Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [OH-].[Na+].[N+:3]([C:6]1[CH:19]=[CH:18][CH:17]=[C:16]2[C:7]=1[C:8](=[O:21])[C:9]1[CH2:10][CH2:11][CH2:12][CH2:13][C:14]=1[C:15]2=[O:20])([O-])=O.[H][H]>[Pd].COCCO>[NH2:3][C:6]1[C:7]2[C:8](=[O:21])[C:9]3[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:15](=[O:20])[C:16]=2[CH:17]=[CH:18][CH:19]=1
Reactant: [H][H]
Reactant: O=C1C2=C(CCCC2)C(=O)c2c1cccc2[N+](=O)[O-]
Agent: [Pd]
Agent: [Na+]
Agent: [OH-]
Solvent: COCCO
Product: Nc1cccc2c1C(=O)c1ccccc1C2=O
Yield: 110.8 %

Procedure:
0.026 Gram of a 5% palladium on carbon catalyst and 3.0 grams of a 20% aqueous sodium hydroxide solution were added to a mixture of 2.6 grams of 5-nitrotetrahydroanthraquinone and 101 grams of methyl cellosolve, into which was fed hydrogen for having hydrogen absorbed at room temperature under normal pressure in the 5-nitro compound in an amount of 1.1 mols per mol of the 5-nitro compound. A small amount of reddish brown crystals were precipitated. The reaction solution was subjected to filtration, followed by washing with methyl cellosolve. The filtrate and washings were combined together and neutralized with dilute sulfuric acid. Then, the resultant solution was concentrated under reduced pressure to obtain crystals which were separated by filtration, washed with methanol and then with water, and dried to obtain 2.5 grams of 1-aminoanthraquinone. The purity was 97.8% and the yield was 93.3%.
Reaction SMILES: [CH3:1][N:2]([CH3:4])[NH2:3].C[Al](C)C.C([O:11][C:12](=O)[CH2:13][O:14][C:15]1[CH:44]=[CH:43][C:18]([CH2:19][C:20]2[C:21]3[CH:42]=[CH:41][CH:40]=[CH:39][C:22]=3[S:23][C:24]=2[C:25]2[CH:30]=[CH:29][C:28]([O:31][CH2:32][CH2:33][N:34]3[CH2:38][CH2:37][CH2:36][CH2:35]3)=[CH:27][CH:26]=2)=[CH:17][CH:16]=1)C.O>C1(C)C=CC=CC=1>[CH3:1][N:2]([CH3:4])[NH:3][C:12](=[O:11])[CH2:13][O:14][C:15]1[CH:16]=[CH:17][C:18]([CH2:19][C:20]2[C:21]3[CH:42]=[CH:41][CH:40]=[CH:39][C:22]=3[S:23][C:24]=2[C:25]2[CH:26]=[CH:27][C:28]([O:31][CH2:32][CH2:33][N:34]3[CH2:35][CH2:36][CH2:37][CH2:38]3)=[CH:29][CH:30]=2)=[CH:43][CH:44]=1
Reactant: CN(C)N
Reactant: CCOC(=O)COc1ccc(Cc2c(-c3ccc(OCCN4CCCC4)cc3)sc3ccccc23)cc1
Agent: C[Al](C)C
Solvent: O
Solvent: Cc1ccccc1
Product: CN(C)NC(=O)COc1ccc(Cc2c(-c3ccc(OCCN4CCCC4)cc3)sc3ccccc23)cc1
Reaction time: 1 h
Yield: 64.5 %

Procedure:
A solution of 1,1-dimethyl hydrazine (0.1 mL, 1.3 mmol) in toluene (5 mL) was added to a solution of trimethyl aluminum (1.3 mL, 1.0M/toluene) in toluene (20 mL) at 0-5° C. The cooling bath was removed and the mixture stirred for 60 minutes. A solution of 3-[4-(2-ethoxy-2-oxoethoxy)benzyl]-2-[4-[2-(1-pyrrolidinyl)ethoxy]phenyl]-benzo[b]thiophene (310 mg, 0.6 mmol) in toluene (5-10 mL) was added and the mixture refluxed for 60 minutes, cooled, decomposed with water, and extracted with CH2Cl2:i-PrOH (3:1). The organic phase was washed with brine, dried over sodium sulfate, and evaporated in vacuo. The residue was chromatographed on silica gel, eluting with a gradient (CH2Cl2/5% MeOH/0-1% Et3N) to give the title compound as an amorphous solid (205 mg, 65%).
Reaction SMILES: [C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)(=[O:3])[CH3:2].C([O-])(=O)C.[NH4+].N[C:16]1([O:25]O)[CH2:21][CH:20]([CH3:22])[CH2:19][C:18]([CH3:24])([CH3:23])[CH2:17]1>C(O)C>[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)(=[O:3])[CH3:2].[CH3:22][CH:20]1[CH2:19][C:18]([CH3:24])([CH3:23])[CH2:17][C:16](=[O:25])[CH2:21]1
Reactant: CC1CC(C)(C)CC(N)(OO)C1
Agent: CC(=O)[O-]
Agent: [NH4+]
Solvent: CCO
Solvent: CC(=O)c1ccccc1
Product: CC1CC(=O)CC(C)(C)C1
Reaction time: 8 h

Procedure:
To a stirred solution of acetophenone (24.3 g.) in ethanol (50 c.c.) containing ammonium acetate (1.6 g.) and kept at or below 0°C, was added 1-amino-3,3,5-trimethylcyclohexyl hydroperoxide (17.3 g.; pure). The solution was kept at 0°C overnight and then worked up as in the previous Examples to give unreacted acetophenone and dihydroisophorone, and a fraction (4.8 g.), b.p. 126° - 130°/0.5 mm. with a peroxide equivalent of 407, shown by mass spectroscopy to contain the peroxide ##SPC26##
Reaction SMILES: [CH2:1]([C:3]1([O:35][C:36](=[O:45])[O:37][CH2:38][C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C:8]2[CH:9]=[C:10]3[N:18]([C:19](=[O:20])[C:7]=2[CH2:6][O:5][C:4]1=[O:34])[CH2:17][C:16]1[C:15]([CH2:21][CH2:22][Si:23]([CH2:26][CH2:27][CH2:28][OH:29])([CH3:25])[CH3:24])=[C:14]2[CH:30]=[CH:31][CH:32]=[CH:33][C:13]2=[N:12][C:11]3=1)[CH3:2].[O:46]1[CH:50]=[CH:49][CH:48]=[C:47]1[C:51](Cl)=[O:52]>CN(C)C1C=CN=CC=1.ClCCl>[CH2:38]([O:37][C:36]([O:35][C:3]1([CH2:1][CH3:2])[C:8]2[CH:9]=[C:10]3[N:18]([C:19](=[O:20])[C:7]=2[CH2:6][O:5][C:4]1=[O:34])[CH2:17][C:16]1[C:15]([CH2:21][CH2:22][Si:23]([CH3:25])([CH3:24])[CH2:26][CH2:27][CH2:28][O:29][C:51]([C:47]2[O:46][CH:50]=[CH:49][CH:48]=2)=[O:52])=[C:14]2[CH:30]=[CH:31][CH:32]=[CH:33][C:13]2=[N:12][C:11]3=1)=[O:45])[C:39]1[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=1
Reactant: CCC1(OC(=O)OCc2ccccc2)C(=O)OCc2c1cc1n(c2=O)Cc2c-1nc1ccccc1c2CC[Si](C)(C)CCCO
Reactant: O=C(Cl)c1ccco1
Agent: CN(C)c1ccncc1
Solvent: ClCCl
Product: CCC1(OC(=O)OCc2ccccc2)C(=O)OCc2c1cc1n(c2=O)Cc2c-1nc1ccccc1c2CC[Si](C)(C)CCCOC(=O)c1ccco1
Temperature: 21 °C
Reaction time: 5 h

Procedure:
A mixture of Compound 53 (162 mg, 0.26 mmol), 4-dimethylaminopyridine (63 mg, 0.52 mmol), and 2-furoyl chloride (62 mg, 0.47 mmol) in 6.0 mL of dichloromethane was stirred at 21° C. for 5 hours. The reaction was quenched with saturated sodium bicarbonate solution, and aqueous layer was extracted with dichloromethane. The combined organic layers were dried over sodium sulfate and concentrated to afford a crude product, which was chromatographed to give the desired product.
Reaction SMILES: [C:1]([BH3-])#[N:2].[Na+].[I:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][C:7]=1[CH2:14][CH2:15][CH:16](C)N.[C:19]1([CH2:25][CH:26]=O)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.Cl>CO>[I:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][C:7]=1[CH2:14][CH2:15][CH2:16][N:2]([CH2:1][CH2:14][C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:6]=1)[CH2:26][CH2:25][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1
Reactant: [BH3-]C#N
Reactant: COc1ccc(I)c(CCC(C)N)c1
Reactant: O=CCc1ccccc1
Agent: Cl
Agent: [Na+]
Solvent: CO
Product: COc1ccc(I)c(CCCN(CCc2ccccc2)CCc2ccccc2)c1
Temperature: 125 °C
Reaction time: 1 h
Yield: 26 %

Procedure:
A sample of 3.7 g (59 mmole) of sodium cyanoborohydride was added to a solution of 6.0 g (19.7 mmole) of 2 iodo-5-methoxy-α-methylbenzenepropanamine and 14.2 ml (0.12 mole) of phenylacetaldehyde in 60 ml of MeOH. Methanolic hydrogen chloride was added dropwise. After 16 hr the mixture was made frankly acidic by addition of methanolic hydrogen chloride. The mixture was stirred for one hour. The MeOH was evaporated in vacuo and the residue partitioned between ether and NaOH solution. The ether was evaporated in vacuo. The residue was redissolved in ether and ethereal hydrogen chloride added. The ether was decanted from the precipitated gum and the gum washed twice with ether. The gum was partitioned between NaOH solution and ether. The ether was washed with brine, dried and the solvent evaporated in vacuo. The volatile by products were removed by heating the residue up to 125° C. at 0.005 mm Hg in a Kugelrohr. The pot residue contained 9.1 g 26% yield of the title compound as a pale yellow oil.
Reaction SMILES: [Cl-].[Al+3].[Cl-].[Cl-].[Cl:5][C:6]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:7]=1[C:8](Cl)=[O:9].[CH3:16][O:17][C:18]([C:20]1[CH:29]=[CH:28][C:23]2[S:24][C:25]([CH3:27])=[CH:26][C:22]=2[CH:21]=1)=[O:19].C(OCC)(=O)C>C(Cl)Cl>[Cl:5][C:6]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:7]=1[C:8]([C:26]1[C:22]2[CH:21]=[C:20]([C:18]([O:17][CH3:16])=[O:19])[CH:29]=[CH:28][C:23]=2[S:24][C:25]=1[CH3:27])=[O:9]
Reactant: COC(=O)c1ccc2sc(C)cc2c1
Reactant: O=C(Cl)c1ccc(Cl)cc1Cl
Agent: [Al+3]
Agent: [Cl-]
Solvent: ClCCl
Solvent: CCOC(C)=O
Product: COC(=O)c1ccc2sc(C)c(C(=O)c3ccc(Cl)cc3Cl)c2c1
Temperature: 25 °C
Reaction time: 4 h

Procedure:
Aluminum chloride (1.24 g, 9.3 mmol) was dispersed in methylene chloride (10 ml), and 2,4-dichlorobenzoyl chloride (0.97 g, 4.7 mmol) and then 5-(methoxycarbonyl)-2-methylbenzo[b]thiophene(0.8 g, 3.9 mml) were added thereto. The mixture was stirred at room temperature for 4 hr. The reaction mixture was poured into ice water and ethyl acetate was added. The mixture was extracted. The organic layer was washed twice with a saturated aqueous solution of sodium hydrogencarbonate and once with brine, and dried over anhydrous sodium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to give the objective compound (1.5 g, quantitative) as pale yellow crystals.
Reaction SMILES: [CH2:1]([NH:8][C:9]([C:11]1[S:15][C:14]([NH2:16])=[N:13][C:12]=1[CH2:17][N:18]([CH2:21][CH3:22])[CH2:19][CH3:20])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:23](Cl)(=[O:30])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C(N(CC)CC)C>O1CCCC1.CN(C)C1C=CN=CC=1>[C:23]([NH:16][C:14]1[S:15][C:11]([C:9]([NH:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[O:10])=[C:12]([CH2:17][N:18]([CH2:21][CH3:22])[CH2:19][CH3:20])[N:13]=1)(=[O:30])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1
Reactant: O=C(Cl)c1ccccc1
Reactant: CCN(CC)Cc1nc(N)sc1C(=O)NCc1ccccc1
Agent: CN(C)c1ccncc1
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CCN(CC)Cc1nc(NC(=O)c2ccccc2)sc1C(=O)NCc1ccccc1
Temperature: 25 °C
Yield: 31.1 %

Procedure:
To a solution of 2-amino-4-diethylaminomethylthiazole-5-carboxylic acid benzylamide (0.052 g, 0.16 mmol) in tetrahydrofuran (5 mL) at 0° C. were added benzoyl chloride (0.04 mL, 0.34 mmol), 4-dimethylaminopyridine (catalytical amount) and triethylamine (0.3 mL, 2.10 mmol). The reaction mixture was allowed to warm to ambient temperature over 18 h then concentrated in vacuo. The crude product was purified by flash column chromatography eluting with methanol/dichloromethane (1/40 to 20/80) to afford the title compound (0.021 g); MS (ES+) m/z 423 (M+1).
Reaction SMILES: Cl.COCCCOC(C1C=CC=CC=1)C1CCCNC1.CSC(SC)=C[N+]([O-])=O.C(N(C(C)C)CC)(C)C.[CH3:39][O:40][CH2:41][CH2:42][CH2:43][O:44][CH:45]([C:59]1[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1)[CH:46]1[CH2:51][CH2:50][CH2:49][N:48](/[C:52](/SC)=[CH:53]/[N+:54]([O-:56])=[O:55])[CH2:47]1.[NH2:65][C@@H:66]([CH2:76][CH:77]1[CH2:82][CH2:81][CH2:80][CH2:79][CH2:78]1)[CH2:67][NH:68][C:69](=[O:75])[O:70][C:71]([CH3:74])([CH3:73])[CH3:72]>C(#N)C>[CH3:39][O:40][CH2:41][CH2:42][CH2:43][O:44][CH:45]([C:59]1[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1)[CH:46]1[CH2:51][CH2:50][CH2:49][N:48]([C:52]([NH:65][C@@H:66]([CH2:76][CH:77]2[CH2:78][CH2:79][CH2:80][CH2:81][CH2:82]2)[CH2:67][NH:68][C:69](=[O:75])[O:70][C:71]([CH3:74])([CH3:72])[CH3:73])=[CH:53][N+:54]([O-:56])=[O:55])[CH2:47]1
Reactant: COCCCOC(c1ccccc1)C1CCCN(/C(=C/[N+](=O)[O-])SC)C1
Reactant: CC(C)(C)OC(=O)NC[C@@H](N)CC1CCCCC1
Agent: COCCCOC(c1ccccc1)C1CCCNC1
Agent: CSC(=C[N+](=O)[O-])SC
Agent: Cl
Solvent: CC#N
Solvent: CCN(C(C)C)C(C)C
Product: COCCCOC(c1ccccc1)C1CCCN(C(=C[N+](=O)[O-])N[C@H](CNC(=O)OC(C)(C)C)CC2CCCCC2)C1
Reaction time: 2 h
Yield: 6.6 %

Procedure:
3-((3-Methoxypropoxy)(phenyl)methyl)piperidine hydrochloride (177 mg, 0.59 mmol), 1,1-bis(methylthio)-2-nitroethene (117 mg, 0.71 mmol, 1.2 equiv), and diisopropylethylamine (500 μL, 2.8 mmol, 5 equiv) were dissolved in acetonitrile (5 mL) and put on a shaker for 2 h. LC-MS indicated the presence of 3-((3-methoxypropoxy)(phenyl)methyl)-1-((Z)-1-(methylthio)-2-nitrovinyl)piperidine. Tert-butyl (S)-2-amino-3-cyclohexylpropylcarbamate (˜300 mg, 1.17 mmol, 2 equiv) was added to the mixture and shaking was continued overnight. The mixture was concentrated and purified by prep HPLC to afford tert-butyl (S)-2-(1-(3-((3-methoxypropoxy)(phenyl)methyl)piperidin-1-yl)-2-nitrovinylamino)-3-cyclohexylpropylcarbamate (22 mg, 6.6%). LC-MS (3 min) tR=1.92 min. m/z 589 (M+1).
Reaction SMILES: [Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:12]=[C:11]([C:13](O)=[O:14])[N:10]=[C:9]2[C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=2[Cl:23])=[CH:4][CH:3]=1.C(N(C(C)C)CC)(C)C.F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)[C:44]2[CH:45]=[CH:46][CH:47]=C[C:43]=2[N:42]=[N:41]1.NN1CCCCC1>C(#N)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:12]=[C:11]([C:13]([NH:41][N:42]3[CH2:47][CH2:46][CH2:45][CH2:44][CH2:43]3)=[O:14])[N:10]=[C:9]2[C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=2[Cl:23])=[CH:4][CH:3]=1
Reactant: CN(C)C(On1nnc2ccccc21)=[N+](C)C
Reactant: O=C(O)c1cn(-c2ccc(Br)cc2)c(-c2ccc(Cl)cc2Cl)n1
Agent: F[P-](F)(F)(F)(F)F
Agent: NN1CCCCC1
Solvent: CC#N
Solvent: CCN(C(C)C)C(C)C
Product: O=C(NN1CCCCC1)c1cn(-c2ccc(Br)cc2)c(-c2ccc(Cl)cc2Cl)n1
Reaction time: 16 h
Yield: 56.2 %

Procedure:
Part B: To a stirred suspension of 1-(4-bromophenyl)-2-(2,4-dichlorophenyl)-1H-imidazole-4-carboxylic acid (1.23 gram, 2.99 mmol) in dry acetonitrile (40 mL) is successively added diisopropylethylamine (DIPEA) (1.15 mL, 6.6 mmol), O-benzotriazol-1-yl-N,N,N′,N′-tetramethyluronium hexafluorophos-phate (HBTU) (1.36 gram, 3.6 mmol) and 1-aminopiperidine (0.39 mL, 3.6 mmol). After stirring for 16 hours, the resulting mixture is concentrated in vacuo. The residue is dissolved in ethylacetate and an aqueous NaHCO3 solution is added. The ethylacetate layer is collected, washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo to give a crude solid. This solid is further purified by recrystallisation from acetonitrile to give 1-(4-bromophenyl)-2-(2,4-dichlorophenyl)-N-(piperidin-1-yl)-1H-imidazole-4-carboxamide (830 mg, 56% yield). Melting point: 219–221° C.
Reaction SMILES: CC(C(Cl)(F)F)(C(F)F)[C:3]([F:6])([F:5])[F:4].[Cl:14][C:15]([Cl:18])=[CH:16][CH3:17].FC([I:23])(F)F>>[Cl:14][C:15]([Cl:18])([I:23])[CH:16]([C:3]([F:6])([F:5])[F:4])[CH3:17]
Reactant: FC(F)(F)I
Reactant: CC(C(F)F)(C(F)(F)F)C(F)(F)Cl
Reactant: CC=C(Cl)Cl
Product: CC(C(F)(F)F)C(Cl)(Cl)I

Procedure:
CH3C(CF3)(CF2H)CF2Cl (HCFC-3571mps) may be prepared as follows. Commercially available 1,1-dichloropropene may be reacted with commercially available trifluoromethyl iodide to form 1,1-dichloro-1-iodo-2-trifluoromethylpropane which may be dehydrohalogenated to form 1,1-dichloro-2-trifluoromethyl-1-propene. The 1,1-dichloro-2-trifluoromethyl-1-propene may be hydrogenated to form 1,1-dichloro-2-trifluoromethylpropane which may be fluorinated to form l,1-difluoro-2-trifluoromethylpropane. The 1,1-difluoro-2-trifluoromethylpropane may be dehydrogenated to form 1,1-difluoro-2-trifluoromethy-1-propene which may be reacted with commercially available trifluoromethyl iodide to form 1,1-difluoro-1-iodo-2,2-trifluoromethylpropane. The 1,1-difluoro-1-iodo-2,2-trifluoromethylpropane may be chlorinated to form 1-chloro-1,1-difluoro-2,2-trifluoromethylpropane which may be hydrogenated to form 1-chloro-1,1-difluoro-2-difluoromethyl-2-trifluoromethylpropane.
Reaction SMILES: [C:1]12([CH2:12][C:11](=[O:13])[O:10][C:8](=[O:9])[CH2:7]1)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]2.[CH:14]1([NH2:20])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1.Cl>ClCCl.O>[CH:14]1([NH:20][C:11]([CH2:12][C:1]2([CH2:7][C:8]([OH:10])=[O:9])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]2)=[O:13])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1
Reactant: NC1CCCCC1
Reactant: O=C1CC2(CCCCC2)CC(=O)O1
Agent: Cl
Solvent: ClCCl
Solvent: O
Product: O=C(O)CC1(CC(=O)NC2CCCCC2)CCCCC1
Temperature: 25 °C
Reaction time: 8 h
Yield: 115.9 %

Procedure:
A mixture of 1,1-cyclohexanediacetic anhydride (0.911 g, 5.0 mmol) and cyclohexylamine (0.63 mL, 5.5 mmol) in dichloromethane (10.0 mL) was stirred overnight at room temperature. The reaction mixture was diluted with H2O (5 mL) and the aqueous layer was acidified to pH-5 using 6 N HCl. The organic layer was collected. The aqueous layer was extracted with additional dichloromethane (5 mL). The organic extracts were combined, dried with sodium sulfate, filtered and concentrated to dryness to give crude title compound (1.63 g, 95% purity). (m/z): [M+H]+ calcd for C16H27NO3, 282.21; found 282.5.
Reaction SMILES: CS(C)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[CH2:19]([C:21]1[CH:30]=[C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][C:36]([C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][C:40]=3[C:45]3[N:46]=[N:47][N:48]([C:50]([C:63]4[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=4)([C:57]4[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=4)[C:51]4[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=4)[N:49]=3)=[CH:35][CH:34]=2)[C:28]2[C:23](=[CH:24][CH:25]=[C:26]([O:69][CH2:70][CH2:71][OH:72])[N:27]=2)[N:22]=1)[CH3:20].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>ClCCl.C(N(CC)CC)C>[CH2:19]([C:21]1[CH:30]=[C:29]([O:31][CH2:32][C:33]2[CH:34]=[CH:35][C:36]([C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][C:40]=3[C:45]3[N:46]=[N:47][N:48]([C:50]([C:63]4[CH:64]=[CH:65][CH:66]=[CH:67][CH:68]=4)([C:57]4[CH:58]=[CH:59][CH:60]=[CH:61][CH:62]=4)[C:51]4[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=4)[N:49]=3)=[CH:37][CH:38]=2)[C:28]2[C:23](=[CH:24][CH:25]=[C:26]([O:69][CH2:70][CH:71]=[O:72])[N:27]=2)[N:22]=1)[CH3:20]
Reactant: CCc1cc(OCc2ccc(-c3ccccc3-c3nnn(C(c4ccccc4)(c4ccccc4)c4ccccc4)n3)cc2)c2nc(OCCO)ccc2n1
Agent: O=C(O)CC(O)(CC(=O)O)C(=O)O
Agent: O=P12OP3(=O)OP(=O)(O1)OP(=O)(O2)O3
Solvent: CCN(CC)CC
Solvent: ClCCl
Solvent: CS(C)=O
Product: CCc1cc(OCc2ccc(-c3ccccc3-c3nnn(C(c4ccccc4)(c4ccccc4)c4ccccc4)n3)cc2)c2nc(OCC=O)ccc2n1
Temperature: 25 °C
Reaction time: 1 h
Yield: 46.1 %

Procedure:
DMSO (2.0 ml) and phosphorus pentoxide (4.0 g) were added to a solution of 2-ethyl-6-(2-hydroxyethoxy)-4-[(2'-(2-triphenylmethyl-2H-tetrazol-5-yl)biphenyl-4-yl)methoxy]-1,5-naphthyridine (1.0 g) in dichloromethane (20 ml) at 0° C. The mixture was stirred at ambient temperature for 1 hour and then cooled again to 0° C. Triethylamine (0.69 ml) was added and stirring was continued for 30 minutes. 1M citric acid solution (20 ml) was added and the organic phase was separated and dried (MgSO4). The solvent was removed by evaporation and the residue was purified by flash chromatography, eluting with ethyl acetate/hexane (1:1 v/v), to give 2-ethyl-6-(formylmethoxy)-4-[(2'-(2-triphenylmethyl-2H-tetrazol-5-yl)biphenyl-4-yl)methoxy]-1,5-naphthyridine (B) (0.46 g), m.p. 168°-169° C. (after trituration with ether; NMR (d6 -DMSO): 1.25(t, 3H), 2.9(q, 2H), 5.0(s, 2H), 5.35(s, 2H), 6.8-6.95(m, 6H), 7.1-7.85(m, 19H), 8.25(d, 1H), 9.7(s, 1H).
Reaction SMILES: [C:1]([OH:5])(=[O:4])[CH:2]=[CH2:3].[CH3:6][CH2:7][CH3:8]>C(O)(=O)C>[C:1]([OH:5])(=[O:4])[CH:2]=[CH2:3].[CH2:6]=[CH:7][CH3:8].[CH:1]([CH:2]=[CH2:3])=[O:4]
Reactant: CCC
Agent: C=CC(=O)O
Solvent: CC(=O)O
Product: C=CC
Product: C=CC=O

Procedure:
There are few references reported in the literature relating to the production of acrylic acid from propane. U.S. Pat. No. 5,198,580 (Standard Oil) discloses a process for partial oxidation of propane to yield acrylic acid, propylene, acrolein, acetic acid and carbon oxides. The process involves the reaction of propane in admixture with a molecular oxygen-containing gas in a reaction zone with a catalyst containing Bib, Moc, Vv, Aa, Dd, Ee, Ox; where A is one or more of K, Na, Li, Cs and TI; D is one or more of Fe, Ni, Co, Zn, Ce and La; E is one or more of W, Nb, Sb, Sn, P, Cu, Pb, B, Mg, Ca and Sr; a, d and e is each from 0 to 10; b is from 0.1 to 10; c is from 0.1 to 20; v is from 0.1 to 10; c:b is from 2:1 to 30:1 and v:b is from 1.5:1 to 8:1. The acrylic acid yield achieved using the bismuth molybdate type of catalyst at a pressure of 138 kPag (20 psig) and a temperature of 400° C. is 5.4% at 19% conversion of propane.
Reaction SMILES: COC([N:5]1[CH:14]=[C:13]2[C:7]([CH:8]([O:27][C:28](=O)C)[N:9]=[C:10]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[Cl:26])[C:11]3[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][C:12]=32)=[CH:6]1)=O.[OH-].[Na+]>O1CCCC1.CO.O>[Cl:19][C:17]1[CH:16]=[CH:15][C:12]2[C:13]3[C:7](=[CH:6][NH:5][CH:14]=3)[CH:8]([O:27][CH3:28])[N:9]=[C:10]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[Cl:26])[C:11]=2[CH:18]=1
Reactant: COC(=O)n1cc2c(c1)C(OC(C)=O)N=C(c1ccccc1Cl)c1cc(Cl)ccc1-2
Agent: [Na+]
Agent: [OH-]
Solvent: CO
Solvent: O
Solvent: C1CCOC1
Product: COC1N=C(c2ccccc2Cl)c2cc(Cl)ccc2-c2c[nH]cc21
Reaction time: 0.5 h

Procedure:
A mixture of 1.0 g (2.2 mmol) of 4-(acetyloxy)-8-chloro-6-(2-chlorophenyl)-2H,4H-pyrrolo[3,4-d][2]benzazepine-2-carboxylic acid methyl ester and 2.5 ml of 3 N aqueous sodium hydroxide solution in a mixture of 25 ml of tetrahydrofuran and 10 ml of methanol was stirred at 0° for 30 min. The mixture was diluted with water and extracted with methylene chloride. The methylene chloride solution was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and concentrated at reduced pressure to dryness. The residue was triturated with a mixture of ether and methylene chloride to give a cream colored solid, mp 215°-218°. Recrystallization from a mixture of tetrahydrofuran and hexane gave tan prisms, mp 221°-224°.
Reaction SMILES: [OH:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([NH:9][CH2:10][C:11]([OH:13])=[O:12])=[CH:5][CH:4]=1.C(N(CC)CC)C.[C:21]([O:25][C:26](N=[N+]=[N-])=[O:27])([CH3:24])([CH3:23])[CH3:22]>O.O1CCCC1>[C:21]([O:25][C:26]([N:9]([C:6]1[CH:5]=[CH:4][C:3]([CH2:2][OH:1])=[CH:8][CH:7]=1)[CH2:10][C:11]([OH:13])=[O:12])=[O:27])([CH3:24])([CH3:23])[CH3:22]
Reactant: O=C(O)CNc1ccc(CO)cc1
Reactant: CC(C)(C)OC(=O)N=[N+]=[N-]
Solvent: CCN(CC)CC
Solvent: C1CCOC1
Solvent: O
Product: CC(C)(C)OC(=O)N(CC(=O)O)c1ccc(CO)cc1
Temperature: 25 °C
Reaction time: 8 h
Yield: 62.5 %

Procedure:
To a solution of p-hydroxymethylphenylglycine (8.0 g, 0.044 mole) and triethylamine (8.8 g., 0.087 mole) in 160 ml water was added t-butoxycarbonyl azide (6.95 g., 0.049 mole) dissolved in 120 ml tetrahydrofuran. After stirring overnight at room temperature, the reaction mixture was washed twice with 200 ml. portions of ether. The aqueous layer was covered with ether and in an ice bath was acidified to pH 3-3.5 with 3N hydrochloric acid. The acidic solution was extracted three times with 200 ml portions of ether. The combined ether layers were washed with saturated sodium chloride solution, dried, and the ether evaporated under reduced pressure. The resulting oil was triturated with chloroform-hexane and the solid filtered off to give N-t-butoxycarbonyl-p-hydroxymethylphenylglycine (7.74 g, 63% yield), m.p. 139°-141.5° (dec.).
Reaction SMILES: [F:1][C:2]([F:22])([F:21])[C:3]([N:5]1[CH2:11][CH:10]([CH:12]([CH3:14])[CH3:13])[C:9]2[CH:15]=[C:16]([Br:20])[C:17]([OH:19])=[CH:18][C:8]=2[CH2:7][CH2:6]1)=[O:4].[CH2:23](Br)[CH:24]=[CH2:25]>ClCCl.Cl>[F:22][C:2]([F:1])([F:21])[C:3]([N:5]1[CH2:11][CH:10]([CH:12]([CH3:14])[CH3:13])[C:9]2[CH:15]=[C:16]([Br:20])[C:17]([O:19][CH2:25][CH:24]=[CH2:23])=[CH:18][C:8]=2[CH2:7][CH2:6]1)=[O:4]
Reactant: C=CCBr
Reactant: CC(C)C1CN(C(=O)C(F)(F)F)CCc2cc(O)c(Br)cc21
Agent: Cl
Solvent: ClCCl
Product: C=CCOc1cc2c(cc1Br)C(C(C)C)CN(C(=O)C(F)(F)F)CC2
Temperature: 20 °C
Reaction time: 3 h
Yield: 58.2 %

Procedure:
A solution of N-trifluoroacetyl-8-bromo-7-hydroxy-1-isopropyl-2,3,4,5-tetrahydro-1H-3-benzazepine (0.017 g, 0.045 mmol) in dichloromethane (1 mL) was treated with N′″-tert-butyl-N,N,N′,N′,N′,N″,N″-hexamethylphosphorimidic triamide (0.016 g, 0.068 mmol), allyl bromide (0.011 g, 0.09 mmol) and stirred for 3 hours at 20° C. The product mixture was diluted with 10% aqueous HCl, extracted twice with dichloromethane (20 mL), and concentrated. Flash chromatography (10% EtOAc in hexanes, silica) resulted in 0.011 g of a clear oil. MS calculated for C18H21BrF3NO2+H: 420, observed: 420.