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CAS No. : | 1851-22-5 | MDL No. : | MFCD00128857 |
Formula : | C5H4ClNO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NEXUNCTUUDERGR-UHFFFAOYSA-N |
M.W : | 129.54 | Pubchem ID : | 123133 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P280-P337+P313-P305+P351+P338-P302+P352-P332+P313-P362 | UN#: | N/A |
Hazard Statements: | H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With triethylamine In acetonitrile for 20 h; Heating / reflux | S-Chloro-pyridine^-carbonitrile (145-C).; To a solution of compound 145-B, (22.37 g, 172.7 mmol) in acetonitrile (175 mL) was added triethylamine (48 mL, 346 mmol) and TMS-CN (56 mL, 420 mmol). The solution was heated at reflux for 20 h then evaporated in vacuo. The residue was partitioned between EtOAc (250 mL), 10percent aqueous Na2CO3 (50 mL), and filtered over celite. The organic portion of the filtrate was washed with 10percent aqueous Na2CO3 (2X50 mL), brine (50 mL), and the organics dried over Na2SO4, filtered, and evaporated in vacuo to afford a dark crystalline residue, which was dissolved in warm diethyl ether (200 mL), filtered, and evaporated in vacuo to afford compound 145-C as a tan-orange powder (23.41 g, 98percent). 1H-NMR (DMSO-rfβ): δ 7.78-7.84 (m, IH), 8.30 (d, IH), 8.73 (d, IH); MS: m/z 139.1 (MH+). |
98% | With triethylamine In acetonitrile for 20 h; Reflux | 3-chloro-pyridine-2-carbonitrile (145-C). To a solution of compound 145-B, (22.37 g, 172.7 mmol) in acetonitrile (175 mL) was added triethylamine (48 mL, 346 mmol) and TMS-CN (56 mL, 420 mmol). The solution was heated at reflux for 20 h then evaporated in vacuo. The residue was partitioned between EtOAc (250 mL), 10percent aqueous Na2CO3 (50 mL), and filtered over celite. The organic portion of the filtrate was washed with 10percent aqueous Na2CO3 (2*50 mL), brine (50 mL), and the organics dried over Na2SO4, filtered, and evaporated in vacuo to afford a dark crystalline residue, which was dissolved in warm diethyl ether (200 mL), filtered, and evaporated in vacuo to afford compound 145-C as a tan-orange powder (23.41 g, 98percent). 1H-NMR (DMSO-d6): δ 7.78-7.84 (m, 1H), 8.30 (d, 1H), 8.73 (d, 1H); MS: m/z 139.1 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.1% | With dihydrogen peroxide; acetic acid In water at 70℃; for 6h; | 2 Preparation of N-oxido-3-chloropyridine: 56.77g (0.5 mol) 3-chloropyridine, 170.00g, 30% (1.5 mol) aqueous hydrogen peroxide, 120.00g (2 mol) acetic acid were added to a 500 ml three-mouth flask. Under stirring condition, 70 °C react for 6h. evaporating water, recovering acetic acid, by adding saturated sodium carbonate solution and mixing, to make the system is alkaline, after evaporating the water, by adding chloroform washing, filters the demineralization, recovery chloroform, vacuum distillation 61.58g, N-oxido-3-chloropyridine, yield 95.10%. |
92% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; | |
86% | With dihydrogen peroxide; acetic acid In water at 80℃; for 20h; | 8 3-Chloro-pyridine 1-oxide (145-B).; To a solution of 3-chloropyridine, (22.71 g, 200 mmol) in acetic acid (80 mL) was added hydrogen peroxide solution (30% aqueous, 40 mL), and the mixture was heated at 80 C for 15 h. Additional hydrogen peroxide solution (30% aqueous, 5 mL) was added to the reaction mixture and the heating continued an additional 5 h. After cooling, the reaction mixture was quenched20 into a solution OfNaHSO3 in water (400 mL), using starch-iodine paper to confirm the destruction of excess hydrogen peroxide. The mixture was evaporated in vacuo and partitioned between water (100 mL)and dichloromethane (250 mL). The organics were washed with saturated NaHCO3 solution (2X100 mL), and brine (100 mL). The combined aqueous layers were extracted with dichloromethane (8X100 mL),the organic extracts were combined, dried over Na2SO4, filtered, and evaporated in vacuo. The organic residue was partitioned between dichloromethane/water, treated with solid NaHCO3, and filtered. The aqueous washes from the first extraction were treated with NaHCO3, extracted with dichloromethane (3X100 mL), and the combined organics dried with Na2SO4, filtered, and evaporated in vacuo to afford compound 145-B as an orange oil (22.37 g, 86%). 1H-NMR (DMSO-rfβ): δ 7.40-7.53 (m, 2H), 8.22 (d, IH), 8.52 (s, IH); MS: m/z 130.1 (MH+). |
86% | With dihydrogen peroxide In water; acetic acid at 80℃; for 20h; | 8 Example 8 3-chloro-pyridine 1-oxide (145-B). To a solution of 3-chloropyridine, (22.71 g, 200 mmol) in acetic acid (80 mL) was added hydrogen peroxide solution (30% aqueous, 40 mL), and the mixture was heated at 80° C. for 15 h. Additional hydrogen peroxide solution (30% aqueous, 5 mL) was added to the reaction mixture and the heating continued an additional 5 h. After cooling, the reaction mixture was quenched into a solution of NaHSO3 in water (400 mL), using starch-iodine paper to confirm the destruction of excess hydrogen peroxide. The mixture was evaporated in vacuo and partitioned between water (100 mL) and dichloromethane (250 mL). The organics were washed with saturated NaHCO3 solution (2*100 mL), and brine (100 mL). The combined aqueous layers were extracted with dichloromethane (8*100 mL), the organic extracts were combined, dried over Na2SO4, filtered, and evaporated in vacuo. The organic residue was partitioned between dichloromethane/water, treated with solid NaHCO3, and filtered. The aqueous washes from the first extraction were treated with NaHCO3, extracted with dichloromethane (3*100 mL), and the combined organics dried with Na2SO4, filtered, and evaporated in vacuo to afford compound 145-B as an orange oil (22.37 g, 86%). 1H-NMR (DMSO-d6): δ 7.40-7.53 (m, 2H), 8.22 (d, 1H), 8.52 (s, 1H); MS: m/z 130.1 (MH+). |
84% | With dihydrogen peroxide; methyltrioxorhenium(VII) In dichloromethane; water for 17h; Ambient temperature; | |
80% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 16h; | 201 EXAMPLE 201, COMPOUND 201: N1-(3,5-dimethyl-pyridin-2-ylmethyl)-N1-(3-morpholin-4-yl-piridin-2-ylmethyl)-butane-1,4-diamine (HBr salt) EXAMPLE 201 COMPOUND 201: N1-(3,5-dimethyl-pyridin-2-ylmethyl)-N1-(3-morpholin-4-yl-piridin-2-ylmethyl)-butane-1,4-diamine (HBr salt) A mixture of 3-chloro-pyridine (1.14 g, 10.0 mmol) and 3-chloroperoxybenzoic acid (77%, 4.5 g, 20 mmol) in CH2Cl2 (30 mL) was stirred at room temperature for 16 h. Saturated aqueous NaHCO3 (10 mL) was added, and the mixture was extracted with CH2Cl2 (5*30 mL). The extracts were combined and dried over anhydrous Na2SO4. After filtration the solvent was removed by evaporation under vacuum, and the residue was purified by flash chromatography on a silica gel column (EtOAc), affording 3-chloro-pyridine-1-oxide as a pale yellow solid (1.03 g, 80%). |
79% | With dihydrogen peroxide In AcOH | 44.A 44A. 44A. 3-Chloropyridine-N-oxide Commercially available 3-chloropyridine (11.4 g, 100 mmol) was dissolved in AcOH (60 mL) and 30% hydrogen peroxide (15 mL) was added. The mixture was heated to 70° C. for 12 h. The cooled mixture was concentrated under reduced pressure. The residue was diluted with chloroform (50 mL) and solid potassium carbonate (20 g) was added and the mixture stirred for 1 h, after which it was filtered and concentrated to give a yellow-green oil (10.21 g, 79%), which by NMR contained ~8% of starting material. The oil was used directly without further purification. |
79% | With dihydrogen peroxide In acetic acid | 44.A 44A. 44A. 3-Chloropyridine-N-oxide Commercially available 3-chloropyridine (11.4 g, 100 mmol) was dissolved in AcOH (60 mL) and 30% hydrogen peroxide (15 mL) was added. The mixture was heated to 70° C. for 12 h. The cooled mixture was concentrated under reduced pressure. The residue was diluted with chloroform (50 mL) and solid potassium carbonate (20 g) was added and the mixture stirred for 1 h, after which it was filtered and concentrated to give a yellow-green oil (10.21 g, 79%), which by NMR contained ~8% of starting material. The oil was used directly without further purification. |
76% | With 3-chloro-benzenecarboperoxoic acid In chloroform at 20℃; | Synthesis of 3-chloro-pyridine -N- oxide 3.00 g (26 mmol) of 3-chloropyridine was added to 60 g of chloroform, and 6.69 g (29 mmol) of 75% m chloroperbenzoic acid was added thereto. After stirring overnight at room temperature, 60 mL of water was added for extraction. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained residue was purified by column chromatography to obtain 2.6 g (yield 76%) of the title compound. |
74% | With dihydrogen peroxide In acetic acid at 80℃; for 10h; | |
74% | With 3-chloro-benzenecarboperoxoic acid In chloroform at 0 - 20℃; for 20h; | |
53% | With dihydrogen peroxide; acetic anhydride 1)room temp., 5h 2) 60-65 deg C, 30h; | |
47% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; | |
With dihydrogen peroxide; acetic acid | ||
With 3-chloro-benzenecarboperoxoic acid | ||
With dihydrogen peroxide; potassium carbonate In acetic acid | A A. A. 3-Chloropyridine-1-oxide (775A) Commercially available 3-chloropyridine (11.36 g, 100 mmol) was dissolved in 60 mL of acetic acid and 30% hydrogen peroxide (15 mL) was added. The reaction mixture was heated to 70° C. for 16 h. The cooled reaction mixture was diluted with chloroform and stirred with solid potassium carbonate. The mixture was filtered and solvent removed in vacuo to give compound 775A (10.21 g, 79%) as a yellow-green oil. | |
With dihydrogen peroxide; methyltrioxorhenium(VII) In dichloromethane; water at 20℃; for 6h; | 19 A mixture of 3-chloropyridine (2.30 g, 20.30 mmol), and methyl rhenium trioxide (25 mg, 0.1 mmol) in methylene chloride (10 mL) was treated with 30% aqueous hydrogen peroxide (5 mL, 50 mmol) and stirred for 6h at room temperature. The biphasic reaction mixture was then treated with a catalytic amount of manganese (IV) oxide (5 mg) and stirred until oxygen evolution ceased. Following phase separation, the aqueous layer was extracted with methylene chloride, and the combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give 3-chloropyridine 1-oxide (2.50 g) as a solid, mp 56-58 0C (Lit. 59-60 0C). 1HNMR (300 MHz, C6D6): 7.80-8.40 (m, 2H), 6.50-6.80 ppm (m, 2H). 13C NMR (300 MHz, C6D6): 138.79, 137.76, 132.85, 125.46, 123.41. MW=130 confirmed by LC-MS, t,= 0.38 min (Method E) MH+=131. | |
Stage #1: 3-Chloropyridine With dihydrogen peroxide In water; acetic acid at 0 - 120℃; for 22.7h; Stage #2: With potassium carbonate In water; acetic acid at 20℃; | ||
With Candida antarctica lipase B; D-glucose; glucose oxidase from A. Niger; oxygen In aq. phosphate buffer; ethyl acetate at 20℃; for 1h; Green chemistry; | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 12h; | ||
With dihydrogen peroxide In water; acetic anhydride at 0 - 20℃; | 10.1 Example 10; 3-ETHYL-2- [2-(3-FLUORO-PHENYL)-IMIDAZOL-1-YLMETHYL] -3H-IMIDAZO[4,5-C] PYRIDINE; 1. Preparation of 3-Chloro-4-nitro-pyridine-1-oxide Example 10 3-ETHYL-2- [2-(3-FLUORO-PHENYL)-IMIDAZOL-1-YLMETHYL] -3H-IMIDAZO[4,5-C] PYRIDINE [0212] [CHEMMOL-00024] 1. Preparation of 3-Chloro-4-nitro-pyridine-1-oxide [0213] Aqueous 30% H2O2 (60 mL) was added dropwise to a magnetically stirred solution of 3-chloro-pyridine (12 g, 105 mmol) in acetic anhydride (60 mL) under cold conditions (0 to 10° C.). The resulting mixture is allowed to warm to room temperature slowly and stirred overnight. The reaction mixture is quenched with water (50 mL), diluted with toluene and concentrated to obtain crude N-oxide as an oil that is used without further purification. [0214] Fuming H2SO4 (25 mL) is added dropwise to a solution of crude 3-chloro-pyridine-1-oxide in concentrated H2SO4 (25 mL) with cooling (0° C.) and stirring. HNO3 (fuming, 90%, 60 mL) is added carefully to the above mixture with caution to keep the offset of any exotherm under control, and then allowed to warm up to room temperature slowly. The resulting mixture is then heated at 120° C. for 4 hours with stirring, cooled, and poured into ice-cold water, and extracted with CHCl3. The combined organic phase is washed successively with saturated aqueous NaHCO3, water, brine, dried over Na2SO4, and concentrated in vacuo to afford 3-chloro-4-nitro-pyridine-1-oxide as an yellow solid (10 g) ; 1H NMR (300 MHz, CDCl3): 1H NMR (300 MHz, CDCl3): δ 8.31 (d, J=1.5 Hz, 1H) , 8.13 (dd, J=1.5, 5.4 Hz, 1H) 7.95 (d, J=7.2 Hz, 1H) | |
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.51% | With potassium iodide In methanol for 8h; Reflux; | 6 Preparation of N-oxido-3-methoxypyridine: 64.75g (0.5 mol) N-oxido-3-chloropyridine, 32.40g (0.6 mol) sodium methoxide, 3.75g (0.025 mol) potassium iodide and 200 ml methanol were respectively added into 500 ml three-mouth flask, Under stirring conditions, reflux reaction 8h. Afterwards, cooling, and in to the neutral, to recycle the methanol, evaporating the water, and get the 52.82g, N-oxido-3-methoxypyridine, yield 84.51%. |
With methanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.92% | With potassium iodide In ethanol for 8h; Reflux; | 8 Preparation of N-oxido-3-ethoxypyridine: 64.75g (0.5 mol) N-oxido-3-chloropyridine, 40.80g (0.6 mol) sodium ethoxide, 3.75g (0.025 mol) potassium iodide and 200 ml ethanol were respectively added into 500 ml three-mouth flask. Under stirring conditions, reflux reaction 8h. Afterwards, cooling, and in to the neutral, recovering the ethanol, evaporating the water, and get the 57.63g, N-oxido-3-ethoxypyridine, yield 82.92%. |
With ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | for 30h; Reflux; | 1 2.00 g (15 mmol) of 3-chloropyridine-N-oxide was added to 20 g of acetic anhydride and stirred under reflux condition for 30 hours.The reaction mixture was distilled off and the obtained residue was purified by columnPurification by chromatography gave 1.1 g (yield 43%) of the title compound. 0.2 g of 2-acetyloxy-3-chloropyridine was obtained as a by-product. Production of 4-acetyloxy-3chloropyridine could not be confirmed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23.6% | In toluene for 24h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37.5% | With triethylamine In toluene for 12h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In N,N-dimethyl-formamide at 100 - 120℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41.4% | In acetonitrile for 12h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12% | In N,N-dimethyl-formamide for 10h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 19% 2: 3% | In N,N-dimethyl-formamide for 10h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2% | In N,N-dimethyl-formamide for 10h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 17% 2: 5% | In N,N-dimethyl-formamide for 10h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 5% 2: 3% 3: 36% | With N,N-diethylcarbamyl chloride In acetonitrile for 6h; Heating; | |
1: 30% 2: 4% 3: 13% | With N,N-diethylcarbamyl chloride; triethylamine; zinc dibromide In acetonitrile for 6h; Heating; | |
1: 30% 2: 13% 3: 4% | With N,N-diethylcarbamyl chloride; triethylamine; zinc dibromide In acetonitrile for 6h; Heating; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 8% 2: 68% | In chloroform for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | In water at 120℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 16% 2: 3% | In N,N-dimethyl-formamide for 10h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With hydrogen; triethyl phosphite In isopropyl alcohol at 100℃; for 12h; Glovebox; chemoselective reaction; | |
80% | With aluminium(III) iodide In acetonitrile for 6h; Heating; | |
75% | With 1,1,2,2-tetrabutyl-1,2-dichloro distannane In tetrahydrofuran for 1h; Heating; |
75% | With indium(III) chloride In acetonitrile for 1.2h; Heating; | |
72% | With ruthenium trichloride In acetonitrile at 80℃; for 0.833333h; | |
65% | With triethyl-amine; compound In 1,4-dioxane for 2.5h; Heating; | |
10% | With methanesulfonyl chloride; triethylamine In dichloromethane for 18h; 0 deg C to RT; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nitric acid; In sulfuric acid; | EXAMPLE 141B 4-nitro-3-chloropyridine-N-oxide Example 141B was processed as in Caldwell and Martin (J. Heterocyclic Chem., 1980, 17, 989). Example 141A (16.8 g, 130 mmol) in sulfuric acid (25 mL, 98%), fuming sulfuric acid (30% SO3, 10 mL), and nitric acid (60 mL, 90%) was heated at 120 C. for 2 hours, cooled to room temperature, poured into ice water (200 mL), solid ammonium carbonate was added to bring the solution to pH=9, and extracted with methylene chloride (4*100 mL). The extracts were dried (Na2SO4) and concentrated. The residue was recrystallized from ethyl acetate-hexanes to provide a clean first crop of the title compound. Second crop recrystallizations provided mixtures of title compound and side products. MS (DCI/NH3) m/z 194 (37Cl)/192 (35Cl), (M+NH4)+; 177 (37Cl)/175 (35Cl), (M+H)+; 1H NMR (CDCl3, 300 MHz) delta 8.01 (d, 1H), 8.14 (dd, 1H), 8.32 (d, 1H). | |
With sulfuric acid; nitric acid; at 0 - 120℃; for 4h; | Example 10 3-ETHYL-2- [2-(3-FLUORO-PHENYL)-IMIDAZOL-1-YLMETHYL] -3H-IMIDAZO[4,5-C] PYRIDINE [0212] [CHEMMOL-00024] 1. Preparation of 3-Chloro-4-nitro-pyridine-1-oxide [0213] Aqueous 30% H2O2 (60 mL) was added dropwise to a magnetically stirred solution of 3-chloro-pyridine (12 g, 105 mmol) in acetic anhydride (60 mL) under cold conditions (0 to 10 C.). The resulting mixture is allowed to warm to room temperature slowly and stirred overnight. The reaction mixture is quenched with water (50 mL), diluted with toluene and concentrated to obtain crude N-oxide as an oil that is used without further purification. [0214] Fuming H2SO4 (25 mL) is added dropwise to a solution of crude 3-chloro-pyridine-1-oxide in concentrated H2SO4 (25 mL) with cooling (0 C.) and stirring. HNO3 (fuming, 90%, 60 mL) is added carefully to the above mixture with caution to keep the offset of any exotherm under control, and then allowed to warm up to room temperature slowly. The resulting mixture is then heated at 120 C. for 4 hours with stirring, cooled, and poured into ice-cold water, and extracted with CHCl3. The combined organic phase is washed successively with saturated aqueous NaHCO3, water, brine, dried over Na2SO4, and concentrated in vacuo to afford 3-chloro-4-nitro-pyridine-1-oxide as an yellow solid (10 g) ; 1H NMR (300 MHz, CDCl3): 1H NMR (300 MHz, CDCl3): delta 8.31 (d, J=1.5 Hz, 1H) , 8.13 (dd, J=1.5, 5.4 Hz, 1H) 7.95 (d, J=7.2 Hz, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Rk. m. Natrium-methylat, MeOH; | ||
Rk. m. KNH2, fl. NH3, -33grad -> nur 3-Amino-pyridin-N-oxid < intermediaere Bldg. von 2,3-Pyridyn-N-oxid>; | ||
Geschw. der Rk. m. Piperidin, MeOH (konduktometr. Messung); |
Rk. m. Piperidin, Benzol, Erw. -> 3-Piperidino-N-oxid + sehr wenig 4-Piperidino-pyridin-N-oxid; | ||
Geschw.der Rk.mit Piperidin in Me.; | ||
D-Austausch mit CH3OD: ΔH(excit.), ΔS(excit.); | ||
Bestrahlen mit UV-Licht - > geringe Mengen 4-Chlor-2-formyl-pyrrol (3k), 3-Chlor-pyrrol (14); | ||
Photolyse (Cu2+) <Table 2>; | ||
Rk. m. Ti3+-Ionen: Geschw.konst.; ΔH(excit.), ΔS(excit.); | ||
Rk. m. Cr2+-Ionen: Geschw.konst.; ΔH(excit.), ΔS(excit.); | ||
Rk.mit Na2SO3 in W. (10 h 143grad) -> nur Pyridin-3-sulfonsaeure-1-oxyd; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 52% 2: 29% | With pyridine; diphenyl phosphoryl azide at 120℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 30 percent / diethylcarbamoyl chloride, zinc bromide, Et3N / acetonitrile / 6 h / Heating 2: 1.) anisole, mercury(II) acetate, 2.) aq. NaOH, NaBH4 / 1.) TFA, 0 deg C, 15 min, 2.) RT, 1.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dimethylformamide / 100 - 120 °C 2: 11 percent / phosphorus oxychloride / 1 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: dimethylformamide / 100 - 120 °C 2: 14 percent / phosphorus oxychloride / 1 h / Heating 3: 62 percent / 3-chloroperoxybenzoic acid / CH2Cl2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dimethylformamide / 100 - 120 °C 2: 14 percent / phosphorus oxychloride / 1 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: dimethylformamide / 100 - 120 °C 2: 18 percent / phosphorus oxychloride / 1 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: dimethylformamide / 100 - 120 °C 2: 18 percent / phosphorus oxychloride / 1 h / Heating 3: 95 percent / 6 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: dimethylformamide / 100 - 120 °C 2: 14 percent / phosphorus oxychloride / 1 h / Heating 3: 62 percent / 3-chloroperoxybenzoic acid / CH2Cl2 4: 1.) NaH / 1.) DMSO, a) 25 deg C, 30 min, b) 55-65 deg C, 1 h, 2.) DMSO, 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 87 percent / H2O / 24 h / 120 °C 2: 83 percent / Et3N / acetonitrile / 10 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 68 percent / CHCl3 / 4 h / Heating 2: 95 percent / conc. HCl / 8 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 35 percent / conc. and fuming H2SO4,conc. HNO3 / 2 h / Heating 2: 1)room temp.4h,DMF 2) reflux overnight 3: 20 percent / Phosphorus trichloride / CHCl3 / 2 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 35 percent / conc. and fuming H2SO4,conc. HNO3 / 2 h / Heating 2: 1)room temp.4h,DMF 2) reflux overnight |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With dihydrogen peroxide; paraformaldehyde In methanol; acetic acid | 18 Preparation of the Acid: EXAMPLE 18 N-[(3R)-1-azabicyclo[2.2.2]oct-3-yl]thieno[3,2-b]pyridine-2-carboxamide Preparation of the Acid: 3-Chloropyridine (9.5 mL. 99.9 mmol) is dissolved in acetic acid (35 mL) and heated to 98° C. 30% Hydrogen peroxide (28 mL) is added drop-wise, and the reaction stirred for 5 h at 98° C. The reaction is cooled and paraformaldehyde is added so that a negative peroxide test is achieved using starch-iodine paper. The solution is concentrated in vacuo and the crude paste is chromatographed over 600 g slurry-packed silica eluding with 4 L of 2% MeOH/CH2Cl2, 2 L of 4% MeOH/CH2Cl2, and finally 1 L of 10% MeOH/CH2Cl2. The fractions with the desired compound are collected and concentrated to afford 3-chloropyridine 1-oxide (C125) as a pale oil (100% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide; nitric acid; In sulfuric acid; acetic anhydride; | 1. Preparation of 3-Chloro-4-nitro-pyridine-1-oxide Aqueous 30% H2O2 (60 mL) is added dropwise to a magnetically stirred solution of 3-chloro-pyridine (12 g, 105 mmol) in acetic anhydride (60 mL) under cold conditions (0 to 10 C.). The resulting mixture is allowed to warm up to room temperature slowly and then stirred overnight at room temperature. The reaction mixture is quenched with water (50 mL), diluted with toluene and concentrated to obtain the crude N-oxide as an oil in near quantitative yield. Fuming H2SO4 (25 mL) is added dropwise to a solution of crude 3-chloro-pyridine-1-oxide in concentrated H2SO4 (25 mL) under cold conditions (0 C.) with stirring. HNO3 (fuming, 90%, 60 mL) is added carefully to the above mixture with caution to keep the offset of any exotherm under control, and then allowed to warm to room temperature slowly. The resulting mixture is then heated at 120 C. for 4 h with stirring, cooled, poured into ice-cold water, and extracted with CHCl3. The combined organic phase is washed successively with saturated aqueous NaHCO3, water, brine, dried over Na2SO4, and concentrated in vacuo to afford 3-Chloro-4-nitro-pyridine-1-oxide as an yellow solid. 1H NMR (300 MHz, CDCl3): delta 8.31 (d, J=1.5 Hz, 1H), 8.13 (dd, J=1.5, 5.4 Hz, 1H), 7.95 (d, J=7.2 Hz, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With triethylamine; In acetonitrile; for 20h;Heating / reflux; | S-Chloro-pyridine^-carbonitrile (145-C).; To a solution of compound 145-B, (22.37 g, 172.7 mmol) in acetonitrile (175 mL) was added triethylamine (48 mL, 346 mmol) and TMS-CN (56 mL, 420 mmol). The solution was heated at reflux for 20 h then evaporated in vacuo. The residue was partitioned between EtOAc (250 mL), 10% aqueous Na2CO3 (50 mL), and filtered over celite. The organic portion of the filtrate was washed with 10% aqueous Na2CO3 (2X50 mL), brine (50 mL), and the organics dried over Na2SO4, filtered, and evaporated in vacuo to afford a dark crystalline residue, which was dissolved in warm diethyl ether (200 mL), filtered, and evaporated in vacuo to afford compound 145-C as a tan-orange powder (23.41 g, 98%). 1H-NMR (DMSO-rfbeta): delta 7.78-7.84 (m, IH), 8.30 (d, IH), 8.73 (d, IH); MS: m/z 139.1 (MH+). |
98% | With triethylamine; In acetonitrile; for 20h;Reflux; | 3-chloro-pyridine-2-carbonitrile (145-C). To a solution of compound 145-B, (22.37 g, 172.7 mmol) in acetonitrile (175 mL) was added triethylamine (48 mL, 346 mmol) and TMS-CN (56 mL, 420 mmol). The solution was heated at reflux for 20 h then evaporated in vacuo. The residue was partitioned between EtOAc (250 mL), 10% aqueous Na2CO3 (50 mL), and filtered over celite. The organic portion of the filtrate was washed with 10% aqueous Na2CO3 (2*50 mL), brine (50 mL), and the organics dried over Na2SO4, filtered, and evaporated in vacuo to afford a dark crystalline residue, which was dissolved in warm diethyl ether (200 mL), filtered, and evaporated in vacuo to afford compound 145-C as a tan-orange powder (23.41 g, 98%). 1H-NMR (DMSO-d6): delta 7.78-7.84 (m, 1H), 8.30 (d, 1H), 8.73 (d, 1H); MS: m/z 139.1 (MH+). |
With triethylamine; In acetonitrile; | B. 3-Chloro-2-cyanopyridine (775B) 3-Chloropyridine-1-oxide (2.59 g, 20 mmol), trimethylsilyl cyanide (5.95 g, 60 mmol), and triethylamine (4.05 g, 40 mmol) were combined in 40 mL of acetonitrile and reacted as described in example 763A. The solvent was removed in vacuo and the residue partitioned between CH2Cl2 and 3M potassium carbonate. The organic layer was separated, washed with brine, dried (MgSO4), and concentrated in vacuo. Purification of the crude product by silica gel chomatography using 5% ether/CH2Cl2 as the eluent gave compound 775B (1.84 g, 67%) as a white crystalline solid. HPLC: 100% at 1.64 min(YMC S5 ODS column) eluding with 10-90% aqueous methanol containing 0.2% phosphoric acid over a 4 min gradient monitoring at 220 nm. MS (ES): m/z 139.0 [M+H]+. |
With triethylamine; In acetonitrile; for 6h;Heating / reflux; | A mixture of 3-chloropyridine-N-oxide (2.12 g, 16.30 mmol), trimethylsilyl(acetonitrile) (3.25 g, 32.80 mmol), triethylamine (3.30 g, 32.60 mmol) and acetonitrile (10 mL) was heated at reflux for 6h. After concentration under reduced pressure, the resulting residue was basifed with aqueous sodium carbonate (3N) and extracted with methylene chloride. The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give 3- chloropicolinonitrile (1.90 g). The crude product was carried forward without further purification. MW=139 confirmed by LC-MS, tr= 2.33 min (Method E) MH+=MO. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In water | 1 2nd stage Trimethyl-2-(5-chloropyridyl)-ammonium chloride is prepared in accordance with the above specification starting from 32.4 g (0.25 mol) of 3-chloropyridine N-oxide, but without purification of the crude product by column chromatography. The crude product is introduced into 500 ml of 1,2-dichloroethane, and gaseous hydrogen chloride is added at 50° C. for 30 hours. The mixture is then concentrated, the residue is taken up in water and the mixture is brought to pH 9-10 with dilute sodium hydroxide solution and extracted three times with methylene chloride. The combined organic phases are dried over sodium sulphate, filtered and concentrated on a rotary evaporator. The crude product is then purified by column chromatography. 19.7 g (53% of theory, based on the 3-chloropyridine N-oxide employed) of 2,5-dichloropyridine are obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4 g (78%) | With sodium methylate In methanol; water | 2 3-Methoxypyridine-N-oxide STR17 EXAMPLE 2 3-Methoxypyridine-N-oxide STR17 A solution of 3-chloropyridine-N-oxide (5.3g, 40 mmol) and 25% NaOMe in MeOH (25 ml) was refluxed for 24 hours under an argon atmosphere. The solvent was removed under reduced pressure and the residue was treated with CH2 Cl2 and water. The organic phase was separated and dried (Na2 SO4) and the solvent removed to give a residue which was triturated with hexane to yield 4 g (78%) of product as a crystalline solid, m.p. 99°-101° C. The structural assignment is supported by the proton NMR spectrum. Anal. calcd. for C6 H7 NO2: C, 57.59; H, 5.64; N, 11.19. Found: C, 57.48; H, 5.70; N, 11.02. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60 g (60%) | In acetic acid | 1 3-Chloropyridin-N-oxide STR16 EXAMPLE 1 3-Chloropyridin-N-oxide STR16 A solution of 3-chloropyridine (89.7 g, 0.79 mol) and 30% aqueous H2 O2 (135 ml) in HOAc (800 ml) was refluxed for 4 hrs. and then stirred overnight at 25° C. The reaction mixture was evaporated on the rotary evaporator using an oil pump to give an oily residue that was further heated at 60° C. under high vacuum for 1 hour. Upon cooling to 4° C., the oily residue crystallized. The crystalline mass was triturated with ether, filtered and air dried to give 60 g (60%) of the titled product, m.p. 87°-88° C. The structural assignment is supported by the proton NMR spectrum. Anal. calcd. for C5 H4 ClNO: C, 46.36; H, 3.11; N, 10.81; Cl, 27.37. Found: C, 46.11; H, 3.08; N, 10.45; Cl, 27.11. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; sodium hydrogensulfite;aluminum nickel; In water; | EXAMPLE 5 18.7 kg of sodium bisulfite were dissolved in 55.8 liters of water and the pH was adjusted to a pH of 9 to 9.5 with 14.4 kg of sodium hydroxide. To the solution were added 11.7 kg of raw 3-chloro-pyridine-N-oxide and the mixture was heated in an autoclave to 145 C. The reaction mixture was stirred at 145 C. for 17 hours (during the reaction, a pressure of 4 to 5 bars resulted). After completion of the reaction, cooling to 90 C. took place. 1 kg of sodium hydroxide (50 weight %) was added to adjust to alkaline and in a nitrogen atmosphere, 0.5 kg of Raney nickel were added. The suspension was heated to 100 to 110 C. and at this temperature, hydrogen was pressed on with 7 bars. Hydrogenation was carried out for 16 hours and then the mixture was cooled to 70 C. and the catalyst was separated with a pressure filter. The pyridine-3-sulfonic acid was isolated as in Example 4 and purified. | |
With hydrogenchloride; sodium hydroxide; dihydrogen peroxide; sodium sulfite;aluminum nickel; In ethanol; water; ethylene glycol; isopropyl alcohol; | EXAMPLE 6 252 g of sodium sulfite were dissolved in 700 of water and to this solution were added 129.6 g of raw 3-chloro-pyridine-N-oxide. In a nitrogen atmosphere, the reaction mixture was heated to 145 C. and stirred for 17 hours at this temperature. Subsequent cooling to 60 C. took place and 35 ml of ethanol, 35 g of sodium hydroxide (50%) and 14 g of Raney nickel were added. The suspension was again heated to 100 C. and hydrogenated at 7 bars for 6 hours. Cooling to 50 C. took place and the catalyst was filtered off. Sulfite still contained in the reaction solution was oxidized with 30 ml of hydrogen peroxide (70%) and at this point, approximately 400 ml of water were distilled from the reaction mixture in vacuo and 400 ml of glycol were added. Additional water was distilled off until the liquid phase temperature had risen to 100 C. Without further distillation, the temperature was increased to 130 C. by decreasing the vacuum. The hot suspension was filtered and the residue was washed with 100 ml of hot glycol. From the combined filtrate, glycol was distilled off until a residue remained which was still stirrable and which after cooling was mixted with 500 ml of concentrated hydrochloric acid and stirred for one hour at 35 C. Sodium chloride precipitate was filtered off and washed with 100 ml of concentrated hydrochloric acid. The filtrates were purified and concentrated to the limit of stirrability. Then, 300 ml of isopropanol were added at 80 C. The suspension was cooled to 20 C. and filtered. The filter cake was washed with 100 ml of isopropanol and the yield of the raw acid was 80 to 83%. For further purification, the product was dissoleved in 260 ml of water and after the addition of 5 g of activated charcoal (Eponit), stirring took place for 30 minutes at 80 C. followed by filtering. From the filtrate, approximately 170 ml of water were distilled off and after cooling to 70 C., 350 ml of ethanol were added. After cooling to 20 C., the precipitated pyridine-3-sulfonic acid was filtered off and then washed with 100 ml of methanol to obtain a yield of pure pyridine-3-sulfonic acid of between 77 to 80% with a purity of 99%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 32 5-[[[5-(Decyloxy)-2-pyridinyl]carbonyl]amino]pentanoic acid Following the procedure of Examples 22 and 23 except substituting 5-chloropyridine N-oxide for 4-chloropyridine N-oxide, decyl alcohol for nonyl alcohol, and substituting <strong>[29840-57-1]ethyl 5-aminovalerate hydrochloride</strong> for ethyl 4-aminobutyrate hydrochloride, the title compound is obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With water-d2; potassium carbonate at 190℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine / acetonitrile / 20 h / Reflux 2: potassium carbonate / acetonitrile / 3 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: triethylamine / acetonitrile / 20 h / Reflux 2: potassium carbonate / acetonitrile / 3 h / Reflux 3: copper(I) bromide; sodium nitrite; hydrogen bromide / water / 2.17 h / Cooling with ice |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: triethylamine / acetonitrile / 20 h / Reflux 2: potassium carbonate / acetonitrile / 3 h / Reflux 3: copper(I) bromide; sodium nitrite; hydrogen bromide / water / 2.17 h / Cooling with ice 4: hydrogenchloride; lithium hydroxide monohydrate / water; tetrahydrofuran / 72 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: triethylamine / acetonitrile / 20 h / Reflux 2: potassium carbonate / acetonitrile / 3 h / Reflux 3: copper(I) bromide; sodium nitrite; hydrogen bromide / water / 2.17 h / Cooling with ice 4: hydrogenchloride; lithium hydroxide monohydrate / water; tetrahydrofuran / 72 h 5: N-ethyl-N,N-diisopropylamine; diphenyl phosphoryl azide / dichloromethane / 16 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With silver (II) carbonate; caesium carbonate; tricyclohexylphosphine tetrafluoroborate; palladium(II) bromide In 1,4-dioxane at 150℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1,4-dioxane / 20 °C 2: silver(l) oxide / 1,4-dioxane / 24 h / 60 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With copper(l) iodide; lithium tert-butoxide In toluene at 100℃; for 1h; Microwave irradiation; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With copper(l) iodide; lithium tert-butoxide In toluene at 100℃; for 1h; Microwave irradiation; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With triethylamine at 50℃; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium iodide / methanol / 6 h / Reflux 2: hydrazine hydrate; pyrographite; iron(III) chloride / ethanol / 4 h / 70 °C | ||
Multi-step reaction with 2 steps 1: potassium iodide / methanol / 8 h / Reflux 2: hydrazine hydrate; pyrographite; iron(III) chloride / ethanol / 4 h / 70 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium iodide / ethanol / 8 h / Reflux 2: hydrazine hydrate; pyrographite; iron(III) chloride / ethanol / 3 h / 70 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.88% | With potassium iodide In ethanol for 8h; Reflux; | 9 Preparation of N-oxido-3-ethoxypyridine: 64.75g (0.5 mol) N-oxido-3-chloropyridine, 50.40g (0.6 mol) potassium ethanolate, 3.75g (0.025 mol) potassium iodide and 200 ml ethanol were respectively added into 500 ml three-mouth flask. Under stirring conditions, reflux reaction 8h. Afterwards, cooling, and in to the neutral, recovering the ethanol, water washing after two, separating, and get the 51.35g, N-oxido-3-ethoxypyridine, yield 73.88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.7% | With potassium iodide In methanol for 6h; Reflux; | 7 Preparation of N-oxido-3-methoxypyridine: 64.75g (0.5 mol) N-oxido-3-chloropyridine, 36.00g (0.6 mol) potassium methoxide, 3.75g (0.025 mol) potassium iodide and 200 ml methanol were respectively added into 500 ml three-mouth flask. Under stirring conditions, reflux reaction 6h. Afterwards, cooling, and in to the neutral, to recycle the methanol, evaporating the water, and get the 47.31g, N-oxido-3-methoxypyridine, yield 75.70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With 4-nitro-benzoyl chloride; triethylamine In neat (no solvent) at 20 - 50℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: sulfuric acid; nitric acid / 4 h / 0 - 120 °C 2: potassium carbonate / tetrahydrofuran; acetonitrile / 0 - 20 °C 3: hydrogen / palladium 10% on activated carbon / methanol / 48 h / 2585.81 - 3102.97 Torr |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sulfuric acid; nitric acid / 4 h / 0 - 120 °C 2: potassium carbonate / tetrahydrofuran; acetonitrile / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: acetonitrile / 60 - 70 °C 2: 3-(diphenylphosphoryl)-6-methoxy-1-methylquinolin-2(1H)-one; sodium hydrogencarbonate / acetonitrile / 20 °C / Sealed tube; Inert atmosphere; Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | In acetonitrile at 60 - 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With dipotassium peroxodisulfate; palladium diacetate; silver carbonate; trifluoroacetic acid In acetonitrile at 110℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile at 80℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: acetonitrile / 24 h / 80 °C 2: eosin / dimethyl sulfoxide / 12 h / 20 °C / Inert atmosphere; Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 39% 2: 24% | With eosin; caesium carbonate; p-benzoquinone In methanol at -78 - 20℃; for 72h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | Stage #1: 3-chloropyridine-N-oxide With bis(trifluoromethanesulfonyl)amide at 20℃; for 0.0833333h; Glovebox; Inert atmosphere; Stage #2: 3,3-Dimethylbut-1-yne With [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) at 20℃; for 12h; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sulfuric acid; sodium nitrate 2: molybdenum hexacarbonyl / N,N-dimethyl-formamide / 23 h / 70 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: sulfuric acid; sodium nitrate 2: molybdenum hexacarbonyl / N,N-dimethyl-formamide / 23 h / 70 °C / Inert atmosphere 3: potassium hydroxide; 18-crown-6 ether / toluene / 4 h / 20 °C / Dean-Stark |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: Cs2CO3 2: acetic anhydride; triethylamine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Cs2CO3 | 17 Example 18 Preparation of 3-(2-chloro-4-fluorophenoxy)pyridine-N-oxide Example 18 2-Chloro-4-fluorophenol 1.5 g, 3-chloropyridine-N-oxide 1.6 g, cesium carbonate 4.9 g and dimethylformamide 10 mL were mixed at room temperature, and the mixture was heated to 140° C. and stirred for 20 hours. The resulting reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with chloroform 50 mL. The resulting organic layer was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3-(2-chloro-4-fluorophenoxy)pyridine-N-oxide 1.2 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 19 5-Amino-2-chloro-4-fluorophenol 3.3 g, 3-chloropyridine-N-oxide 3.1 g, tripotassium phosphate 12.7 g and dimethylformamide 10 mL were mixed at room temperature, and the mixture was heated to 140 C. and stirred for 22 hours. The resulting reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with chloroform 50 mL. The resulting organic layer was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3-(5-amino-2-chloro-4-fluorophenoxy)pyridine-N-oxide 2.2 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide | 34 Example 34 Example 34 3-Chloropyridine 200.2 g, water 31.3 g, sodium tungstate dihydrate 5.9 g and 98% concentrated sulfuric acid 14.1 g were mixed at room temperature, and the mixture was heated to 60° C. To the mixture kept at 60° C., 30% aqueous hydrogen peroxide solution 217.5 g was added dropwise over 11 hours. The mixture was stirred at 60° C. overnight, cooled to 35° C., and 22% aqueous sodium sulfite solution 300.8 g, 48% aqueous sodium hydroxide solution 102.2 g and NMP 197.9 g were added thereto, and the resulting mixture was separated with a separatory funnel to obtain an organic layer containing 3-chloropyridine-N-oxide 647.8 g (content: 30.0%, yield: 85%). |
Tags: 1851-22-5 synthesis path| 1851-22-5 SDS| 1851-22-5 COA| 1851-22-5 purity| 1851-22-5 application| 1851-22-5 NMR| 1851-22-5 COA| 1851-22-5 structure
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P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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