117873-72-0|2,6-Dibromo-4-methoxypyridine| Ambeed

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Quality Control of [ 117873-72-0 ] Purity: 96% SDS Specification

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Product Details of [ 117873-72-0 ]

CAS No. :	117873-72-0
Formula :	C₆H₅Br₂NO
M.W :	266.92
SMILES Code :	COC1=CC(Br)=NC(Br)=C1
MDL No. :	MFCD11036227
InChI Key :	FBLLPCQLOGKHAL-UHFFFAOYSA-N
Pubchem ID :	10901569

Safety of [ 117873-72-0 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302-H315-H319-H332-H335
Precautionary Statements:	P261-P280-P305+P351+P338

Computational Chemistry of [ 117873-72-0 ] Show Less

Physicochemical Properties

Num. heavy atoms	10
Num. arom. heavy atoms	6
Fraction Csp3	0.17
Num. rotatable bonds	1
Num. H-bond acceptors	2.0
Num. H-bond donors	0.0
Molar Refractivity	46.13
TPSA ? Topological Polar Surface Area: Calculated from Ertl P. et al. 2000 J. Med. Chem.	22.12 Å²

Lipophilicity

Log P_o/w (iLOGP)? iLOGP: in-house physics-based method implemented from Daina A et al. 2014 J. Chem. Inf. Model.	2.38
Log P_o/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry	2.87
Log P_o/w (WLOGP)? WLOGP: Atomistic method implemented from Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.	2.62
Log P_o/w (MLOGP)? MLOGP: Topological method implemented from Moriguchi I. et al. 1992 Chem. Pharm. Bull. Moriguchi I. et al. 1994 Chem. Pharm. Bull. Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.	1.67
Log P_o/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com	2.71
Consensus Log P_o/w? Consensus Log P_o/w: Average of all five predictions	2.45

Water Solubility

Log S (ESOL):? ESOL: Topological method implemented from Delaney JS. 2004 J. Chem. Inf. Model.	-3.68
Solubility	0.0556 mg/ml ; 0.000208 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Soluble
Log S (Ali)? Ali: Topological method implemented from Ali J. et al. 2012 J. Chem. Inf. Model.	-2.99
Solubility	0.271 mg/ml ; 0.00101 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Soluble
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com	-3.86
Solubility	0.037 mg/ml ; 0.000139 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Soluble

Pharmacokinetics

GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg	High
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg	Yes
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) and tested on 415 molecules (test set) 10-fold CV: ACC=0.72 / AUC=0.77 External: ACC=0.88 / AUC=0.94	No
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) and tested on 3000 molecules (test set) 10-fold CV: ACC=0.83 / AUC=0.90 External: ACC=0.84 / AUC=0.91	Yes
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) and tested on 3000 molecules (test set) 10-fold CV: ACC=0.80 / AUC=0.86 External: ACC=0.80 / AUC=0.87	No
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) and tested on 2075 molecules (test set) 10-fold CV: ACC=0.78 / AUC=0.85 External: ACC=0.71 / AUC=0.81	No
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) and tested on 1068 molecules (test set) 10-fold CV: ACC=0.79 / AUC=0.85 External: ACC=0.81 / AUC=0.87	No
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) and tested on 2579 molecules (test set) 10-fold CV: ACC=0.77 / AUC=0.85 External: ACC=0.78 / AUC=0.86	No
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from Potts RO and Guy RH. 1992 Pharm. Res.	-5.89 cm/s

Druglikeness

Lipinski? Lipinski (Pfizer) filter: implemented from Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev. MW ≤ 500 MLOGP ≤ 4.15 N or O ≤ 10 NH or OH ≤ 5	0.0
Ghose? Ghose filter: implemented from Ghose AK. et al. 1999 J. Comb. Chem. 160 ≤ MW ≤ 480 -0.4 ≤ WLOGP ≤ 5.6 40 ≤ MR ≤ 130 20 ≤ atoms ≤ 70	None
Veber? Veber (GSK) filter: implemented from Veber DF. et al. 2002 J. Med. Chem. Rotatable bonds ≤ 10 TPSA ≤ 140	0.0
Egan? Egan (Pharmacia) filter: implemented from Egan WJ. et al. 2000 J. Med. Chem. WLOGP ≤ 5.88 TPSA ≤ 131.6	0.0
Muegge? Muegge (Bayer) filter: implemented from Muegge I. et al. 2001 J. Med. Chem. 200 ≤ MW ≤ 600 -2 ≤ XLOGP ≤ 5 TPSA ≤ 150 Num. rings ≤ 7 Num. carbon > 4 Num. heteroatoms > 1 Num. rotatable bonds ≤ 15 H-bond acc. ≤ 10 H-bond don. ≤ 5	0.0
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat implemented from Martin YC. 2005 J. Med. Chem.	0.55

Medicinal Chemistry

PAINS? Pan Assay Interference Structures: implemented from Baell JB. & Holloway GA. 2010 J. Med. Chem.	0.0 alert
Brenk? Structural Alert: implemented from Brenk R. et al. 2008 ChemMedChem	1.0 alert: heavy_metal
Leadlikeness? Leadlikeness: implemented from Teague SJ. 1999 Angew. Chem. Int. Ed. 250 ≤ MW ≤ 350 XLOGP ≤ 3.5 Num. rotatable bonds ≤ 7	No; 1 violation:MW<0.0
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties, trained on 12'782'590 molecules and tested on 40 external molecules (r² = 0.94)	1.87

Application In Synthesis of [ 117873-72-0 ]

* 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.

Downstream synthetic route of [ 117873-72-0 ]

[ 117873-72-0 ] Synthesis Path-Downstream 1~35

1
[ 67-56-1 ]
[ 2408-70-0 ]
[ 117873-72-0 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1948,vol. 67,p. 381,383.

2
[ 117873-72-0 ]
[ 10163-34-5 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1948,vol. 67,p. 381,383.

3
[ 2408-70-0 ]
[ 124-41-4 ]
[ 117873-72-0 ]
[ 117873-73-1 ]

References: [1]Chemische Berichte,1989,vol. 122,p. 589 - 592.

4
[ 117873-72-0 ]
[ 117873-74-2 ]

References: [1]Chemische Berichte,1989,vol. 122,p. 589 - 592.

5
[ 117873-72-0 ]
[ 5932-27-4 ]
1-(6-Bromo-4-methoxy-pyridin-2-yl)-1H-pyrazole-3-carboxylic acid ethyl ester [ No CAS ]
[ 188626-14-4 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.

6
[ 124-41-4 ]
[ 175422-04-5 ]
[ 117873-72-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With methanol; In tetrahydrofuran; at 20℃; for 2h;	To a solution of compound S1 (2 g, 7.11 mmol) in THF (15 mL) was added MeONa/MeOH solution (1.2 mL, 6.05 mmol, 1.3 M). The reaction was stirred at room temperature for 2 hrs and quenched with water. The resulting mixture was extracted with EtOAc twice. The combined organic phases were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated to dryness. The residue was purified by silica gel column eluted with (PE/Acetone=30/1) to give the title compound (1.45 g, 70% yield) as a white solid.

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.
[2]Patent: WO2017/35353,2017,A1 .Location in patent: Paragraph 0905.

7
[ 2408-70-0 ]
methanol. NaOH-solution [ No CAS ]
[ 117873-72-0 ]
[ 276251-83-3 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1948,vol. 67,p. 381,383.

8
[ 437710-07-1 ]
[ 117873-72-0 ]

References: [1]Journal of Organic Chemistry,2002,vol. 67,p. 3272 - 3276.

9
[ 117873-72-0 ]
[ 75-07-0 ]
2,6-dibromo-4-methoxy-α-methylpyridine-3-methanol [ No CAS ]

References: [1]Journal of Organic Chemistry,2002,vol. 67,p. 3272 - 3276.

10
[ 117873-72-0 ]
[ 630-18-2 ]
[ 862202-10-6 ]

Yield	Reaction Conditions	Operation in experiment
86%		2,6-Dibromo-4-methoxy pyridine (6) was obtained in 80% yield when 2,4,6-tribromopyridine (5) was allowed to react with sodium methoxide (1.2 eq) in refluxing methanol. The compound (6) was treated using n-butyl lithium (1.2 eq.), was allowed to react with pivalonitrile (1.2 eq.) for 150 minutes at -78C and was refluxed for two hours in two normal sulfuric acid to yield ketone isomer (7) in 86% yield. An optically active alcohol (8) was obtained in 93% yield and in 90% ee optical purity from compound (7) through hydrogen transfer type asymmetric reduction of formic acid (4.3 eq.) and triethylamine (2.5 eq.) using the asymmetric ruthenium catalyst (RuCl[(S,S]-Tsdpen)(p-cumene), 0.01 eq.) as the catalyst. The compound (8) was converted to a camphor ester using the acid chloride, an optical resolution process was conducted using re-crystallization (75% yield, diastereomer ratio = >99/<1) and saponified again to obtain an almost optically pure alcohol (7, quant.). The compound (7) was subjected to homo coupling using a palladium catalyst [PdCl2(PhCN)2-TDAE] to yield a pyridine isomer (9) (Chemical formula 5) in 36% yield (diastereomer ratio =>99.5/<0.5).

References: [1]Synthesis,2005,p. 2176 - 2182.
[2]Patent: EP1724251,2006,A1 .Location in patent: Page/Page column 5; 9.

11
[ 117873-72-0 ]
(R)-1-(6-bromo-4-methoxypyridin-2-yl)-2,2-dimethylpropan-1-ol [ No CAS ]

References: [1]Synthesis,2005,p. 2176 - 2182.

12
[ 117873-72-0 ]
[ 862202-11-7 ]

References: [1]Synthesis,2005,p. 2176 - 2182.

13
[ 117873-72-0 ]
(S,S)-6,6'-bis(1-hydroxy-2,2-dimethylpropyl)-4,4'-dimethoxy-2,2'-bipyridine [ No CAS ]

References: [1]Synthesis,2005,p. 2176 - 2182.

14
[ 1122-96-9 ]
[ 117873-72-0 ]

References: [1]Journal of Organic Chemistry,2002,vol. 67,p. 3272 - 3276.

15
[ 626-05-1 ]
[ 117873-72-0 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.
[2]Chemische Berichte,1989,vol. 122,p. 589 - 592.
[3]Inorganic Chemistry,2019.

16
[ 25373-69-7 ]
[ 117873-72-0 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.
[2]Chemische Berichte,1989,vol. 122,p. 589 - 592.

17
[ 117873-72-0 ]
[ 188626-16-6 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.

18
[ 117873-72-0 ]
[ 188626-17-7 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.

19
[ 117873-72-0 ]
[1-(6-{3-[(Bis-carboxymethyl-amino)-methyl]-pyrazol-1-yl}-4-methoxy-pyridin-2-yl)-1H-pyrazol-3-ylmethyl]-carboxymethyl-amino}-acetic acid [ No CAS ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.

20
[ 117873-72-0 ]
[ 188626-18-8 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.

21
[ 98027-81-7 ]
[ 117873-72-0 ]

References: [1]Helvetica Chimica Acta,1997,vol. 80,p. 86 - 96.
[2]Chemische Berichte,1989,vol. 122,p. 589 - 592.

22
[ 117873-72-0 ]
[ 117873-76-4 ]

References: [1]Chemische Berichte,1989,vol. 122,p. 589 - 592.

23
[ 117873-72-0 ]
[ 117873-75-3 ]

References: [1]Chemische Berichte,1989,vol. 122,p. 589 - 592.

24
[ 117873-72-0 ]
[ 117873-77-5 ]

References: [1]Chemische Berichte,1989,vol. 122,p. 589 - 592.

25
[ 117873-72-0 ]
[ 98-17-9 ]
[ 192447-50-0 ]

Yield	Reaction Conditions	Operation in experiment
	In hexane; N,N-dimethyl-formamide; mineral oil;	(1) Production of 2-bromo-4-methoxy-6-{3-(trifluoromethyl)phenoxy} pyridine as an intermediate product 3.34 g (0.1871.1 mol) of 3-(trifluoromethyl) phenol was dissolved in about 30 ml of dimethyl formamide. The solution was further mixed with 0.78 g (ca. 60% in mineral oil; 0.01871.04 mol) of sodium hydride and then with 5.00 g (0.0187 mol) of <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong>. After stirring at about 120 C. for about 2 hours, the mixture was allowed to stand for cooling to room temperature. After the reaction solution was distributed with hexane-saturated sodium bicarbonate water, the organic phase of the obtained solution was washed with saturated brine and dried with anhydrous sodium sulfate. The resultant solution was concentrated and then purified by silica gel column chromatography (eluding solution: ethyl acetate/hexane), and the obtained product was subjected to recrystallization using hexane, thereby obtaining an aimed product. Yield by weight: 3.23 g; yield by percentage: 50%; solid; melting point: 57 to 60 C.; 1 H-NMR (60 MHz, CDCl3, delta): 3.75 (3H, s), 6.26 (1H, d, J=2 Hz), 6.75 (1H, d, J=2 Hz), 7.0-7.6 (4H, complex).
	In hexane-saturated sodium bicarbonate water; hexane; N,N-dimethyl-formamide; mineral oil;	(1) <Production of 2-bromo-4-methoxy-6-[3-(trifluoromethyl)phenoxy] pyridine as an intermediate product> 3-(trifluoromethyl) phenol (3.34 g; 0.01871.1 mol) was dissolved in dimethyl formamide (about 30 ml). Further, sodium hydride [0.78 g (ca. 60% in mineral oil), 0.01871.0 mol] and then <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong> (5.00 g, 0.0187 mol) were added to the solution. The obtained solution was stirred at about 120 C. for about 2 hours and, thereafter, allowed so as to stand and cooled to room temperature. The obtained reaction solution was distributed in hexane-saturated sodium bicarbonate water. The organic phase separated from the reaction solution was washed with saturated brine, and dried with anhydrous sodium sulfate. The resultant solution was concentrated and then purified by silica gel column chromatography (eluding solution: ethyl acetate/hexane), and the obtained purified product was subjected to recrystallization using hexane, thereby obtaining an aimed product. Yield weight: 3.23 g; yield percentage: 50%; solid; melting point: 57 to 60 C.; 1 H-NMR (60 MHz, CDCl3, delta): 3.75(3H, s), 6.26(1H, d, J=2 Hz), 6.75(1H, d, J=2 Hz), 7.0-7.6(4H, complex).
	In hexane-saturated sodium bicarbonate water; hexane; N,N-dimethyl-formamide; mineral oil;	(1) Production of 2-bromo-4-methoxy-6-[3-(trifluoromethyl)phenoxy] pyridine as an intermediate 3-(trifluoromethyl) phenol (3.34 g; 0.01871.1 mol) was dissolved in dimethyl formamide (hereinafter referred to merely as "DMF") (approximately 30 ml). Further, sodium hydride [0.78 g (ca. 60% in mineral oil), 0.01871.0 mol] and then <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong> (5.00 g, 0.0187 mol) were added to the solution. The obtained solution was stirred at about 120 C. for about 2 hours and, thereafter, allowed to stand so as to be cooled to room temperature. The obtained reaction solution was distributed in hexane-saturated sodium bicarbonate water. The organic phase separated from the reaction solution was washed with saturated brine, and dried with anhydrous sodium sulfate. The resultant solution was concentrated and then purified by silica gel column chromatography (eluding solution: ethyl acetate/hexane), and the obtained purified product was subjected to recrystallization using hexane, thereby obtaining an aimed product. Yield weight: 3.23 g; yield by percentage: 50%; solid; melting point: 57 to 60 C.; 1H-NMR (60 MHz, CDCl3, delta): 3.75(3H, s), 6.26(1H, d, J=2 Hz), 6.75(1H, d, J=2 Hz), 7.0-7.6(4H, complex).

References: [1]Patent: US6339045,2002,B1 .Location in patent: Example 1.
[2]Patent: US6005112,1999,A .
[3]Patent: US6159901,2000,A .
[4]Patent: US6200933,2001,B1 .

26
[ 117873-72-0 ]
[ 827-99-6 ]
[ 193074-41-8 ]

Yield	Reaction Conditions	Operation in experiment
	In hexane; N,N-dimethyl-formamide; mineral oil;	(1) Production of 2-bromo-4-methoxy-6-{3-(trifluoromethoxy)phenoxy} pyridine as an intermediate product 2.00 g (0.009371.2 mol) of 3-(trifluoromethoxy) phenol was dissolved in about 20 ml of dimethyl formamide. The solution was further mixed with 0.39 g (ca. 60percent in mineral oil; 0.009371.04 mol) of sodium hydride and then with 2.50 g (0.00937 mol) of <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong>. After stirring at about 110° C. for about 4 hours, the mixture was allowed to stand for cooling to room temperature. After the reaction solution was distributed with hexane-saturated sodium bicarbonate water, the organic phase of the obtained solution was washed with saturated brine and dried with anhydrous sodium sulfate. The resultant solution was concentrated and then purified by silica gel column chromatography (eluding solution: ethyl acetate/hexane), and the obtained product was subjected to recrystallization using hexane, thereby obtaining an aimed product. Yield by weight: 1.40 g; yield by percentage: 41percent; oily substance; 1 H-NMR (60 MHz, CDCl3, delta): 3.73 (3H, s), 6.25 (1H, d, J=2 Hz), 6.69 (1H, d, J=2 Hz), 6.7-7.5 (4H, complex).

References: [1]Patent: US6339045,2002,B1 .Location in patent: Example 2.
[2]Patent: US6005112,1999,A .

27
[ 67-56-1 ]
[ 175422-04-5 ]
[ 117873-72-0 ]

Yield	Reaction Conditions	Operation in experiment
		Methanol (1.48 g, 46.1 mmol) is slowly added to a cooled suspension (00C) of NaH (2.12 g, 53.2 mmol, 60% dispersion in mineral oil, washed with hexane prior to <n="85"/>use) in THF (20 ml_). Upon completion of the addition the mixture is stirred at 00C for 150 min before 2,6-dibromo-4-nitropyridine (10.0 g, 35.4 mmol) is added. The temperature rises to 14C. The mixture is stirred at rt for 3 h before the reaction is quenched with sat. aq. NH4CI solution. The mixture is diluted with water and extracted twice with EA (250 ml_). The combined org. extracts are dried over MgSO4, filtered and concentrated. The crude product is purified by CC on silica gel eluting with DCM to give 2,6-dibromo-4-methoxy-pyridine (6.43 g) as an off-white solid; LC-MS: tR = 0.90 min, [M+1]+ = 267.75.
		a) Methanol (1.48 g, 46.1 mmol) is slowly added to a cooled suspension (0 C.) of NaH (2.12 g, 53.2 mmol, 60% dispersion in mineral oil, washed with hexane prior to use) in THF (20 mL). Upon completion of the addition the mixture is stirred at 0 C. for 150 min before 2,6-dibromo-4-nitropyridine (10.0 g, 35.4 mmol) is added. The temperature rises to 14 C. The mixture is stirred at rt for 3 h before the reaction is quenched with sat. aq. NH4Cl solution. The mixture is diluted with water and extracted twice with EA (250 mL). The combined org. extracts are dried over MgSO4, filtered and concentrated. The crude product is purified by CC on silica gel eluting with DCM to give 2,6-dibromo-4-methoxy-pyridine (6.43 g) as an off-white solid; LC-MS: tR=0.90 min, [M+1]+=267.75.

References: [1]Patent: US6339045,2002,B1 .Location in patent: Example 1.
[2]Patent: WO2009/24905,2009,A1 .Location in patent: Page/Page column 83-84.
[3]Patent: US2011/212998,2011,A1 .Location in patent: Page/Page column 30.

28
[ 117873-72-0 ]
C₆H₅BrLiNO [ No CAS ]

References: [1]Patent: US6339045,2002,B1 .Location in patent: Example 8.

29
[ 117873-72-0 ]
ethyl acetate-saturated sodium bicarbonate water [ No CAS ]
[ 3173-56-6 ]
N-benzyl-6-bromo-4-methoxy-2-pyridine carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; n-butyllithium; In diethyl ether; hexane;	Production Example 5 Production of N-benzyl-6-bromo-4-methoxy-2-pyridine carboxamide (compound No. I-9) 1.0 g (0.0037 mol) of <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong> was suspended in about 15 ml of diethyl ether. While cooling the suspension in a dry ice-acetone bath in an argon atmosphere, 2.6 ml of about 1.6M hexane solution of BuLi (0.00371.1 mol) was added to the suspension, followed by stirring for about 10 minutes. After 0.75 g (0.00371.5 mol) of benzyl isocyanate dissolved in about 5 ml of diethyl ether was added to the reaction solution, the bath was removed and stirred at room temperature for about 40 minutes. The reaction solution was mixed with about 5 ml of 1N hydrochloric acid aqueous solution, and then distributed with ethyl acetate-saturated sodium bicarbonate water, followed by washing with saturated brine. The organic phase of the obtained solution was dried with anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography (eluding solution: ethyl acetate/hexane), thereby obtaining an aimed product. Yield by weight: 1.04 g; yield by percentage: 86%; solid; melting point: 107 to 111 C.; 1 H-NMR (60 MHz, CDCl3, delta): 3.75 (3H, s), 4.52 (2H, d, J=6 Hz), 6.94 (1H, d, J=2 Hz), 7.20 (5H, s), 7.59 (1H, d, J=2 Hz), 7.8-8.4 (1H, br).

References: [1]Patent: US6005112,1999,A .

30
[ 175422-04-5 ]
[ 117873-72-0 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; methanol; mineral oil;	(1) Production of 2,6-dibromo-4-methoxy pyridine as an intermediate product 1.49 g (ca. 60% in mineral oil; 0.03551.05 mol) of sodium hydride was washed with hexane and suspended in tetrahydrofuran. The suspension was mixed with 1.70 g (0.03551.5 mol) of methanol and then with 10.00 g (0.0355 mol) of 2,6-dibromo-4-nitropyridine, and stirred at room temperature for about one hour. Further, the suspension was mixed with 0.2 g (ca. 60% in mineral oil; 0.03550.14 mol) of sodium hydride, and stirred for about one hour. Next, 1.0 g (0.03550.9 mol) of methanol was added to the suspension, and after it was determined that no foaming was caused therein, the reaction solution was distributed with ethyl acetate-saturated sodium bicarbonate water. The organic phase of the obtained reaction solution was washed with saturated brine, dried with anhydrous sodium sulfate and then concentrated, thereby obtaining an aimed product. Yield by weight: 9.27 g; yield by percentage: 98%; solid; melting point: 131 to 133 C.; 1 H-NMR (60 MHz, CDCl3, delta): 3.79 (3H, s), 6.89 (2H, s).
	In tetrahydrofuran; methanol; mineral oil;	(1) Synthesis of an Intermediate, 2,6-dibromo-4-methoxypyridine Sodium hydride (1.49 g (ca.60% in mineral oil), 0.03551.05 mol) was washed with hexane and suspended in tetrahydrofuran, and methanol (1.70 g, 0.03551.5 mol) was added thereto. Then, 2,6-dibromo-4-nitropyridine (10.00 g, 0.0355 mol) was added thereto and the resultant solution was stirred for about 1 hour at room temperature. Additional sodium hydride (0.2 g (Ca.60% in mineral oil), 0.03550.14 mol) was added, then the resultant solution was stirred for about 1 hour. After it was confirmed that there was no bubbling with the addition of methanol (1.0 g, 0.03550.9 mol), the reaction solution was partitioned between ethyl acetate and aqueous saturated sodium hydrogen carbonate. The obtained organic layer was washed with aqueous saturated sodium chloride, dried over anhydrous sodium sutfate and thereafter concentrated to obtain the end product. Yield: 9.27 g (98%). Solid. Melting point: 131 to 133 C. 1 H-NMR (60 MHz, CDCl3, delta): 3.79(3H, s), 6.89(2H, s).

References: [1]Patent: US6005112,1999,A .
[2]Patent: US5691277,1997,A .

31
[ 117873-72-0 ]
ethyl acetate-saturated sodium bicarbonate water [ No CAS ]
[ 1795-48-8 ]
N-(i-propyl)-6-bromo-4-methoxy-2-pyridine carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; n-butyllithium; In diethyl ether; hexane;	Production Example 6 Production of N-(i-propyl)-6-bromo-4-methoxy-2-pyridine carboxamide (compound No. I-10) 1.0 g (0.0037 mol) of <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong> was suspended in about 15 ml of diethyl ether. While cooling the suspension in a dry ice-acetone bath in an argon atmosphere, 2.6 ml of about 1.6M hexane solution of BuLi (0.00371.1 mol) was added to the suspension, followed by stirring for about 10 minutes. After 0.64 g (0.00372.0 mol) of i-propyl isocyanate dissolved in about 5 ml of diethyl ether was added to the reaction solution, the bath was removed and stirred at room temperature for about 40 minutes. The reaction solution was mixed with about 5 ml of 1N hydrochloric acid aqueous solution, and then distributed with ethyl acetate-saturated sodium bicarbonate water, followed by washing with saturated brine. The organic phase of the obtained solution was dried with anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography (eluding solution: ethyl acetate/hexane), thereby obtaining an aimed product. Yield by weight: 0.76 g; yield by percentage: 74%; solid; melting point: 70 to 76 C.; 1 H-NMR (60 MHz, CDCl3, delta): 1.25 (6H, d, J=6.4 Hz), 3.82 (3H, s), 3.8-4.6 (1H, mult.), 6.98 (1H, d, J=2 Hz), 7.0-7.9 (1H, br), 7.61 (1H, d, J=2 Hz).

References: [1]Patent: US6005112,1999,A .

32
[ 117873-72-0 ]
ethyl acetate-saturated sodium bicarbonate water [ No CAS ]
[ 622-58-2 ]
N-(4-methylphenyl)-6-bromo-4-methoxy-2-pyridine carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; n-butyllithium; In diethyl ether; hexane;	(2) Production of N-(4-methylphenyl)-6-bromo-4-methoxy-2-pyridine carboxamide (compound No. I-7) 2.0 g (0.0075 mol) of <strong>[117873-72-0]2,6-dibromo-4-methoxy pyridine</strong> was added to about 30 ml of diethyl ether. While cooling the obtained solution in a dry ice-acetone bath in an argon atmosphere, the solution was mixed with 6.0 ml of about 1.6M hexane solution of BuLi (0.00751.3 mol), followed by stirring for about 10 minutes. After 2.0 g (0.00752.0 mol) of 4-methylphenyl isocyanate dissolved in about 5 ml of diethyl ether was added to the reaction solution, the bath was removed and stirred at room temperature for about 40 minutes. The reaction solution was mixed with about 10 ml of 1.2N hydrochloric acid aqueous solution, and then distributed with ethyl acetate-saturated sodium bicarbonate water, followed by washing with saturated brine. The organic phase of the obtained solution was dried with anhydrous sodium sulfate, concentrated and subjected to silica gel column chromatography (eluding solution: ethyl acetate/hexane) to separate a main fraction therefrom. The fraction was concentrated and then subjected to precipitation using hexane, thereby obtaining an aimed product. Yield by weight: 1.38 g; yield by percentage: 57%; solid; melting point: 153 to 157 C.; 1 H-NMR (60 MHz, CDCl3, delta): 2.28 (3H, s), 3.82 (3H, s), 7.02 (1H, d, J=2 Hz), 7.09 (2H, d, J=8 Hz), 7.56 (2H, d, J=8 Hz), 7.68 (1H, d, J=2 Hz), 9.53 (1H, s).

References: [1]Patent: US6005112,1999,A .

33
[ 117873-72-0 ]
[ 108-95-2 ]
[ 175422-07-8 ]

Yield	Reaction Conditions	Operation in experiment
	In N-methyl-acetamide; mineral oil;	(1) Synthesis of an Intermediate, 2-bromo-4-methoxy-6-phenoxypyridine To a dimethylformamide solution containing phenol (0.58 g, 0.00561.1 mol), sodium hydride (0.24 g (ca.60% in mineral oil)., 0.00561.07 mol) was added. Then, <strong>[117873-72-0]2,6-dibromo-4-methoxypyridine</strong> (1.5 g, 0.0056 mol) was added thereto and the resultant solution was stirred for about 2 hours at about 110 C. Thereafter, the reaction solution was partitioned between hexane and aqueous saturated sodium hydrogen carbonate. The obtained organic layer was washed with aqueous saturated sodium chloride, dried over anhydrous sodium sulfate and thereafter concentrated. The concentrate was purified on a silica gel column, then crystallized from hexane to obtain the end product. Yield: 0.83 g (53%). Oily product. 1 H-NMR (60 MHz, CDCl3, delta): 3.67(3H, s), 6.12(1H, d, J=2.0 Hz), 6.66(1H, d, J=2.0 Hz), 6.8-7.5(5H, complex).

References: [1]Patent: US5691277,1997,A .

34
[ 2408-70-0 ]
[ 124-41-4 ]
[ 117873-72-0 ]

Yield	Reaction Conditions	Operation in experiment
80%	In methanol; for 2.5h;Heating / reflux;	2,6-Dibromo-4-methoxy pyridine (6) was obtained in 80% yield when 2,4,6-tribromopyridine (5) was allowed to react with sodium methoxide (1.2 eq) in refluxing methanol. The compound (6) was treated using n-butyl lithium (1.2 eq.), was allowed to react with pivalonitrile (1.2 eq.) for 150 minutes at -78C and was refluxed for two hours in two normal sulfuric acid to yield ketone isomer (7) in 86% yield. An optically active alcohol (8) was obtained in 93% yield and in 90% ee optical purity from compound (7) through hydrogen transfer type asymmetric reduction of formic acid (4.3 eq.) and triethylamine (2.5 eq.) using the asymmetric ruthenium catalyst (RuCl[(S,S]-Tsdpen)(p-cumene), 0.01 eq.) as the catalyst. The compound (8) was converted to a camphor ester using the acid chloride, an optical resolution process was conducted using re-crystallization (75% yield, diastereomer ratio = >99/<1) and saponified again to obtain an almost optically pure alcohol (7, quant.). The compound (7) was subjected to homo coupling using a palladium catalyst [PdCl2(PhCN)2-TDAE] to yield a pyridine isomer (9) (Chemical formula 5) in 36% yield (diastereomer ratio =>99.5/<0.5).

References: [1]Patent: EP1724251,2006,A1 .Location in patent: Page/Page column 5; 9.

35
[ 117873-72-0 ]
[ 115-19-5 ]
[ 1032413-82-3 ]

References: [1]Journal of Organic Chemistry,2008,vol. 73,p. 4650 - 4661.

Historical Records

Technical Information

• Alkyl Halide Occurrence • General Reactivity • Grignard Reaction • Hiyama Cross-Coupling Reaction • Kinetics of Alkyl Halides • Kumada Cross-Coupling Reaction • Nomenclature of Ethers • Preparation of Amines • Preparation of Ethers • Reactions of Alkyl Halides with Reducing Metals • Reactions of Amines • Reactions of Dihalides • Reactions of Ethers • Stille Coupling • Substitution and Elimination Reactions of Alkyl Halides • Suzuki Coupling

Related Functional Groups of
[ 117873-72-0 ]

Bromides

A477759 [220616-68-2]

2,6-Dibromopyridin-4-ol

Similarity: 0.95

A130368 [89488-29-9]

2-Bromo-4-methoxypyridine

Similarity: 0.84

A164095 [79491-45-5]

2,6-Dibromo-3-methoxypyridine

Similarity: 0.81

A110818 [17117-13-4]

2-Bromo-4-ethoxypyridine

Similarity: 0.81

A170223 [36953-40-9]

2-Bromo-4-hydroxypyridine

Similarity: 0.79

Ethers

A130368 [89488-29-9]

2-Bromo-4-methoxypyridine

Similarity: 0.84

A164095 [79491-45-5]

2,6-Dibromo-3-methoxypyridine

Similarity: 0.81

A110818 [17117-13-4]

2-Bromo-4-ethoxypyridine

Similarity: 0.81

A147692 [1206984-48-6]

2-Bromo-4-(difluoromethoxy)pyridine

Similarity: 0.76

A272744 [1211520-71-6]

2,5-Dibromo-4-methoxypyridine

Similarity: 0.73

Related Parent Nucleus of
[ 117873-72-0 ]

Pyridines

A477759 [220616-68-2]

2,6-Dibromopyridin-4-ol

Similarity: 0.95

A130368 [89488-29-9]

2-Bromo-4-methoxypyridine

Similarity: 0.84

A164095 [79491-45-5]

2,6-Dibromo-3-methoxypyridine

Similarity: 0.81

A110818 [17117-13-4]

2-Bromo-4-ethoxypyridine

Similarity: 0.81

A170223 [36953-40-9]

2-Bromo-4-hydroxypyridine

Similarity: 0.79

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CAS No.: 117873-72-0

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