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CAS No. 1060811-62-2, is a pyridines compound, with a molecular weight of 176.00, molecular formula C6H3Cl2NO, Ambeed provides reports for batches of (such as HPLC, GC).

CAS No. : 1060811-62-2 Catalog No.: {[proInfo.prAm]}

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CAS No. :1060811-62-2MDL No. :MFCD12025485
Formula :C6H3Cl2NOInChI Key :AKYJFAHYRMPRDS-UHFFFAOYSA-N
M.W :176.00Pubchem ID :21698042
Boiling Point :-
Synonyms :

Computed Properties

TPSA : 30 H-Bond Acceptor Count : 2
XLogP3 : 1.9 H-Bond Donor Count : 0
SP3 : 0.00 Rotatable Bond Count : 1

Safety

Signal Word:WarningClassN/A
Precautionary Statements:P280-P305+P351+P338UN#:N/A
Hazard Statements:H302Packing Group:N/A
GHS Pictogram:

Application In Synthesis

[ 1060811-62-2 ] Synthesis Path-Upstream   1~12

  • 1
  • [ 73998-95-5 ]
  • [ 1060811-62-2 ]
YieldReaction ConditionsOperation in experiment
90% With manganese(IV) oxide In chloroform at 75℃; for 12.00 h; Part II -- Synthesis of 4,6-dichloropyridine-3-carbaldehyde [0231] (4,6-Dichloropyridin-3-yl)methanol (4.9 g, 28 mmol) was dissolved in CHC13 (100 mL). Mn02 (24 g, 280 mmol) was then added and the reaction mixture was stirred at 75 °C for 12 hours. Next, the reaction was cooled to room temperature, filtered through Celite, and concentrated to give 4,6-dichloropyridine-3-carbaldehyde. Yield 2.9 g (90percent>). LCMS (ESI): calc. C6H3C12N0 = 175; obs. M+H = low ionization.
88.4% With manganese(IV) oxide In dichloromethane at 20℃; (4,6-dichloropyridin-3-yl) methanol (4 g, 22.5 mmol) was dissolved in 200 mL of dichloromethane and then manganese dioxide (13.7 g, 157.6 mmol) was added and reacted at room temperature overnight. The manganese dioxide was removed by filtration through celite and the reaction solution was concentrated under reduced pressure to give 4,6-dichlorotolic aldehyde as a white solid(3.5 g, yield 88.4percent).Step 2, Preparation of intermediate 4,6-dichlorotolic aldehyde
88.4% With manganese(IV) oxide In dichloromethane at 20℃; (4,6-dichloropyridin-3-yl) methanol (4 g, 22.5 mmol) was dissolved in 200 mL of dichloromethane,Manganese dioxide (13.7 g, 157.6 mmol) was then added and allowed to react overnight at room temperature. The manganese dioxide was removed by filtration through celite, and the reaction solution was concentrated under reduced pressure to give 4,6-dichloronicotinic aldehyde (3.5 g, yield 88.4percent) as a white solid.
80% at 20℃; for 4.00 h; Inert atmosphere [01368] To a 2000-nt 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen was placed (4,6-dichloropyridin-3-yl)methanol (78.4 g, 440.41 mmol, 1.00 equiv), dichioromethane (1000 mL), PCC (284.83 g, 1.32 mol, 3.00 equiv) and Silica gel (235 g). The resulting mixture was stined at room temperature for 4 h and concentrated under vacuum. The residue was applied onto a silica gel colunm eluted with ethyl acetate/petroleum ether (0:1-1:6) to afford 62 g (80percent) of 4,6-dichloropyridine-3-carbaldehyde as a white solid.
80% With silica gel; pyridinium chlorochromate In dichloromethane at 20℃; for 4.00 h; Inert atmosphere To a 2000-mL 4-necked round-bottom flask, purged and maintained with an inert atmosphere of nitrogen, was placed (4,6-dichloropyridin-3-yl)methanol (78.4 g, 440.41 mmol, 1.00 equiv), dichloromethane (1000 mL), PCC (284.83 g, 1.32 mol, 3.00 equiv) and Silica gel (235 g). The resulting mixture was stirred at room temperature for 4 h and concentrated under vacuum. The residue was applied onto a silica gel column eluted with ethyl acetate/petroleum ether (0:1-1 :6) to afford 62 g (80percent) of 4,6-dichloropyridine-3-carbaldehyde as a white solid.
72.76% With Dess-Martin periodane In dichloromethane at 0 - 20℃; for 2.00 h; Inert atmosphere To a solution of (4,6-dichloropyridin-3-yl)methanol (4.9 g, 1.0 eq) in DCM (150 mL) at 0°C under nitrogen atmosphere, Dess-Martin periodinane (17.5 g, 1.5 eq) was added and stirred at rt for 2 h while monitoring by TLC. After TLC showed completion of starting material, the solution was quenched with water (20 mL) and filtered through Celite® bed. The filtrate was extracted with DCM (150 mL) and the organic layer was washed with saturated NaHC03 solution (100 mL), brine (100 mL), dried over anhydrous sodium sulphate, filtered and concentrated. The resulting crude was purified by flash chromatography (Combiflash® - Redisep, 120 g) using EtOAc in hexane as the eluent. The 4,6-dichloronicotinaldehyde was eluted at 7percent EtOAc in hexane. The aldehyde fractions were concentrated to obtain aldehyde as off-white solid (3.5 g, 72.76percent). 1H NMR (400 MHz, CDC13): δ 10.432 (s, 1H), 8.842 (s, 1H), 7.489 (s, 1H).
1.53 g
Stage #1: With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -78℃; for 0.50 h; Inert atmosphere
Stage #2: With triethylamine In dichloromethane at -78℃; for 0.50 h;
A solution of oxalyl chloride (2.32 mL, 26.963 mmol) in DCM (30 mL) was cooled down to -78 °C. To this solution was added DMSO (3.83 mL, 53.922 mmol) dropwise under nitrogen atmosphere. The reaction mixture was stirred at the same temperature for another 30 min. To this reaction mixture was added a solution of (4,6-dichloro-3- pyridyl)methanol (1.6 g, 8.987 mmol) in DCM (10 mL), and then the reaction mixture was stirred for 30 min. Then, to this stirred reaction mixture was added triethylamine (11.2 mL, 80.883 mmol). The reaction mixture was stirred at the same temperature for another 30 min. The progress of reaction was monitored by TLC. After completion of reaction, the mixture was quenched with saturated sodium bicarbonate solution (30 mL). The product was extracted using DCM (2x50 mL). The combined organic layer was again washed with water (3x30 mL) and finally with brine solution (30 mL). The organic layer was separated, dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford 4,6-dichloropyridine-3-carbaldehyde (1.53 g) as a light yellow solid

Reference: [1] Patent: WO2013/169704, 2013, A2. Location in patent: Paragraph 0231
[2] Patent: CN106810558, 2017, A. Location in patent: Paragraph 0158; 0162; 0163
[3] Patent: CN106810559, 2017, A. Location in patent: Paragraph 0162; 0167; 0170; 0171
[4] Patent: WO2016/128529, 2016, A1. Location in patent: Paragraph 01364; 01367; 01368
[5] Patent: WO2018/15410, 2018, A1. Location in patent: Paragraph 0284; 0288-0290
[6] Patent: WO2015/38417, 2015, A1. Location in patent: Page/Page column 77
[7] Patent: WO2015/103355, 2015, A1. Location in patent: Paragraph 0163
  • 2
  • [ 40296-46-6 ]
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YieldReaction ConditionsOperation in experiment
87.52% With diisobutylaluminium hydride In dichloromethane at -78℃; for 1.00 h; To a solution of 202.1 (lOg, 0.045mmol, l .Oeq) in dichloromethane (lOOmL) at -78°C, diisobutyl aluminium hydride (54mL, 0.054mmol, 1.2eq) was added. Reaction mixture was stirred at -78°C for lh. After completion of reaction, methanol was slowly added to the reaction mixture at -78°C followed by addition of IN HC1 and extracted with dichloromethane. Organic layer was combined, washed with brine solution, dried over sodium sulphate and concentrated under reduced pressure to obtain 206.1. (7.0g, 87.52 percent). MS(ES): m/z 175.48 [M]+
80% With diisobutylaluminium hydride In dichloromethane; toluene at -60 - -50℃; for 3.33 h; Inert atmosphere A stirred -60 °C solution of ethyl 4,6-dichloronicotinate (4.0 g, 18.2 mmol) in DCM (70mL) was treated dropwise with diisobutylaluminum hydride (1 M in toluene) (20.0 mL,20.0 mmol) over 20 mins (temperature -50 °C to -60 °C during addition), and stirred at -60°C for 3 hours. The reaction was quenched by dropwise addition of 1M HC1 (50 mL) andstirred for 1 hour. Extra DCM (100 mL) was added, the layers separated, and the aqueouslayer was extracted with another portion of DCM (100 mL). The combined organic layerswere washed with brine, dried and evaporated to give a crude solid which was purified byflash silica chromatography, elution gradient 0 to 20percent EtOAc in heptane. Pure fractions were evaporated to dryness to afford 4,6-dichloronicotinaldehyde (2.55 g, 80percent) as a white crystalline solid. ‘H NMR (500 MHz, DMSO-d6, 27 °C) 8.02 (1H, d), 8.80 (1H, t), 10.25 (1H, s). m/z: ES+ [M+MeOH2]+ 208.
65% With diisobutylaluminium hydride In dichloromethane at -78℃; for 3.00 h; To a solution of ethyl 4,6-dichloronicotinate (500 mg, 2.43 mmol) in DCM at - 78°C, DIBAL-H (2.67 mL, 2.67 mmol) was added dropwise and stirred for 3h at -78°C. The mixture was allowed to warm up to 0°C then water (0.12 mL) was added dropwise to the mixture followed by aq. NaOH (15percent, 0.12 mL). H20 (0.3 mL) was added then the mixture was warmed up to room temperature and stirred for 15 min and the organic layer collected, dried over MgS04 and filtered with the filtrate concentrated to give the desired product with was used without further purification (280 mg, Yield 65percent). LCMS (m/z): 176.1 [M+H]+.
Reference: [1] Patent: WO2018/71794, 2018, A1. Location in patent: Paragraph 00950; 00951
[2] Patent: WO2018/19793, 2018, A1. Location in patent: Page/Page column 127
[3] Patent: WO2014/100695, 2014, A1. Location in patent: Paragraph 00436
[4] Patent: US2014/315902, 2014, A1. Location in patent: Paragraph 0327; 0328
[5] Patent: WO2015/38417, 2015, A1
[6] Patent: US2016/115164, 2016, A1. Location in patent: Paragraph 0312
[7] Patent: WO2016/134320, 2016, A1. Location in patent: Page/Page column 74
[8] Patent: WO2016/134294, 2016, A1. Location in patent: Paragraph 0181
[9] Patent: WO2016/134314, 2016, A1. Location in patent: Page/Page column 49
[10] Patent: CN106810558, 2017, A
[11] Patent: CN106810559, 2017, A
[12] Patent: WO2018/218100, 2018, A1. Location in patent: Page/Page column 68; 69
  • 3
  • [ 65973-52-6 ]
  • [ 1060811-62-2 ]
YieldReaction ConditionsOperation in experiment
73% With diisobutylaluminium hydride In dichloromethane at -78℃; for 3.00 h; 4,6-Dichloropyridine-3-carbaldehyde To the solution of methyl 4, β-dichloropyridine-S-carboxylate (20 g, 91.32 mmol) in CH2CI2 (200 ml) at -78 0C was added DIBAL-H (1.5 N in CH2Cl2) (100.4 mmol, 64 ml) dropwise and stirred for 3 h at -78 0C. The reaction mixture was quenched with 1.5 N HCl at -78 0C and was allowed to stir at room temperature for 1 hour. The reaction mixture was extracted with CH2Cl2, which was washed with brine and dried (NaSO4). The solvent was removed and the residue was purified by flash column chromatography using ethyl acetate-petroleum ether as eluent to give product as a white solid. Yield: 12 g (73percent). MS (ES) MH+: 177.2 for C6H3Cl2NO.
45%
Stage #1: With diisobutylaluminium hydride In dichloromethane at -70℃; for 0.50 h;
Stage #2: With hydrogenchloride In dichloromethane; water
To a solution of methyl 4,6-dichloronicotinate (370 g, 1.8 mol) in dichloromethane (4500 mL) was added diisobutylaluminum hydride (1.00 M in dichloromethane, 1974 mL) at -70 °C. The reaction was stirred at -70 °C for 30 min, quenched with 2M HCl, and extracted with dichloromethane (2x). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude material was purified via flash chromatography on silica gel (eluent: 30percent EtOAc in heptane) to give 4,6-dichloronicotinaldehyde (76.8 g, yield 45percent). LCMS (ESI) [M+H]+ = 177.9; lH NMR (400 MHz, CDC13): δ 10.44 (d, J= 1.6 Hz, 1H), 8.84 (d, J= 2.0 Hz, 1H), 7.50 (s, 1H).
Reference: [1] Journal of the Chinese Chemical Society, 2016, vol. 63, # 9, p. 758 - 769
[2] Patent: WO2009/10801, 2009, A1. Location in patent: Page/Page column 70
[3] Patent: WO2014/210354, 2014, A1. Location in patent: Page/Page column 41
[4] Patent: WO2012/96813, 2012, A1. Location in patent: Page/Page column 42
[5] Patent: WO2013/169704, 2013, A2
[6] Patent: WO2015/103355, 2015, A1
  • 4
  • [ 40296-46-6 ]
  • [ 73998-95-5 ]
  • [ 1060811-62-2 ]
YieldReaction ConditionsOperation in experiment
33.5% With diisobutylaluminium hydride In dichloromethane; toluene at -78℃; for 0.50 h; Inert atmosphere To a stirred solution of ethyl 4,6-dichloronicotinate (36.8 g, 1.0 eq) in DCM (250 mL) at -78°C under nitrogen atmosphere, DiBAL-H (1.2 eq, 1M solution in toluene) was added drop wise and stirred at -78°C for 30 min while monitoring by TLC. After TLC showed completion of starting material, the solution was quenched with saturated ammonium chloride solution (50 mL) at -78°C and diluted with DCM (1 L). The layers were separated and the organic layer was washed with brine (200 mL), dried over anhydrous sodium sulphate, filtered and concentrated. The resulting crude material was purified by flash chromatography (Combiflash® - Redisep, 120 g) using EtOAc in hexane as the eluent. The 4,6-dichloronicotinaldehyde was eluted at 7percent EtOAc in hexane and the (4,6-dichloropyridin-3-yl)methanol was eluted at 10percent EtOAc in hexane. The aldehyde fractions were concentrated to obtain aldehyde as white solid (9.86 g, 33.5percent). 1H NMR (400 MHz, CDC13): δ 10.428 (s, 1H), 8.837 (s, 1H), 7.489 (s, 1H). The alcohol fractions were concentrated to obtain alcohol as off-white solid (4.314 g). 1H NMR (400 MHz, DMSO-d6): δ 8.455 (s, 1H), 7.761 (s, 1H), 5.601 (d, 1H), 4.594 (d, 2H).
Reference: [1] Patent: WO2015/38417, 2015, A1. Location in patent: Page/Page column 76; 77
  • 5
  • [ 1830-54-2 ]
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Reference: [1] Patent: WO2014/210354, 2014, A1
[2] Journal of the Chinese Chemical Society, 2016, vol. 63, # 9, p. 758 - 769
  • 6
  • [ 79398-27-9 ]
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Reference: [1] Patent: WO2014/210354, 2014, A1
[2] Journal of the Chinese Chemical Society, 2016, vol. 63, # 9, p. 758 - 769
  • 7
  • [ 73027-79-9 ]
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Reference: [1] Patent: WO2016/128529, 2016, A1
[2] Patent: WO2018/15410, 2018, A1
  • 8
  • [ 6975-44-6 ]
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Reference: [1] Patent: WO2015/38417, 2015, A1
[2] Patent: WO2015/38417, 2015, A1
  • 9
  • [ 105-50-0 ]
  • [ 1060811-62-2 ]
Reference: [1] Patent: WO2015/38417, 2015, A1
[2] Patent: WO2015/38417, 2015, A1
  • 10
  • [ 61043-19-4 ]
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Reference: [1] Journal of the Chinese Chemical Society, 2016, vol. 63, # 9, p. 758 - 769
  • 11
  • [ 26452-80-2 ]
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Reference: [1] Patent: WO2018/218100, 2018, A1
  • 12
  • [ 134031-21-3 ]
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Reference: [1] Patent: WO2018/218100, 2018, A1

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