCC
Reactant: CC(C)(C)C(=O)c1ccccc1
Agent: CC(C)(C)[O-]
Agent: [K+]
Solvent: C1CCCCC1
Solvent: C1CCOC1
Product: CC(C)(C)C(=Cc1cn(C(c2ccccc2)(c2ccccc2)c2ccccc2)cn1)c1ccccc1
Temperature: 25 °C
Reaction time: 0.25 h

Procedure:
To a stirred suspension of (1-trityl-1H-imidazol-4-ylmethyl)-phosphonic acid diethyl ester (341 mg; CAS 473659-21-1) at r.t. in THF (7.5 ml) under an argon atmosphere was added potassium tert-butylate (83 mg). The mixture was then stirred at r.t. for 15 minutes, and 2,2-dimethylpropiophenone (0.1 ml) was added in one portion. The mixture (clear brown orange solution) was heated to 80° C. and stirring at that temperature was continued for 24 hours. The reaction mixture was directly adsorbed on silica gel. The product was isolated by chromatography (gradient: cyclohexane→cyclohexane/EtOAc 65:35) to give 4-(3,3-dimethyl-2-phenyl-but-1-enyl)-1-trityl-1H-imidazole (135 mg; not completely pure) as light yellow solid. MS (ISP): 243.2 ([Trt]+)
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4]([CH:8]([OH:29])[CH2:9][NH:10][CH:11]([CH3:28])[CH2:12][C:13]2[CH:27]=[CH:26][C:16]3[O:17][C:18]([C:23]([OH:25])=[O:24])([C:20]([OH:22])=[O:21])[O:19][C:15]=3[CH:14]=2)[CH:5]=[CH:6][CH:7]=1.[CH2:30]([O:37][CH2:38][CH2:39][CH2:40]O)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.Cl>C(Cl)(Cl)Cl.CO>[CH2:30]([O:37][CH2:38][CH2:39][CH2:40][O:24][C:23]([C:18]1([C:20]([O:22][CH2:40][CH2:39][CH2:38][O:37][CH2:30][C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)=[O:21])[O:17][C:16]2[CH:26]=[CH:27][C:13]([CH2:12][C@H:11]([NH:10][CH2:9][C@@H:8]([C:4]3[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[CH:3]=3)[OH:29])[CH3:28])=[CH:14][C:15]=2[O:19]1)=[O:25])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1
Reactant: OCCCOCc1ccccc1
Reactant: CC(Cc1ccc2c(c1)OC(C(=O)O)(C(=O)O)O2)NCC(O)c1cccc(Cl)c1
Agent: Cl
Solvent: ClC(Cl)Cl
Solvent: CO
Product: C[C@H](Cc1ccc2c(c1)OC(C(=O)OCCCOCc1ccccc1)(C(=O)OCCCOCc1ccccc1)O2)NC[C@H](O)c1cccc(Cl)c1
Yield: 38 %

Procedure:
The title compound was prepared as a yellow gum from 5-{2-[2-(3-chloro-phenyl)-2-hydroxy-ethylamino]-propyl}-benzo[1,3]dioxole-2,2-dicarboxylic acid and 3-benzyloxy-propanol according to the procedure of Example 1; yield: 38%; Rf =0.52 (9/1 CHCl3 /MeOH); 1H NMR (300 MHz, CDCl3): δ 1.32 (d, 3H), δ 2.00 (m, 4H), δ 2.75 (m, 1H), δ 3.30 (s, 2H), δ 3.50 (m, 4H), δ 4.40 (br m, 12H), δ 5.49 (s, 1H), δ 6.68-6.85 (m, 3H), δ 7.24-7.40 (m, 13H), δ 7.43 (s, 1H); MS (ES) m/z (relative intensity): 518 (M+ -HCl, 100).
Reaction SMILES: [OH:1][C:2]([CH3:13])([CH3:12])[CH2:3]/[CH:4]=[N:5]/[S:6]([C:8]([CH3:11])([CH3:10])[CH3:9])=[O:7].[CH:14]1([Mg]Br)[CH2:16][CH2:15]1.[NH4+].[Cl-]>C(Cl)Cl>[CH:14]1([CH:4]([NH:5][S:6]([C:8]([CH3:11])([CH3:10])[CH3:9])=[O:7])[CH2:3][C:2]([OH:1])([CH3:13])[CH3:12])[CH2:16][CH2:15]1
Reactant: Br[Mg]C1CC1
Reactant: CC(C)(O)C/C=N/S(=O)C(C)(C)C
Agent: [Cl-]
Agent: [NH4+]
Solvent: ClCCl
Product: CC(C)(O)CC(NS(=O)C(C)(C)C)C1CC1
Temperature: 25 °C

Procedure:
To a stirred solution of N-[(1E)-3-hydroxy-3-methylbutylidene]-2-methylpropane-2-sulfinamide (0.6 g, 2.9 mmol) in DCM (18 mL) was added cyclopropylmagnesium bromide (0.5 M in THF, 17.5 mL, 8.8 mmol) at −78° C. The reaction mixture was allowed to warm to room temperature as the bath did (2 h). The mixture was treated with sat'd NH4Cl solution, and extracted with EtOAc. The organic layer was washed with brine, dried (sodium sulfate), concentrated, and purified by flash chromatography to give the title compound.
Reaction SMILES: [CH2:1]1[O:13][C:12]2[CH:11]=[C:10]3[C:5]([C:6]([NH:14][CH2:15][CH2:16][N:17]([CH3:19])[CH3:18])=[CH:7][CH:8]=[N:9]3)=[CH:4][C:3]=2[O:2]1.C(N(CC)CC)C.[Br:27][C:28]1[C:36]([N+:37]([O-:39])=[O:38])=[CH:35][CH:34]=[CH:33][C:29]=1[C:30](Cl)=[O:31]>C(Cl)Cl>[CH2:1]1[O:13][C:12]2[CH:11]=[C:10]3[C:5]([C:6]([N:14]([CH2:15][CH2:16][N:17]([CH3:19])[CH3:18])[C:30](=[O:31])[C:29]4[CH:33]=[CH:34][CH:35]=[C:36]([N+:37]([O-:39])=[O:38])[C:28]=4[Br:27])=[CH:7][CH:8]=[N:9]3)=[CH:4][C:3]=2[O:2]1
Reactant: O=C(Cl)c1cccc([N+](=O)[O-])c1Br
Reactant: CN(C)CCNc1ccnc2cc3c(cc12)OCO3
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: CN(C)CCN(C(=O)c1cccc([N+](=O)[O-])c1Br)c1ccnc2cc3c(cc12)OCO3
Yield: 73.9 %

Procedure:
To a solution of compound 7 (259 mg, 1.0 mmol) and triethylamine (0.5 mL) in dry CH2Cl2 (20 mL) was added a solution of 2-bromo-3-nitrobenzoic acid chloride in 20 mL of CH2Cl2 (which was prepared by refluxing of 295 mg, 1.2 mmol of 2-bromo-3-nitrobenzoic acid in 10 mL of thionyl chloride for 4 h). The reaction mixture was heated to reflux for 6 h. The reaction mixture was allowed to cool and then washed with saturated NaHCO3 solution, water and brine and dried over Na2SO4. Solvent was removed in vacuo to give 360 mg of a yellow solid (73.9%); mp 96–97° C.; 1H NMR (CDCl3) δ 2.30 (s, 6H), 2.62 (t, 2H, J=6.6), 3.59–3.69 (m, 1H), 4.53–4.67 (m, 1H), 6.18 (d, 2H, J=5.2), 7.05 (d, 1H, J=7.8), 7.14 (d, 1H, J=7.4) 7.28–7.36 (m, 3H) 7.50 (dd, 1H, J=1.2, 7.8), 8.55 (d, 1H, J=3.8); 13C NMR (CDCl3) δ 45.4, 46.5, 56.4, 97.8, 102.3, 106.7, 112.2, 119.5, 122.6, 125.2, 127.7, 129.7, 140.8, 144.6, 148.3, 148.5, 149.5, 151.4, 166.9
Reaction SMILES: [NH3:1].[Cl:2][C:3]1[CH:4]=[CH:5][C:6]([O:19][C@H:20]([C:22]2[N:26]([CH3:27])[C:25]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][C:29]=3[C:34]([F:37])([F:36])[F:35])=[N:24][N:23]=2)[CH3:21])=[C:7]([C:9]2[O:13][C:12]([C:14]([O:16]CC)=O)=[N:11][N:10]=2)[CH:8]=1.O>C(O)C>[Cl:2][C:3]1[CH:4]=[CH:5][C:6]([O:19][C@H:20]([C:22]2[N:26]([CH3:27])[C:25]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][C:29]=3[C:34]([F:36])([F:35])[F:37])=[N:24][N:23]=2)[CH3:21])=[C:7]([C:9]2[O:13][C:12]([C:14]([NH2:1])=[O:16])=[N:11][N:10]=2)[CH:8]=1
Reactant: CCOC(=O)c1nnc(-c2cc(Cl)ccc2O[C@@H](C)c2nnc(-c3ccccc3C(F)(F)F)n2C)o1
Reactant: N
Solvent: O
Solvent: CCO
Product: C[C@H](Oc1ccc(Cl)cc1-c1nnc(C(N)=O)o1)c1nnc(-c2ccccc2C(F)(F)F)n1C
Temperature: 25 °C
Reaction time: 1 h

Procedure:
A 29% aqueous ammonia solution (0.3 ml) was added to a solution of ethyl 5-{5-chloro-2-[(1S)-1-{4-methyl-5-[2-(trifluoromethyl)phenyl]-4H-1,2,4-triazol-3-yl}ethoxy]phenyl}-1,3,4-oxadiazole-2-carboxylate (120 mg) in ethanol (1 ml), followed by stirring at room temperature for one hour. Water was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate solution and then saturated brine in this order, and dried over anhydrous magnesium sulfate, and the solvent was then evaporated under reduced pressure. The residue was powdered with diisopropylether to obtain, as a light yellow solid, 5-{5-chloro-2-[(1S)-1-{4-methyl-5-[2-(trifluoromethyl)phenyl]-4H-1,2,4-triazol-3-yl}ethoxy]phenyl}-1,3,4-oxadiazole-2-carboxamide (86 mg).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12])[CH2:6]Cl.[C:15]1([CH:21]2[CH2:26][NH:25][CH2:24][C:23]3[S:27][CH:28]=[CH:29][C:22]2=3)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>>[C:15]1([CH:21]2[CH2:26][N:25]([CH2:6][C:5]3[CH:4]=[C:3]([O:2][CH3:1])[C:10]([O:11][CH3:12])=[C:9]([O:13][CH3:14])[CH:8]=3)[CH2:24][C:23]3[S:27][CH:28]=[CH:29][C:22]2=3)[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1
Reactant: COc1cc(CCl)cc(OC)c1OC
Reactant: c1ccc(C2CNCc3sccc32)cc1
Product: COc1cc(CN2Cc3sccc3C(c3ccccc3)C2)cc(OC)c1OC

Procedure:
3,4,5-Trimethoxy-benzyl chloride is condensed with 4-phenyl-4,5,6,7-tetrahydro-thieno[2,3-c]pyridine (Example 3), according to the procedure of Example 8.
Reaction SMILES: C(OC([N:8]1[C:12]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([Br:20])[CH:15]=2)([CH3:13])[CH2:11][O:10][S:9]1(=[O:22])=[O:21])=O)(C)(C)C.C(Cl)Cl>C(O)(C(F)(F)F)=O>[Br:20][C:16]1[CH:15]=[C:14]([C:12]2([CH3:13])[CH2:11][O:10][S:9](=[O:22])(=[O:21])[NH:8]2)[CH:19]=[CH:18][CH:17]=1
Reactant: CC(C)(C)OC(=O)N1C(C)(c2cccc(Br)c2)COS1(=O)=O
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: CC1(c2cccc(Br)c2)COS(=O)(=O)N1
Reaction time: 3 h
Yield: 91 %

Procedure:
3-(tert-Butoxycarbonyl)-4-(3-bromophenyl)-4-methyl-[1,2,3]-oxathiazolidine-2,2-dioxide (DC4; R6=Me) (10.8 g, 28 mmol) was dissolved in 25% TFA in DCM (40 mL, 5 eq) and the mixture was left standing at RT for 3 h. The mixture was concentrated in vacuo to give 7.3 g (91%) of 4-(3-bromophenyl)-4-methyl-[1,2,3]-oxathiazolidine-2,2-dioxide as a yellow oil. 1H NMR (CDCl3) 7.59 (t, J=1.8 Hz, 1H), 7.48-7.52 (m, 1H), 7.39-7.42 (m, 1H), 7.30 (t, J=8.1 Hz, 1H), 4.59 (m, 2H), 1.82 (s, 3H).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([C@H:13]([CH3:17])[C:14](O)=[O:15])[CH:7]=[CH:6]2.C(Cl)(=O)C([Cl:21])=O>CN(C=O)C.C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([C@H:13]([CH3:17])[C:14]([Cl:21])=[O:15])[CH:7]=[CH:6]2
Reactant: O=C(Cl)C(=O)Cl
Reactant: COc1ccc2cc([C@H](C)C(=O)O)ccc2c1
Solvent: C1CCOC1
Solvent: CN(C)C=O
Product: COc1ccc2cc([C@H](C)C(=O)Cl)ccc2c1
Reaction time: 0.05 h

Procedure:
A mixture of (S)-6-methoxy-α-methyl-2-naphthaleneacetic acid (23.09 g) and THF (41 mL) is agitated until dissolution is achieved. Oxalyl chloride (17.5 mL) is added to the flask followed by DMF (3 drops) and heptanes (50 mL). The mixture is stirred for approximately 2 hours. The resulting slurry is filtered, washed with heptane (15 mL) and aspirated for 3 minutes and vacuum dried to give 17.44 g.
Reaction SMILES: [Cl:1][CH2:2][CH2:3][NH:4][C:5]([NH:7][C@@H:8]1[O:16][C@H:15]([CH2:17][OH:18])[C@@H:13]([OH:14])[C@H:11]([OH:12])[C@H:9]1[OH:10])=[O:6].[N:19]([O-])=[O:20].[Na+].O>C(O)=O>[Cl:1][CH2:2][CH2:3][N:4]([N:19]=[O:20])[C:5]([NH:7][C@@H:8]1[O:16][C@H:15]([CH2:17][OH:18])[C@@H:13]([OH:14])[C@H:11]([OH:12])[C@H:9]1[OH:10])=[O:6]
Reactant: O=C(NCCCl)N[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O
Reactant: O=N[O-]
Agent: [Na+]
Solvent: O
Solvent: O=CO
Product: O=NN(CCCl)C(=O)N[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O
Yield: 98.3 %

Procedure:
A solution of 0.60 g of 1-(2-chloroethyl)-3-(β-D-glucopyranosyl)urea in 15 ml of 99% formic acid was admixed with 282 mg of sodium nitrite under ice-cooling and stirring. The mixture was stirred for 1 hour under ice-cooling to effect the nitrosation. The reaction mixture, after addition of 15 ml of cold water thereto, was ice-cooled for 30 minutes and then treated with 5 ml of Amberlite IR-120 (H+ form) for the removal of sodium cation. The reaction mixture so treated was concentrated to dryness below 30° C. by distilling off the solvent under a reduced pressure. The residue was taken up into a small volume of n-propanol and the solution was admixed with a volume of petroleum ether to give a precipitate. The precipitate which deposited was collected by filtration and then dried in a desiccator under vacuum, affording 0.65 g of the titled compound as an amorphous solid of pale yellow color. Yield 92%. mp. 85° C. (decomposition). [α]D16 -14° (c 0.5, methanol).
Reaction SMILES: CS(O)(=O)=O.[NH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][OH:13].[C:14]([OH:25])(=O)[CH2:15][CH2:16][S:17][S:18][CH2:19][CH2:20][C:21]([OH:23])=[O:22]>C(C(C)=O)C(C)C>[C:21]([O:23][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][NH2:6])(=[O:22])[CH2:20][CH2:19][S:18][S:17][CH2:16][CH2:15][C:14]([O:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][NH2:6])=[O:25]
Reactant: O=C(O)CCSSCCC(=O)O
Reactant: NCCCCCCO
Agent: CS(=O)(=O)O
Solvent: CC(=O)CC(C)C
Product: NCCCCCCOC(=O)CCSSCCC(=O)OCCCCCCN
Temperature: 120 °C
Reaction time: 0.17 h

Procedure:
2.0 g of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, under an atmosphere of nitrogen and at 70° C., to 2.3 g of 6-amino-1-hexanol (manufactured by Tokyo Chemical Industry Co., Ltd.). After stirring for 10 minutes, 2.1 g of 3,3′-dithiodipropionic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was heated to 120° C. and then stirred at 110° C. for 3 hours. Following completion of the reaction, the reaction mixture was cooled to room temperature and then added gradually to 50 mL of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.). After stirring for 2 hours, the precipitated crystals were collected by vacuum filtration and washed with acetone, yielding the methanesulfonate salt of di(6-aminohexyl) 3,3′-dithiodipropionate.
Reaction SMILES: [C:1](#[N:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[NH4+].[N:11]([Na])=[N+:12]=[N-:13]>CN(C=O)C.[Cl-].[Li+]>[C:2]1([C:1]2[NH:13][N:12]=[N:11][N:8]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: N#Cc1ccccc1
Reactant: [N-]=[N+]=N[Na]
Agent: [Cl-]
Agent: [Li+]
Agent: [NH4+]
Solvent: CN(C)C=O
Product: c1ccc(-c2nnn[nH]2)cc1
Temperature: 100 °C
Reaction time: 8 h
Yield: 91.7 %

Procedure:
A solution of benzonitrile (60.0 g, 581.9 mmol, 1.0 equiv) in DMF (anhydrous) (600 mL) was placed in a flask that had been purged and maintained with an inert atmosphere of nitrogen. Ammonium chloride (40.5 g, 757.2 mmol, 1.3 equiv) was added, followed by the addition of lithium chloride (2.0 g, 47.2 mmol, 0.1 equiv). To the mixture was added azidosodium (49.4 g, 756.8 mmol, 1.3 equiv). The resulting solution was stirred overnight, while maintaining the temperature at 100° C. The solids were filtered out and washed with EtOAc. The filtrates were combined and concentrated in vacuo. The residue was dissolved in a 10% NaOH aqueous solution (350 ml). The resulting solution was extracted with EtOAc (100 mL) and the aqueous layers were combined. The pH value of the solution was adjusted to 2 with concentrated HCl. The solids were filtered out and dried over reduced pressure to yield 5-phenyl-1H-tetrazole (78.0 g) as a white solid. ES m/z: [M+H]+ calcd for C7H6N4, 147.1. Found 147.1.
Reaction SMILES: [CH:1]1([C:7]([O:9]C)=O)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[NH2:11][NH2:12].O>C(O)(C)C>[CH:1]1([C:7]([NH:11][NH2:12])=[O:9])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1
Reactant: NN
Reactant: COC(=O)C1CCCCC1
Solvent: CC(C)O
Solvent: O
Product: NNC(=O)C1CCCCC1

Procedure:
28 Grams of methyl cyclohexylcarboxylate and 15 g of 85%--NH2NH2.H2O were dissolved in 50 ml of isopropyl alcohol, and the solution was refluxed by heating for 10 hours. The reaction mixture was concentrated, and the crystals precipitated by adding water were collected by filtration, then the crystals were washed with water, then recrystallized from water to yield 20 g of cyclohexane-carbohydrazide in the form of colorless needle-like crystals. Melting point: 155.5°-156.5° C.
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([OH:9])=[CH:4][C:3]=1[N:10]1[C:14](=[O:15])[N:13]([CH:16]([F:18])[F:17])[C:12]([CH3:19])=[N:11]1.C(=O)([O-])[O-].[K+].[K+].[Cl:26][C:27]1[CH:28]=[C:29]([N+:34]([O-:36])=[O:35])[CH:30]=[CH:31][C:32]=1F>CN(C)C=O>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([O:9][C:32]2[CH:31]=[CH:30][C:29]([N+:34]([O-:36])=[O:35])=[CH:28][C:27]=2[Cl:26])=[CH:4][C:3]=1[N:10]1[C:14](=[O:15])[N:13]([CH:16]([F:17])[F:18])[C:12]([CH3:19])=[N:11]1
Reactant: Cc1nn(-c2cc(O)c(Cl)cc2Cl)c(=O)n1C(F)F
Reactant: O=[N+]([O-])c1ccc(F)c(Cl)c1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CN(C)C=O
Product: Cc1nn(-c2cc(Oc3ccc([N+](=O)[O-])cc3Cl)c(Cl)cc2Cl)c(=O)n1C(F)F
Temperature: 25 °C
Reaction time: 18 h
Yield: 69.8 %

Procedure:
A mixture of 10.0 g (0.032 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one, 5.52 g (0.040 mole) of potassium carbonate, and 7.02 g (0.040 mole) of 3-chloro-4-fluoronitrobenzene in 60 ml of N,N-dimethylformamide was stirred at room temperature for approximately 18 hours. The reaction mixture was poured into ice-water. This aqueous mixture was extracted with diethyl ether. The extract :;as dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel to yield 10.4 g of 1-[2,4-dichloro-5-(2-chloro-4-nitrophenoxy)phenyl]-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 135°-135.5° C., compound 179 of Table 1.
Reaction SMILES: [CH:1]([O:4][CH:5]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:6](=[O:13])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)([CH3:3])[CH3:2].[CH:20]([Si:22]([O:27][CH3:28])([O:25][CH3:26])[O:23][CH3:24])=[CH2:21]>C1(C)C=CC=CC=1>[CH:1]([O:4][CH:5]([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[C:6](=[O:13])[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][C:12]=1[CH2:21][CH2:20][Si:22]([O:27][CH3:28])([O:25][CH3:26])[O:23][CH3:24])([CH3:3])[CH3:2]
Reactant: C=C[Si](OC)(OC)OC
Reactant: CC(C)OC(C(=O)c1ccccc1)c1ccccc1
Solvent: Cc1ccccc1
Product: CO[Si](CCc1ccccc1C(=O)C(OC(C)C)c1ccccc1)(OC)OC
Reaction time: 8 h
Yield: 65.8 %

Procedure:
10.17 g (40 mmol) of benzoin isopropyl ether, 6.7 ml (44 mmol) of vinyltrimethoxysilane, 335 mg (0.4 mmol) of RuH2 (CO) (PPh3)3 and 75 ml of anhydrous toluene were mixed and stirred at reflux for 2 hours. At intervals of 2 hours, a further 3×200 mg (0.2 mmol) of RuH2 (CO) (PPh3)3 were added. The mixture was left to stand overnight, a further 200 mg (0.2 mmol) of RuH2 (CO) (PPh3)3 and 1 ml (6.6 mmol) of vinyltrimethoxysilane were added, the mixture was stirred at reflux for 8 hours, concentrated and worked up by chromatography (Florisil or silica gel, CH2Cl2 /ethyl acetate/heptane mixtures). 10.6 g of oil were obtained which after distillation in a bulb tube (220° C., 0.08 mbar) gave 9.0 g (56%) of a yellowish oil. 1H-NMR (DCDl3): 0.61-0.96 ppm (2H, mc, Et-H2); 1.21 ppm (6H, d, isopropyl-CH3, 3JH,H =6.2 Hz); 2.61 ppm (2H, mc, Et-H1); 3.53 ppm (9H, s, Si(OCH3)3); 3.71 ppm (1H, hept, sec. isopropyl-H); 5.55 ppm (1H, s, benzoin-H); 7.14-7.39 ppm (8H, m, Ph-H); 7.51 ppm (1H, dd, Ph-H6)