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Chemical Structure| 14047-29-1
Chemical Structure| 14047-29-1
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Product Details of [ 14047-29-1 ]

CAS No. :14047-29-1 MDL No. :MFCD00151801
Formula : C7H7BO4 Boiling Point : -
Linear Structure Formula :- InChI Key :SIAVMDKGVRXFAX-UHFFFAOYSA-N
M.W : 165.94 Pubchem ID :312183
Synonyms :

Calculated chemistry of [ 14047-29-1 ]

Physicochemical Properties

Num. heavy atoms : 12
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.0
Num. rotatable bonds : 2
Num. H-bond acceptors : 4.0
Num. H-bond donors : 3.0
Molar Refractivity : 43.23
TPSA : 77.76 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -7.06 cm/s

Lipophilicity

Log Po/w (iLOGP) : 0.0
Log Po/w (XLOGP3) : 0.35
Log Po/w (WLOGP) : -0.94
Log Po/w (MLOGP) : -0.13
Log Po/w (SILICOS-IT) : -1.35
Consensus Log Po/w : -0.41

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.56

Water Solubility

Log S (ESOL) : -1.33
Solubility : 7.81 mg/ml ; 0.0471 mol/l
Class : Very soluble
Log S (Ali) : -1.55
Solubility : 4.71 mg/ml ; 0.0284 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -0.65
Solubility : 36.8 mg/ml ; 0.222 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.47

Safety of [ 14047-29-1 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H303-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 14047-29-1 ]

* 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.

  • Upstream synthesis route of [ 14047-29-1 ]
  • Downstream synthetic route of [ 14047-29-1 ]

[ 14047-29-1 ] Synthesis Path-Upstream   1~29

  • 1
  • [ 109-04-6 ]
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  • [ 4385-62-0 ]
YieldReaction ConditionsOperation in experiment
91% With potassium carbonate In water; acetonitrile for 24 h; Reflux; Inert atmosphere Example 155 A4-(pyridin-2-yl)benzoic acid; To a solution of 4-boronobenzoic acid (1.66 g, 10 mmol) and 2-bromopyridine (1.72 g, 11 mmol) in acetonitrile (40 mL) and water (40 mL), potassium carbonate (5.5 g, 40 mmol), bis(triphenylphosphine)palladium(II) chloride (400 mg, 0.37 mmol) were added. The mixture was degassed and purged withed nitrogen. The mixture was stirred under reflux for 24 h. Then the hot suspension was filtered and concentrated to half of the original volume and washed with dichloromethane. The aquatic phase was adjusted to pH=4 with hydrochloric acid (1 M) and filtrated, washed with water. The residue was dried in vacuum to obtain 1.81 g of white solid of 4-(pyridin-2-yl)benzoic acid. Yield: 91percent. LC-MS (ESI) m/z: 200 (M+1)+.
85%
Stage #1: With sodium carbonate In water; acetonitrile at 90℃;
4-pyridin-2-ylbenzoic acid
To a solution of 4-(dihydroxyboryl)benzoic acid (1.03 g, 6.21 mmol) and 2-bromopyridine (0.59 mL, 6.21 mmol) in ACN (20 mL) was added sodium carbonate (0.396 g, 3.74 mmol) in water (20 mL).
The reaction mixture was degassed with argon and then tetrakis(triphenylphosphine)palladium (0.108 g, 0.09 mmol) was added.
The reaction mixture was allowed to stir at 90° C. overnight and then filtered.
The solution was concentrated to remove ACN and the aqueous solution was washed with DCM.
The aqueous solution was acidified with 1N HCl and the resulting white precipitate was filtered and dried to give 4-pyridin-2-ylbenzoic acid (1.06 g, 85percent). LCMS: (FA) ES+200.1.
84% With sodium carbonate In acetonitrile at 90℃; for 20 h; Example 107 10-(4-PYRIDIN-2-YLBENZOYL)-N-(PYRIDIN-3-YLMETHYL)-10,11-DIHYDRO-5H-PYRROLO[2,1-C][1,4]BENZODIAZEPINE-3-CARBOXAMIDE Step A. 4-Pyridin-2-ylbenzoic acid; To a suspension of 4-carboxybenzeneboronic acid (0.660 g, 3.98 mmol) and 2-bromopyridine (0.38 mL, 3.98 mmol) in dry acetonitrile (20 mL) was added 0.4 M aqueous sodium carbonate (20 mL) and mixture purged with nitrogen for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.240 g) was then added and the reaction mixture heated to 90° C. for 20 hours. The hot mixture was filtered through celite and concentrated in vacuo to remove acetonitrile. The resulting aqueous suspension was diluted with water (20 mL), washed with dichloromethane (2.x.40 mL), and then acidified to pH 6 by the addition of concentrated hydrochloric acid. The resulting white suspension was diluted with water (20 mL), filtered and the solid product dried in vacuo at 50° C. overnight to give the title compound (0.662 g, 84percent) as a white solid, m.p. 232-234° C. MS [(+)ESI, m/z]: 200 [M+H]+ MS [(-)ESI, m/z]: 198 [M-H]- Anal. Calcd for C12H9NO2: C, 72.35; H, 4.55; N, 7.03. Found: C, 72.04; H, 4.38; N, 6.89.
75% With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In water; acetonitrile at 90℃; for 48 h; Inert atmosphere 5.1.4
4-Pyridin-2-ylbenzoic acid (5a)
Pd(PPh3)4 (0.6 g, 0.5 mmol) was added to a degassed solution of 4-Carboxyphenyl-boronic acid (2a) (2.0 g, 12 mmol), 2-bromopyridine (1. 58 g, 10 mmol) and Cs2CO3 (13.0 g, 30 mmol) in 50 ml acetonitrile and 50 ml water.
The reaction mixture was heated at 90 °C in an oil bath and stirred under nitrogen for 48 h.The hot suspension was filtered and the filtrate distilled by rotary evaporation to remove acetonitrile.
Water was added and the mixture was exacted with ethyl acetate (3 * 30 ml).
The aqueous layer was acidified with conc. HCl and exacted with ethyl acetate three times.
The combined organic layer was washed with brine and dried over Na2SO4, filtered, and concentrated by rotary evaporation to give the crude product, which was isolated by flash chromatography on silica gel to obtain the targeted compound (1.5 g, 75percent), mp.: 238-240 °C.
The intermediates 4-pyridin-3-ylbenzoic acid (5b), 4-(4- methylpyridin-2-yl)benzoic acid (5c), 4-(6-methylpyridin-3 -yl)benzoic acid (5d), 4-(2-thienyl)benzoic acid (5e) and 4-(1,3-thiazol-2-yl)benzoic acid (5f) were prepared by commercially available materials 3-bromo-pyridine, 2-bromo-4-methylpyridine, 5-bromo-2-methylpyridine, 2-bromothiophene and 2-bromo-1,3-thiazole respectively using the general procedure described above.

Reference: [1] Patent: US2009/197863, 2009, A1, . Location in patent: Page/Page column 73
[2] Patent: US2008/171754, 2008, A1, . Location in patent: Page/Page column 94-95
[3] Patent: US2006/287522, 2006, A1, . Location in patent: Page/Page column 52
[4] European Journal of Medicinal Chemistry, 2015, vol. 101, p. 780 - 789
[5] Synlett, 2000, # 6, p. 829 - 831
[6] Patent: US2005/85512, 2005, A1, . Location in patent: Page/Page column 10
[7] European Journal of Inorganic Chemistry, 2012, # 7, p. 1025 - 1037
[8] RSC Advances, 2014, vol. 4, # 97, p. 54775 - 54787
[9] Patent: CN104262238, 2016, B, . Location in patent: Paragraph 0046; 0047; 0048
  • 2
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  • [ 14047-29-1 ]
  • [ 4385-76-6 ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate In water; acetonitrile at 100℃; for 24 h; Inert atmosphere Example 159 A4-(pyridin-4-yl)benzoic acid; To a solution of 4-boronobenzoic acid (1.66 g, 10 mmol) and 4-bromopyridine (1.72 g, 11 mmol) in acetonitrile (40 mL) and water (40 mL), potassium carbonate (5.5 g, 40 mmol), Bis(triphenylphosphine)palladium(II) chloride (400 mg, 0.37 mmol) was added. The mixture was degassed and purged withed nitrogen. The mixture was stirred at 100° C. for 24 h. Then the hot suspension was filtered and concentrated to half of the original volume and washed with dichloromethane. The aquatic phase was adjusted to pH=3 with hydrochloric acid (1 M) and filtrated, washed with water. The residue was dried in vacuum to obtain 1.8 g of white solid of 4-(pyridin-4-yl)benzoic acid. Yield: 90percent. LC-MS (ESI) m/z: 200 (M+1)+.
Reference: [1] Archiv der Pharmazie, 2008, vol. 341, # 8, p. 478 - 484
[2] Patent: US2009/197863, 2009, A1, . Location in patent: Page/Page column 74
  • 3
  • [ 14047-29-1 ]
  • [ 19524-06-2 ]
  • [ 4385-76-6 ]
Reference: [1] Synlett, 2000, # 6, p. 829 - 831
[2] Patent: CN106008565, 2016, A, . Location in patent: Paragraph 0027; 0034; 0035
  • 4
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  • [ 14047-29-1 ]
  • [ 29886-62-2 ]
Reference: [1] Synlett, 2000, # 6, p. 829 - 831
[2] European Journal of Medicinal Chemistry, 2015, vol. 101, p. 780 - 789
[3] Patent: CN104262238, 2016, B, . Location in patent: Paragraph 0082; 0083
  • 5
  • [ 14047-29-1 ]
  • [ 53355-29-6 ]
Reference: [1] Patent: CN106565643, 2017, A,
  • 6
  • [ 104-92-7 ]
  • [ 14047-29-1 ]
  • [ 725-14-4 ]
Reference: [1] Journal of Organic Chemistry, 2009, vol. 74, # 16, p. 6283 - 6286
  • 7
  • [ 14047-29-1 ]
  • [ 4334-88-7 ]
YieldReaction ConditionsOperation in experiment
85.5%
Stage #1: With hydrogenchloride In ethanol at 70℃; for 1 h; Heating / reflux
Stage #2: at 20℃;
Preparation of 4-(ethoxycarbonyl)benzeneboronic acid.
4-Carboxybenzeneboronic acid (350 mg, 2.109 mmol) was dissolved in ethanol (10 ML, absolute) in a 100 ML 3-neck round bottom flask, fitted with a condenser, thermometer, stirbar and rubber plug.An ethanol/HCl mixture (10 ML, PH approximately 3.0) was added, and the mixture was heated at reflux (70° C.) for one hour.The reaction mixture was then allowed to cool to room temperature and stirred overnight.The reaction mixture was concentrated in a vacuum, then dissolved in ethyl acetate, and washed with water.The organic layer was dried with potassium carbonate, filtered, and concentrated under reduced pressure, yielding 520 mg white solid.This material was purified via silica gel chromatography, utilizing a Chromatotron with a 6000 μm rotor in a 1:1 hexane:ethyl acetate solvent system, yielding 470 mg of a co-eluding mixture of unreacted starting material and product.This mixture was purified by reverse phase chromatography on a Vydac C-18 column on a gradient of 5 to 70percent of 0.1percent trifluoroacetic acid/acetonitrile in water yielding the intermediate title compound (350 mg, 85.5percent) as a white solid.
Electrospray-MS 195.0 (M*+1).
Reference: [1] Patent: US2003/225266, 2003, A1, . Location in patent: Page 25
[2] Patent: US2002/55631, 2002, A1,
[3] Patent: US2002/86887, 2002, A1,
  • 8
  • [ 64-17-5 ]
  • [ 14047-29-1 ]
  • [ 4334-88-7 ]
YieldReaction ConditionsOperation in experiment
95.2% at 50 - 65℃; Autoclave; Industrial scale In a 20L reactor, 8.0 Kg of absolute ethanol was added p-carboxyphenyl boronic acid and 1.66 Kg (10 mol), stirring the reactor was heated to 50 , temperature 50 ~ 65 thionyl chloride was added dropwise to the kettle (1.55 Kg, 13 mol), dropwise after the reaction warmed to reflux for 2-3 hours.After completion of the reaction was confirmed (TLC: n-heptane: ethyl acetate = 2: 1), the reaction solution was cooled, the solvent evaporated under reduced pressure, after adding heptane, cooled -10 ~ 0 , stirred for 1 hour was filtered, minus 100 The solid was dried pressure until no impurities confirmation HNMR (HNMR: DMSO-d6In 3.43ppm and 1.21ppm peak) to stop drying.After stirring at room temperature water was added by filtration, dried at room temperature to give a white solid 1.85 Kg, 95.2percent yield,
86.3% at 105 - 110℃; for 24 h; To the condenser with a tube,Dried 1L dry eggplant-shaped bottle in turn by adding 3A molecular sieve dried anhydrous ethanol 400mL,(0.2mol) of 4-carboxyphenylboronic acid, 8mL of concentrated sulfuric acid, and refluxed at 105 ~ 110 for 24 hours. TLC (CHCl3 / MeOH = 10/1)Ethanol was evaporated under reduced pressure to give a white solid, 500 mL of water was added,Saturated NaHCO3 solution 250mL washing, washing to neutral, dry,To obtain 33.5 g of 4-ethoxycarbonylphenylboronic acid (yield: 86.3percent).
Reference: [1] Patent: CN106188117, 2016, A, . Location in patent: Paragraph 0016
[2] Patent: CN105985276, 2016, A, . Location in patent: Paragraph 0076; 0077
[3] Chemistry - A European Journal, 2017, vol. 23, # 26, p. 6441 - 6451
[4] Synlett, 2012, vol. 23, # 12, p. 1751 - 1754
[5] Chemical Communications, 2014, vol. 50, # 52, p. 6886 - 6889
[6] Chemistry - A European Journal, 2015, vol. 21, # 45, p. 16083 - 16090
[7] Inorganic Chemistry, 2017, vol. 56, # 16, p. 9765 - 9771
  • 9
  • [ 7664-93-9 ]
  • [ 14047-29-1 ]
  • [ 4334-88-7 ]
Reference: [1] Patent: US2002/37905, 2002, A1,
[2] Patent: US6297261, 2001, B1,
[3] Patent: US6696475, 2004, B2,
  • 10
  • [ 14047-29-1 ]
  • [ 85107-55-7 ]
Reference: [1] Journal of Chemical Research, 2014, vol. 38, # 12, p. 719 - 721
  • 11
  • [ 14047-29-1 ]
  • [ 63619-51-2 ]
  • [ 158938-08-0 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 3, p. 489 - 493
  • 12
  • [ 626-55-1 ]
  • [ 14047-29-1 ]
  • [ 4385-75-5 ]
YieldReaction ConditionsOperation in experiment
85% With potassium carbonate In water; acetonitrile for 24 h; Reflux; Inert atmosphere Example 157 A4-(pyridin-3-yl)benzoic acid; To a solution of 4-boronobenzoic acid (1.66 g, 10 mmol) and 3-bromopyridine (1.72 g, 11 mmol) in acetonitrile (40 mL) and water (40 mL), potassium carbonate (5.5 g, 40 mmol), bis(triphenylphosphine)palladium(II) chloride (400 mg, 0.37 mmol) were added. The mixture was degassed and purged withed nitrogen. The mixture was stirred under reflux for 24 h. Then the hot suspension was filtered and concentrated to half of the original volume and washed with dichloromethane. The aquatic phase was adjusted to pH=3 with hydrochloric acid (1 M) and filtrated, washed with water. The residue was dried in vacuum to obtain 1.7 g of white solid of 4-(pyridin-3-yl)benzoic acid. Yield: 85percent. LC-MS (ESI) m/z: 200 (M+1)+.
Reference: [1] Patent: US2009/197863, 2009, A1, . Location in patent: Page/Page column 73-74
[2] Archiv der Pharmazie, 2008, vol. 341, # 8, p. 478 - 484
[3] Synlett, 2000, # 6, p. 829 - 831
[4] Patent: US6399656, 2002, B1,
[5] European Journal of Medicinal Chemistry, 2015, vol. 101, p. 780 - 789
  • 13
  • [ 76-09-5 ]
  • [ 14047-29-1 ]
  • [ 180516-87-4 ]
YieldReaction ConditionsOperation in experiment
81% for 2 h; Heating / reflux 4-Carboxyphenylboronic acid (10.0 g, 60.3 mmol) was suspended in 100 mL of toluene and pinnacol added (7.1 g, 60.3 mmol). The reaction was heated to reflux with a Dean-Stark trap attached. The reaction became homogenous upon heating. After 2 h reflux the reaction was allowed to stand overnight and white needles were collected by filtration, rinsed with toluene, and vacuum dried to 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid 12.2 g (81percent). MS (FD MS): M=248. Analysis calculated for C13H17BO4: C, 62.94; H, 6.91 Found: C, 62.71; H, 6.91.
81% for 2 h; Heating / reflux 4-Carboxyphenylboronic acid (10.0 g, 60.3 mmol) was suspended in 100 mL of toluene and pinnacol added (7.1 g, 60.3 mmol). The reaction was heated to reflux with a Dean-Stark trap attached. The reaction became homogenous upon heating. After 2 h reflux the reaction was allowed to stand overnight and white needles were collected by filtration and rinsed with toluene. The title compound was vacuum dried to 12.2 g (81percent).[0153] Mass Spectrum (FD MS): M=248. Analysis calculated for C13H17BO4: percent C, 62.94; percent H, 6.91; Found: percent C, 62.71; percent H, 6.91.
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[2] Journal of Organic Chemistry, 2006, vol. 71, # 20, p. 7915 - 7918
[3] Patent: US2004/6114, 2004, A1, . Location in patent: Page 64
[4] Patent: US6639107, 2003, B1, . Location in patent: Page/Page column 31
[5] Organic letters, 2001, vol. 3, # 6, p. 917 - 920
[6] Patent: US2002/55631, 2002, A1,
[7] Patent: US2002/86887, 2002, A1,
[8] Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 16, p. 5012 - 5016
[9] Patent: WO2015/106292, 2015, A1, . Location in patent: Paragraph 00323; 00330; 00331
[10] Chemistry - An Asian Journal, 2017, vol. 12, # 10, p. 1087 - 1094
[11] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
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  • [ 195457-71-7 ]
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[2] Patent: EP1657242, 2006, A1, . Location in patent: Page/Page column 28-29
[3] Patent: US2007/82952, 2007, A1, . Location in patent: Page/Page column 6
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Reference: [1] Patent: US6096780, 2000, A,
  • 17
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  • [ 99768-12-4 ]
Reference: [1] Patent: US6307056, 2001, B1,
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Reference: [1] Patent: US5866568, 1999, A,
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  • [ 14047-29-1 ]
  • [ 216959-91-0 ]
Reference: [1] Archiv der Pharmazie, 2008, vol. 341, # 8, p. 478 - 484
[2] Synlett, 2000, # 6, p. 829 - 831
  • 22
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  • [ 4595-60-2 ]
  • [ 199678-12-1 ]
YieldReaction ConditionsOperation in experiment
89% With sodium carbonate In acetonitrile at 90℃; for 17 h; Example 105 N-(PYRIDIN-3-YLMETHYL)-10-(4-PYRIMIDIN-2-YLBENZOYL)-10,11-DIHYDRO-5H-PYRROLO[2,1-C][1,4]BENZODIAZEPINE-3-CARBOXAMIDE Step A. 4-Pyrimidin-2-ylbenzoic acid; To a suspension of 4-carboxybenzeneboronic acid (0.660 g, 3.98 mmol) and 2-bromopyrimidine (0.630 g, 3.98 mmol) in dry acetonitrile (20 mL) was added 0.4 M aqueous sodium carbonate (20 mL) and the mixture was purged with nitrogen for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (240 mg) was then added and the reaction mixture heated to 90° C. for 17 hours. The hot reaction mixture was filtered through celite and concentrated in vacuo to remove the acetonitrile. The resulting aqueous suspension was washed with dichloromethane (2.x.30 mL) and then acidified to pH 1 by the addition of concentrated hydrochloric acid. The resulting white suspension was diluted with water (20 mL), filtered and the solid product dried in vacuo at 50° C. overnight to give the title compound (0.709 g, 89percent) as a white solid, m.p. 237° C. MS [(+)ESI, m/z]: 201 [M+H]+ MS [(-)ESI, m/z]: 199 [M-H]- Anal. Calcd for C11H8N2O2: C, 66.00; H, 4.03; N, 13.99. Found: C, 65.72; H, 3.87; N, 14.01.
2 g With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In acetonitrileInert atmosphere; Reflux To a solution of compound 1 (2g, 12.6mmol) and compound 2 (2.2g, 13.2mmol) in CH3CN, was added 0.5M Na2CO3 (2.7g, 25.2mmol) and the mixture was purged with N2 for 10 mm. Pd(PPh3)4 (800mg) was then added and the mixture heated at reflux overnight. The mixture was filtered, diluted with water and extracted with EA. The resulting aqueous mixture was acidified to pH = 1 and a precipitate formed. The precipitate was filtered and dried to give 2g of compound 3.
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[2] Patent: US2006/287522, 2006, A1, . Location in patent: Page/Page column 51
[3] Synlett, 2000, # 6, p. 829 - 831
[4] Patent: WO2016/77232, 2016, A2, . Location in patent: Page/Page column 44; 45
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  • [ 123088-59-5 ]
Reference: [1] Patent: US6297261, 2001, B1,
[2] Patent: US2002/37905, 2002, A1,
[3] Patent: US6696475, 2004, B2,
  • 24
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  • [ 389621-84-5 ]
Reference: [1] Patent: JP2015/214548, 2015, A,
  • 25
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  • [ 115-11-7 ]
  • [ 850568-54-6 ]
Reference: [1] Journal of Organic Chemistry, 2006, vol. 71, # 21, p. 7952 - 7966
  • 26
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  • [ 214360-57-3 ]
Reference: [1] Patent: US6639107, 2003, B1,
  • 27
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  • [ 380430-55-7 ]
Reference: [1] Journal of Chemical Research, 2014, vol. 38, # 12, p. 719 - 721
  • 28
  • [ 14047-29-1 ]
  • [ 6011-14-9 ]
  • [ 1056636-11-3 ]
YieldReaction ConditionsOperation in experiment
87%
Stage #1: With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 40℃; for 3.5 h;
Stage #2: With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 0 - 20℃; for 16 h;
To a suspension of 4-carboxyphenylboronic acid (5.0 g, 30 mmol) in DMF (5 mL) and dichloromethane (200 mL) at 0°C was added oxalylchloride (5.9 mL, 66 mmol) dropwise. <n="54"/>When gas evolution slowed, the ice bath was removed and the reaction allowed to warm to room temperature over 30 min. The reaction was then heated at 4O0C for 3 h by which time all solids had dissolved. The dichloromethane was removed by distillation and the DMF solution cooled to 00C. A solution of aminoacetonitrile hydrochloride (3.05 g, 33 mmol) in DMF (80 rnL) and DIPEA (13 mL, 75 mmol) was then added dropwise. After the addition was complete the ice bath was removed and the solution allowed to stir at room temperature for 16 h. Most of the DMF was then removed in vacuo and the reaction was partitioned between ethyl acetate and 2 M aqueous hydrochloric acid. The aqueous layer was extracted twice further with ethyl acetate and the combined organic fractions dried (Na2SO4) filtered and concentrated under reduced pressure to afford 4-(cyanomethylcarbamoyl)phenylboronic acid as a waxy pale yellow solid (5.34 g, 87percent). 1HNMR (J6-DMSO, 300 MHz) δ 9.18 (IH, br. t, J= 5.1Hz), 7.8-7.9 (4H, m), 4.31 (2H, d, J= 5.4 Hz). LC-MS: rt 0.9 min.; m/z 203.3 [M-H]".
87%
Stage #1: With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 40℃; for 3.5 h;
Stage #2: With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 16 h;
Example 3 - Synthesis of Compound 90; To a suspension of 4-carboxyphenylboronic acid (5.0 g, 30 mmol) in DMF (5 mL) and dichloromethane (200 mL) at 0°C was added oxalylchloride (5.9 mL, 66 mmol) dropwise. When gas evolution slowed, the ice bath was removed and the reaction allowed to warm to room temperature over 30 min. The reaction was then heated at 400C for three hours by which time all solids had dissolved. The dichloromethane was removed by distillation and the DMF solution cooled to 0°C. A solution of aminoacetonitrile hydrochloride (3.05 g, 33 mmol) in DMF (80 mL) and DIPEA (13 mL, 75 mmol) was then added dropwise. After the addition was complete the ice bath was removed and the solution allowed to stir at room temperature for 16 h. Most of the DMF was then removed in vacuo and the reaction was partitioned between ethyl acetate and 2 M aqueous hydrochloric acid. The aqueous layer was extracted twice further with ethyl acetate and the combined organic fractions dried (Na2SO4) filtered and concentrated under reduced pressure to afford 4-(cyanomethylcarbamoyl)phenylboronic acid as a waxy pale yellow solid (5.34 g, 87percent). 1H NMR (300 MHz, J6-DMSO): 9.18 (br. t, J- 5.1Hz, IH), 7.8-7.9 (m, 4H), 4.31 (d, J= 5.4 Hz, 2H); LC-ESI-MS (method B): rt 0.9 min.; m/z 203.3 [M-H]-.
Reference: [1] Patent: WO2009/29998, 2009, A1, . Location in patent: Page/Page column 52-53
[2] Patent: WO2008/109943, 2008, A1, . Location in patent: Page/Page column 60
  • 29
  • [ 14047-29-1 ]
  • [ 575452-22-1 ]
  • [ 1017794-47-6 ]
Reference: [1] Angewandte Chemie - International Edition, 2013, vol. 52, # 32, p. 8290 - 8294[2] Angew. Chem., 2013, vol. 125, # 32, p. 8448 - 8452,5
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