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Product Details of [ 51934-41-9 ]

CAS No. :51934-41-9 MDL No. :MFCD00017344
Formula : C9H9IO2 Boiling Point : -
Linear Structure Formula :- InChI Key :YCBJOQUNPLTBGG-UHFFFAOYSA-N
M.W : 276.07 Pubchem ID :142891
Synonyms :

Calculated chemistry of [ 51934-41-9 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 12
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.22
Num. rotatable bonds : 3
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 55.25
TPSA : 26.3 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.65 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.6
Log Po/w (XLOGP3) : 3.29
Log Po/w (WLOGP) : 2.47
Log Po/w (MLOGP) : 3.11
Log Po/w (SILICOS-IT) : 2.99
Consensus Log Po/w : 2.89

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.8
Solubility : 0.0441 mg/ml ; 0.00016 mol/l
Class : Soluble
Log S (Ali) : -3.52
Solubility : 0.0838 mg/ml ; 0.000304 mol/l
Class : Soluble
Log S (SILICOS-IT) : -3.83
Solubility : 0.0411 mg/ml ; 0.000149 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 0.0
Synthetic accessibility : 1.91

Safety of [ 51934-41-9 ]

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

Application In Synthesis of [ 51934-41-9 ]

* 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 [ 51934-41-9 ]
  • Downstream synthetic route of [ 51934-41-9 ]

[ 51934-41-9 ] Synthesis Path-Upstream   1~49

  • 1
  • [ 51934-41-9 ]
  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
95%
Stage #1: With isopropylmagnesium chloride; lithium chloride In tetrahydrofuran at -15℃; for 0.25 h;
Stage #2: With N,N-dimethyl-formamide In tetrahydrofuran at 0℃; for 2 h;
Stage #3: With ammonia; iodine In tetrahydrofuran; water at 20℃; for 2 h;
General procedure: To a flask containing dried LiCl (0.35 g, 8.24 mmol) was added iPrMgCl (2 M in THF, 4.1 mL) and THF (5 mL) at 15° C. After beingstirred for 15 min, 3-bromo-1-benzonitrile (1.46 g, 8.03 mmol) inTHF (1 mL) was added to the reaction mixture and the obtainedmixture was stirred for 15 min. Then, DMF (1.3 mL, 12 mmol) wasadded at 0° C and the mixture was stirred for 2 h. Then, aq NH3 (7 mL, 28-30percent) and I2 (4.06 g, 16 mmol) were added to the reaction mixture. After being stirred for 2 h at room temperature, the reactionmixture was poured into satd aq Na2SO3 solution and was extracted with CHCl3 (3∗30 mL). The organic layer was dried over Na2SO4 and filtered. After removal of the solvent, the residue waspurified by short column chromatography on silica gel (eluent:hexane/ethyl acetate=9:1, v/v) to provide pure 1,3-dicyanobenzene (0.73 g) in 71percent yield. Most nitriles mentioned in this work are commercially availableand were identified by comparison with the authentic samples.
Reference: [1] Tetrahedron, 2013, vol. 69, # 5, p. 1462 - 1469
  • 2
  • [ 557-21-1 ]
  • [ 51934-41-9 ]
  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
84% With dmap; 1,1'-bis-(diphenylphosphino)ferrocene; nickel(II) chloride hexahydrate; zinc In acetonitrile at 80℃; for 3 h; Inert atmosphere; Sealed tube General procedure: Under argon protection, NiCl2·6H2O (0.05mmo 1,11.9mg), dppf (0.06mmol, 33.3mg), Zn (0·2mmol, 13.0mg), DMAP (1.0mmol, 122.2mg), Zn(CN)2 (0.8mmol) , 93.9mg), p-Chloroanisole (1.0 mmol, 140.6 mg) and acetonitrile (5.0 mL) were sequentially added in a 25.0 mL sealed tube, then directly put it into the oil bath at 60 °C, and heating was stopped after 6h, and cooled to room temperature, the reaction solution was directly filtered through a short silica gel column, washed with dichloromethane, concentrated and purified by silica gel column chromatography( given that the product is most easily pulled out, in order to avoid loss of sample mix, unless otherwise noted, both are wet method). Eluent: petroleum ether / ethyl acetate = 20:1, the product was 117.2 mg as a white solid, yield 88percent, and 1H NMR purity was greater than 98percent.
Reference: [1] Organic Letters, 2017, vol. 19, # 8, p. 2118 - 2121
[2] Patent: CN108623495, 2018, A, . Location in patent: Paragraph 0043; 0045; 0169-0171
  • 3
  • [ 51934-41-9 ]
  • [ 57-13-6 ]
  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
84% With copper (II)-fluoride; 1,10-Phenanthroline; oxygen; lithium carbonate In dimethyl sulfoxide at 150℃; for 36 h; Sealed tube General procedure: Under Oxygen, a reaction tube was charged with p-iodoanisole (46.3 mg, 0.2 mmol), urea (48.0 mg, 0.8 mmol), CuF2 (4.1 mg, 0.04 mmol), L1 (10.8 mg, 0.06 mmol), Li2CO3 (44.3 mg, 0.6mmol) and DMSO (2 mL). The mixture was stirred at 150 oC for 36 h. After the completion of the reaction, monitored by TLC, the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography on silica gel to give the product.
Reference: [1] Tetrahedron Letters, 2013, vol. 54, # 38, p. 5250 - 5252
  • 4
  • [ 51934-41-9 ]
  • [ 21864-90-4 ]
  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
58% With palladium diacetate; copper(II) trifluoroacetate In N,N-dimethyl-formamide at 120℃; for 24 h; Sealed tube General procedure: Aryl halide (0.5 mmol), α-Iminonitrile (0.6 mmol), Cu(TFA)2 (1.0 mmol), Pd(OAc)2(0.1 mmol) and 2ml DMF were added into a 15 ml sealed tube with a magneticstirring bar. Stirred under air at 120°C for 24 h. Monitor the reaction by TLC. Themixture was poured into water (10 ml) and extracted by ethyl acetate (3×10 ml).Dried by Na2SO4 and evaporated. Finally, pure the mixture by silica gel column.
Reference: [1] Synlett, 2018, vol. 29, # 3, p. 359 - 363
  • 5
  • [ 51934-41-9 ]
  • [ 55305-43-6 ]
  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
36% With palladium dichloride; silver(l) oxide In ethanol at 70℃; for 24 h; General procedure: a.Cyanation of aryl iodides.To a solution of aryl iodide (0.5 mmol) in EtOH (5.0 mL) was added NCTS (272 mg, 1.0 mmol), PdCl2 (13.3mg, 0.075 mmol), and Ag2O (57.75 mg, 0.5 mmol). The mixture was stirred at 70 for 24 h under air atmosphere. Then the reaction mixture was cooled to room temperature and filtered through a pad of celite (1.0 g) and rinsed with CH2Cl2 (10.0 mL). The resulting organic solution was concentrated under reduced pressure and further purified by flash chromatography (SiO2, petroleum ether/EtOAc gradient), yielding the corresponding aryl nitriles.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 11, p. 1205 - 1209
  • 6
  • [ 124-38-9 ]
  • [ 51934-41-9 ]
  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
78 %Chromat. With phenylsilane; ammonia; copper(II) acetylacetonate In N,N-dimethyl-formamide at 160℃; for 10 h; Sealed tube Under a nitrogen atmosphere, copper acetylacetonate (20 molpercent, 6.6 mg) and magnets were added to a previously baked 10 mL glass pressure tube. Subsequently, N,N-dimethylformamide (0.5 mL), ethyl 4-iodobenzoate (0.125 mmol, 1.0 equiv., 34.5 mg) and phenylsilane (3.0 equiv., 40.6 mg) were added. The pressure tube was sealed, the tube air was removed and charged with carbon dioxide (0.67 mmol, 5.0 equiv., 15 mL) and ammonia gas (0.67 mmol, 5.0 equiv., 15 mL). After the addition, the glass pressure tube was placed in a metal module that had been preheated to 160°C and stirred for 10 hours. After the reaction was completed, the reaction system was cooled to room temperature and pressure was slowly released. Using dodecane as an internal standard, the yield of the gas chromatography was determined to be 78percent.
Reference: [1] Patent: CN108017557, 2018, A, . Location in patent: Paragraph 0062-0064
  • 7
  • [ 51934-41-9 ]
  • [ 7153-22-2 ]
Reference: [1] New Journal of Chemistry, 2012, vol. 36, # 11, p. 2334 - 2339
  • 8
  • [ 51934-41-9 ]
  • [ 84-58-2 ]
  • [ 7153-22-2 ]
Reference: [1] Chinese Journal of Chemistry, 2013, vol. 31, # 4, p. 449 - 452
  • 9
  • [ 773837-37-9 ]
  • [ 51934-41-9 ]
  • [ 7153-22-2 ]
Reference: [1] Advanced Synthesis and Catalysis, 2017, vol. 359, # 14, p. 2345 - 2351
  • 10
  • [ 51934-41-9 ]
  • [ 143-33-9 ]
  • [ 7153-22-2 ]
Reference: [1] Chemistry Letters, 1998, # 5, p. 425 - 426
  • 11
  • [ 5798-75-4 ]
  • [ 51934-41-9 ]
YieldReaction ConditionsOperation in experiment
91% With copper(I) oxide; <i>L</i>-proline; potassium iodide In ethanol at 110℃; for 30 h; Schlenk technique; Inert atmosphere; Sealed tube General procedure: A Schlenk tube was charged with Cu2O (7.2 mg, 10 molpercent), l-proline (11.5 mg, 20 molpercent), aryl (or heteroaryl) bromide (1 or 3,0.50 mmol), potassium iodide (KI) (249 mg, 0.75 mmol), and EtOH(1.5 mL) under nitrogen atmosphere. The Schlenk tube was sealedwith a teflon valve, and then the reaction mixture was stirred at110C for a period (the reaction progress was monitored by GCanalysis). After the reaction was completed, GC yield of high volatileproduct was determined using an appropriate internal standard(chlorobenzene or 1-chloro-4-methylbenzene) or the solvent wasremoved under reduced pressure. The residue obtained was puri-fied via silica gel chromatography (eluent: petroleum ether/ethylacetate = 10/1) to afford aryl iodides 2a–2o or heteroaryl iodides4a–4g.
Reference: [1] Catalysis Today, 2016, vol. 274, p. 129 - 132
[2] Chemical Communications, 2012, vol. 48, # 33, p. 3993 - 3995
[3] Angewandte Chemie - International Edition, 2015, vol. 54, # 1, p. 263 - 266[4] Angew. Chem., 2015, vol. 127, # 01, p. 265 - 268,4
[5] Catalysis Science and Technology, 2017, vol. 7, # 10, p. 2110 - 2117
  • 12
  • [ 4334-88-7 ]
  • [ 51934-41-9 ]
YieldReaction ConditionsOperation in experiment
82% With perfluoroisopropyl iodide; copper; hydroquinone In N,N-dimethyl-formamide at 20℃; for 24 h; General procedure: (4-Nitrophenyl)boronic acid (0.067 g, 0.4 mmol), copper powder (0.0052 g, 0.08 mmol,), (CF3)2CFI (0.178 g, 0.6 mmol), and DMF (2 mL) were placed in a closed tube with a rubber stopper. The mixture was reacted at room temperature equipped with an air balloon for 24 h. The resulting suspension was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous Na2SO4 and concentrated to dryness. The crude product was purified by flash column chromatography on silica gel using petroleum ether/ethyl acetate = 20: 1 (v/v) as eluent to give 0.086 g of 2j as a light yellow solid (0.35 mmol, 87percent).
Reference: [1] Journal of Fluorine Chemistry, 2016, vol. 189, p. 59 - 67
[2] Chemistry - A European Journal, 2018, vol. 24, # 4, p. 937 - 943
[3] RSC Advances, 2015, vol. 5, # 103, p. 84910 - 84919
  • 13
  • [ 64-17-5 ]
  • [ 619-58-9 ]
  • [ 51934-41-9 ]
YieldReaction ConditionsOperation in experiment
96.1% With hydrogenchloride In water for 2 h; Reflux Synthesis of ethyl 4-iodobenzoate
A mixture of 4-iodobenzoic acid, 25 ml ethyl alcohol and 20 ml solution of dry HCl in ethyl alcohol was refluxed for 2 hours.
The solid was dissolved after 1 hour of boiling.
The reaction solution was cooled to room temperature and evaporated under vacuum to a volume of 10 ml.
A lower organic layer formed with the chemical conversion of the acid to the ester.
The resulting mixture was cooled in an ice bath.
To this mixture 80 ml of diethyl ether, dry sodium hydrogen carbonate (I gram) and 50 grams of ice were added.
This solution was stirred, washed by dissolution of a saturated solution of sodium bicarbonate in 50 ml water and water, dried over sodium sulfate, and evaporated under vacuum, yielding ethyl 4-iodobenzoate as a liquid oil product (5.43 gram, 96.1percent yield) [1H-NMR (CDCl3): d7.8 (s, 1H), d7.79 (s, 1H), 7.6 (s, 1H), d4.4 (d, 2H, J=7.1 Hz), d1.4 (s, 3H)].
95.5% for 5.5 h; Reflux In a 250 mL three-necked flask,Iodobenzoic acid (20.0 g, 80.6 mmol) was dissolved in ethanol (100.0 mL)98percent concentrated sulfuric acid (8.7 g, 88.7 mmol) was slowly added,The reaction was refluxed for 5.5 h.The reaction is completed,The mixture was evaporated to dryness under reduced pressure and the residue was washed with water (20 mL × 2)Vacuum dried to give 4-iodobenzoate 21.3g,Yield 95.5percent.
85% at 100℃; for 24 h; General procedure: A mixture of acid (0.2 mmol), alcohol (0.6 mmol) and GO (50 wtpercent, calculated with the mass of acid) in ethyl alcohol or DCE (1 mL) was placed in a test tube equipped with a magnetic stirring bar. The mixture was stirred at 100 °C for 24 h. After the reaction was finished, filtered the GO, solvent was removed, and the residue was separated by column chromatography to give the pure sample.
Reference: [1] Chemistry - A European Journal, 2009, vol. 15, # 10, p. 2278 - 2288
[2] Patent: US2016/97037, 2016, A1, . Location in patent: Paragraph 0438
[3] Dalton Transactions, 2015, vol. 44, # 19, p. 9269 - 9280
[4] Patent: CN106565761, 2017, A, . Location in patent: Paragraph 0029; 0030; 0053; 0054; 0069; 0070
[5] Synthesis, 2008, # 4, p. 605 - 609
[6] Synlett, 2017, vol. 28, # 8, p. 981 - 985
[7] Bioorganic and Medicinal Chemistry, 2000, vol. 8, # 11, p. 2663 - 2673
[8] Monatshefte fuer Chemie, 1946, vol. 76, p. 29
[9] Justus Liebigs Annalen der Chemie, 1881, vol. 207, p. 327
[10] Chemical & Pharmaceutical Bulletin, 1984, vol. 32, # 12, p. 5044 - 5047
[11] Journal of Medicinal Chemistry, 2004, vol. 47, # 24, p. 5937 - 5944
[12] Phosphorus, Sulfur and Silicon and the Related Elements, 2006, vol. 181, # 9, p. 2079 - 2087
[13] Patent: US6344463, 2002, B1, . Location in patent: Page column 18
[14] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 17, p. 6014 - 6024
[15] Transition Metal Chemistry, 2015, vol. 40, # 6, p. 665 - 671
[16] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 2, p. 355 - 360
[17] RSC Advances, 2018, vol. 8, # 12, p. 6306 - 6314
  • 14
  • [ 94-09-7 ]
  • [ 51934-41-9 ]
Reference: [1] Tetrahedron Letters, 1998, vol. 39, # 25, p. 4533 - 4536
[2] Organic Letters, 2017, vol. 19, # 10, p. 2518 - 2521
[3] Organic Letters, 2010, vol. 12, # 8, p. 1696 - 1699
[4] Organic Letters, 2018, vol. 20, # 17, p. 5167 - 5171
[5] Chemical Science, 2018, vol. 9, # 46, p. 8731 - 8737
  • 15
  • [ 624-38-4 ]
  • [ 109-94-4 ]
  • [ 591-50-4 ]
  • [ 51934-41-9 ]
YieldReaction ConditionsOperation in experiment
69%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5 h;
Stage #2: at -78℃; for 3 h;
Stage #3: With ethanol; iodine; potassium carbonate In tetrahydrofuran; hexane at -78 - 20℃; for 16 h;
General procedure: n-BuLi (1.67 M solution in hexane, 1.32 mL, 2.2 mmol) was added dropwise into a solution of p-bromochlorobenzene (383 mg, 2.0 mmol) in THF (3 mL) at -78 °C for 30 min. Then, ethyl formate (1.6 mL, 20 mmol) was added to the mixture and the obtained mixture was stirred at -78 °C. After 3 h at the same temperature, I2 (1523 mg, 6 mmol), K2CO3 (1382 mg, 10 mmol) and EtOH (3 mL) were added at -78 °C and the mixture was stirred for 14 h at rt. The reaction mixture was quenched with satd aq Na2SO3 (5 mL) and was extracted with CHCl3 (3.x.20 mL). The organic layer was washed with brine and dried over Na2SO4 to provide ethyl 4-chlorobenzoate in 77percent yield. If necessary, the product was purified by short column chromatography (SiO2:hexane:EtOAc=9:1) to give pure ethyl 4-chloro-1-benzoate as a colorless oil.
Reference: [1] Tetrahedron, 2012, vol. 68, # 24, p. 4701 - 4709
  • 16
  • [ 64-17-5 ]
  • [ 623-00-7 ]
  • [ 3058-39-7 ]
  • [ 51934-41-9 ]
YieldReaction ConditionsOperation in experiment
80% at 110℃; for 30 h; Schlenk technique; Inert atmosphere; Sealed tube General procedure: A Schlenk tube was charged with Cu2O (7.2 mg, 10 molpercent), l-proline (11.5 mg, 20 molpercent), aryl (or heteroaryl) bromide (1 or 3,0.50 mmol), potassium iodide (KI) (249 mg, 0.75 mmol), and EtOH(1.5 mL) under nitrogen atmosphere. The Schlenk tube was sealedwith a teflon valve, and then the reaction mixture was stirred at110C for a period (the reaction progress was monitored by GCanalysis). After the reaction was completed, GC yield of high volatileproduct was determined using an appropriate internal standard(chlorobenzene or 1-chloro-4-methylbenzene) or the solvent wasremoved under reduced pressure. The residue obtained was puri-fied via silica gel chromatography (eluent: petroleum ether/ethylacetate = 10/1) to afford aryl iodides 2a–2o or heteroaryl iodides4a–4g.
Reference: [1] Catalysis Today, 2016, vol. 274, p. 129 - 132
  • 17
  • [ 619-58-9 ]
  • [ 51934-41-9 ]
Reference: [1] Patent: US5877207, 1999, A,
[2] Patent: US5958954, 1999, A,
[3] Patent: US5919970, 1999, A,
[4] Patent: US6025388, 2000, A,
[5] Patent: US6037488, 2000, A,
[6] Patent: US5202471, 1993, A,
[7] Patent: US5489584, 1996, A,
[8] Patent: US5534641, 1996, A,
[9] Patent: US5616712, 1997, A,
[10] Patent: US5399561, 1995, A,
[11] Patent: US5688957, 1997, A,
[12] Patent: US4980369, 1990, A,
[13] Patent: US4739098, 1988, A,
[14] Patent: US4810804, 1989, A,
[15] Patent: EP290130, 1991, B1,
[16] Patent: US2004/102360, 2004, A1,
[17] Patent: US3957871, 1976, A,
  • 18
  • [ 348-06-1 ]
  • [ 51934-41-9 ]
Reference: [1] Chemical Science, 2018, vol. 9, # 46, p. 8731 - 8737
  • 19
  • [ 624-38-4 ]
  • [ 131379-16-3 ]
  • [ 37527-56-3 ]
  • [ 47230-38-6 ]
  • [ 51934-41-9 ]
Reference: [1] Bulletin of the Chemical Society of Japan, 2001, vol. 74, # 12, p. 2415 - 2420
  • 20
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  • [ 485817-30-9 ]
  • [ 51934-41-9 ]
Reference: [1] Organometallics, 2016, vol. 35, # 19, p. 3406 - 3412
  • 21
  • [ 125261-30-5 ]
  • [ 51934-41-9 ]
Reference: [1] Journal of the American Chemical Society, 2017, vol. 139, # 25, p. 8621 - 8627
  • 22
  • [ 125261-30-5 ]
  • [ 47230-38-6 ]
  • [ 51934-41-9 ]
Reference: [1] Synlett, 2006, # 6, p. 881 - 884
  • 23
  • [ 619-58-9 ]
  • [ 485817-30-9 ]
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Reference: [1] Organometallics, 2016, vol. 35, # 19, p. 3406 - 3412
  • 24
  • [ 902148-89-4 ]
  • [ 51934-41-9 ]
Reference: [1] Synlett, 2006, # 6, p. 881 - 884
  • 25
  • [ 120-47-8 ]
  • [ 51934-41-9 ]
Reference: [1] Synlett, 2006, # 6, p. 881 - 884
  • 26
  • [ 23239-88-5 ]
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Reference: [1] Journal of the American Chemical Society, 1933, vol. 55, p. 1649,1652
  • 27
  • [ 619-58-9 ]
  • [ 75-03-6 ]
  • [ 51934-41-9 ]
Reference: [1] European Journal of Organic Chemistry, 2013, # 26, p. 5886 - 5892
  • 28
  • [ 64-17-5 ]
  • [ 1711-02-0 ]
  • [ 51934-41-9 ]
Reference: [1] Journal of the Chemical Society. Perkin Transactions 2, 2001, # 9, p. 1620 - 1630
  • 29
  • [ 64-17-5 ]
  • [ 619-44-3 ]
  • [ 51934-41-9 ]
Reference: [1] Inorganic Chemistry, 2017, vol. 56, # 22, p. 13962 - 13974
  • 30
  • [ 51934-41-9 ]
  • [ 10602-00-3 ]
Reference: [1] Journal of the American Chemical Society, 1997, vol. 119, # 27, p. 6345 - 6359
[2] Bulletin of the Chemical Society of Japan, 2016, vol. 89, # 1, p. 27 - 32
[3] Angewandte Chemie - International Edition, 2016, vol. 55, # 47, p. 14852 - 14857[4] Angew. Chem., 2016, vol. 128, # 47, p. 15074 - 15079,6
  • 31
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  • [ 115-19-5 ]
  • [ 10602-00-3 ]
Reference: [1] Synthesis, 2008, # 4, p. 605 - 609
  • 32
  • [ 51934-41-9 ]
  • [ 10602-04-7 ]
Reference: [1] Macromolecules, 2005, vol. 38, # 15, p. 6367 - 6373
[2] Tetrahedron Letters, 2000, vol. 41, # 17, p. 3123 - 3126
[3] Chirality, 2015, vol. 27, # 8, p. 454 - 458
  • 33
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  • [ 123-54-6 ]
  • [ 73013-51-1 ]
Reference: [1] Journal of the American Chemical Society, 2010, vol. 132, # 24, p. 8273 - 8275
  • 34
  • [ 3002-24-2 ]
  • [ 51934-41-9 ]
  • [ 1232578-63-0 ]
  • [ 73013-51-1 ]
Reference: [1] Journal of the American Chemical Society, 2010, vol. 132, # 24, p. 8273 - 8275
  • 35
  • [ 5419-55-6 ]
  • [ 51934-41-9 ]
  • [ 4334-88-7 ]
YieldReaction ConditionsOperation in experiment
92% With n-butyllithium In tetrahydrofuran at -78℃; for 0.5 h; In 500mL three-necked flask,Ethyl 4-iodobenzoate (20.9 g, 75.8 mmol) was dissolved in dry THF (300.0 mL)Triisopropyl borate (42.8 g, 227.4 mmol) was added,The temperature was lowered to -78 ° C and n-butyllithium (9.7 g, 151.6 mmol) was added dropwise.Maintain the reaction temperature 0.5h.The reaction was completed, quenched with saturated aqueous ammonium chloride solution,1mol / L hydrochloric acid to adjust the pH to 1,Ethyl acetate (150.0 mL × 3), the organic phases were combined,Saturated brine (100 mL × 1), dried over anhydrous sodium sulfate,The solvent was distilled off under reduced pressure, the residue was beaten with n-hexane,The filtrate was filtered to give 4-ethoxycarbonyl phenylboronic acid 13.5g, a yield of 92.0percent.
Reference: [1] Patent: CN106565761, 2017, A, . Location in patent: Paragraph 0031; 0032
  • 36
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  • [ 51934-41-9 ]
  • [ 4334-88-7 ]
YieldReaction ConditionsOperation in experiment
94.4% With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; In 500mL three-necked flask,Ethyl 4-iodobenzoate (21.1 g, 76.4 mmol) was dissolved in dry THF (200.0 mL)Tri-n-butyl borate (26.4 g, 114.5 mmol) was added,The temperature was lowered to -78 ° C and n-butyllithium (6.9 g, 106.9 mmol) was added dropwise.Maintain the reaction temperature 1h.The reaction was completed, quenched with saturated aqueous ammonium chloride solution,1mol / L hydrochloric acid to adjust the pH to 1,Ethyl acetate (100.0 mL × 3), the organic phases were combined,Saturated brine (60 mL × 1), dried over anhydrous sodium sulfate,The solvent was distilled off under reduced pressure, the residue was beaten with n-hexane,The filtrate was filtered with 4-ethoxycarbonyl phenylboronic acid 14.0g,Yield 94.4percent.
Reference: [1] Patent: CN106565761, 2017, A, . Location in patent: Paragraph 0055; 0056; 0071; 0072
  • 37
  • [ 51934-41-9 ]
  • [ 4334-88-7 ]
Reference: [1] Journal of Organic Chemistry, 2002, vol. 67, # 15, p. 5394 - 5397
  • 38
  • [ 51934-41-9 ]
  • [ 1066-54-2 ]
  • [ 10602-03-6 ]
Reference: [1] Chemistry Letters, 2013, vol. 42, # 10, p. 1308 - 1310
[2] Patent: CN104151174, 2016, B, . Location in patent: Paragraph 0011; 0020; 0021
  • 39
  • [ 51934-41-9 ]
  • [ 10602-03-6 ]
Reference: [1] Tetrahedron Letters, 2004, vol. 45, # 8, p. 1693 - 1697
[2] Journal of Medicinal Chemistry, 2000, vol. 43, # 20, p. 3736 - 3745
[3] Journal of the American Chemical Society, 1997, vol. 119, # 27, p. 6345 - 6359
[4] Chemistry - A European Journal, 2011, vol. 17, # 34, p. 9320 - 9325
[5] Patent: WO2012/9472, 2012, A2,
[6] Patent: WO2013/20096, 2013, A2,
[7] Journal of the American Chemical Society, 2015, vol. 137, # 1, p. 413 - 419
[8] European Journal of Medicinal Chemistry, 2015, vol. 102, p. 93 - 105
[9] Organic and Biomolecular Chemistry, 2015, vol. 13, # 33, p. 8886 - 8892
  • 40
  • [ 51934-41-9 ]
  • [ 7681-65-4 ]
  • [ 1066-54-2 ]
  • [ 10602-03-6 ]
Reference: [1] Patent: US2002/120006, 2002, A1,
[2] Patent: US6624154, 2003, B1,
  • 41
  • [ 51934-41-9 ]
  • [ 10602-03-6 ]
Reference: [1] Organic Letters, 2018, vol. 20, # 15, p. 4601 - 4605
  • 42
  • [ 51934-41-9 ]
  • [ 107-18-6 ]
  • [ 151864-81-2 ]
YieldReaction ConditionsOperation in experiment
98.8% With tetrabutylammomium bromide; sodium hydrogencarbonate In N,N-dimethyl-formamide; toluene at 20 - 80℃; for 3.25 h; [0043] Ethyl 4-iodobenzoate (200 g, 0.725 mol) and allyl alcohol (63 g, 1.087 mol) are added to a stirred suspension of Sodium bicarbonate (152 g, 1.812 mol), tetrabutyl-ammounium bromide (117 g, 0.362 mol) and Palladium (II) acetate (3.2 g, 0.014 mol) in DMF (600 mL). The reaction mixture is warmed to 75-80° C. for 3-3.5 hours and cooled to 40° C.-50° C. Toluene (1 L) is added to the reaction mixture with vigorous agitation and the mixture is stirred for 15 min at room temperature. The resulting mixture is filtered through a celite pad. The pad is washed with toluene (2.x.200 mL). The filtrate and wash are combined, washed with water (3.x.1 L), evaporated to constant weight at 30° C.-40° C. and 10 mmHg. The crude product 147.5 g (98.8percent, 84percent by HPLC) of 4-(3-Oxo-propyl)-benzoic acid ethyl ester as dark brown oil is obtained and can be used in the next step without further purification. 1H NMR (DMSO-d6): δ1.38(t, 3H), 2.81(t, 2H), 3.03(t, 2H), 4.39(q, 2H), 7.27(d, 2H), 7.98(d, 2H), 9.81 (s, 1H).
84% With potassium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 96 h; A mixture of 150 g (0.54 mol) of ethyl 4-iodobenzoate, 47 g (0.81 mol) of allyl alcohol, 113.4 g (1.35 mol) of potassium hydrogen carbonate, 3.65 g (0.016 mol) of palladium acetate EPO <DP n="45"/>and 174 g (0.54 mol) of tetrabutylammonium bromide in 1875 ml of dimethylformamide is stirred at room temperature for 4 days. The reaction medium is filtered through Celite and then poured into water and extracted with ethyl acetate. The organic phases are combined, washed with water, dried over magnesium sulfate and concentrated on a rotary evaporator under vacuum. The black oil obtained (188 g) is purified by chromatography on a column of silica (dichloromethane). After evaporating off the solvents, the expected compound (94 g; 84percent) is isolated in the form of an orange-yellow oil.
37% With tetrabutylammomium bromide; palladium diacetate; sodium hydrogencarbonate In N,N-dimethyl-formamide at 70℃; for 3 h; Inert atmosphere; Molecular sieve; Sealed tube This compound has been reported and fully characterised.1 To a stirred suspension oftetrabutylammonium bromide (552 mg, 1.71 mmol), sodium hydrogen carbonate (380 mg,4.52 mmol) and 3Å molecular sieves (0.35 g) in DMF (6 mL) was added ethyl-4-iodobenzoate (296 μL, 1.76 mmol) and allyl alcohol (180 μL, 2.65 mmol) under a flow ofnitrogen. Palladium acetate (24.9 mg, 111 μmol) was added and and the reaction sealed andheated to 70oC. After stirring for 3 hours the mixture was filtered through celite, dilutingwith ethyl acetate (40 mL). This was washed with water (40 mL) and back extracted withethyl acatate (2 x 40 mL). The organic extracts were combined, dried (Na2SO4) andconcentrated. Purification by column chromatography (14-16percent EtOAc/Pet ether) gave 10 as a clear oil (135 mg, 0.65 mmol, 37percent).H (400 MHz, CDCl3): 9.82 (1H, s, CHO) 7.97(2H, d, J = 8.3 Hz, ArH), 7.26 (2H, d, J = 8.3 Hz, ArH), 4.36 (2H, q, J = 7.2 Hz, CH2CH3),2.96 - 3.05 (2H, t, J = 7.5Hz, CH2), 2.76 - 2.86 (2H, t, J = 7.5Hz, CH2), 1.38 (3H, t, J = 7.2Hz, CH2CH3); C (100 MHz, CDCl3): 200.9, 166.6, 145.8, 130.0, 128.8, 128.4, 61.0, 44.9,28.1, 14.4.
84 %Chromat. With tetrabutylammomium bromide; sodium hydrogencarbonate In N,N-dimethyl-formamide at 75 - 80℃; for 3 - 3.5 h; EXAMPLE 9
4-(3-Oxo-propyl)-benzoic acid ethyl ester
Ethyl 4-iodobenzoate (200 g, 0.725 mol) and allyl alcohol (63 g, 1.087 mol) are added to a stirred suspension of Sodium bicarbonate (152 g, 1.812 mol), tetrabutyl-ammounium bromide (117 g, 0.362 mol) and Palladium (II) acetate (3.2 g, 0.014 mol) in DMF (600 mL).
The reaction mixture is warmed to 75-80° C. for 3-3.5 hours and cooled to 40° C. -50° C. Toluene (1 L) is added to the reaction mixture with vigorous agitation and the mixture is stirred for 15 min at room temperature.
The resulting mixture is filtered through a celite pad.
The pad is washed with toluene (2*200 mL).
The filtrate and wash are combined, washed with water (3*1 L), evaporated to constant weight at 30° C.-40° C. and 10 mmHg.
The crude product 147.5 g (98.8percent, 84percent by HPLC) of 4-(3-Oxo-propyl)-benzoic acid ethyl ester as dark brown oil is obtained. 1H NMR (DMSO-d6): δ1.38 (t, 3H), 2.81 (t, 2H), 3.03 (t, 2H), 4.39 (q, 2H), 7.27 (d, 2H), 7.98 (d, 2H), 9.81 (s, 1H).
Crude 4-(3-Oxo-propyl)-benzoic acid ethyl ester (52percent purity as determined by HPLC) was dissolved in toluene (80 mL) and combined with water (100 mL). The mixture was stirred. A solution of sodium metabisulfite (55.4 g) and water (130 mL) was added over 45 min to the stirred solution. The reaction mixture was warmed to 32° C. for 1 h. The layers were separated and the aqueous layer was washed with toluene (2*25 mL). The layers were separated. Water (600 mL) and ethyl acetate (150 mL) were added to the aqueous layer. The mixture was stirred and cooled to 2° C. A solution of potassium carbonate (165 g) and water (160 mL) was added over 1 h to the stirred reaction mixture, maintaining an internal temperature of 0-2° C. The reaction mixture was warmed to 20-23° C. in 1 h and then stirred for 2 h. The layers were separated and the aqueous layer was washed with ethyl acetate (2*20 mL). The combined organic layers were washed with water (2*50 mL). The ethyl acetate was removed under reduced pressure at <24° C. to give purified 4-(3-Oxo-propyl)-benzoic acid ethyl ester (20.6 g, 41percent recovery). The purity was 96percent (as determined by HPLC). Mp 109° C.

Reference: [1] Tetrahedron Letters, 1999, vol. 40, # 21, p. 4023 - 4026
[2] Patent: US2005/49296, 2005, A1, . Location in patent: Page/Page column 7-8
[3] Organic Letters, 2009, vol. 11, # 22, p. 5342 - 5345
[4] Journal of Heterocyclic Chemistry, 2004, vol. 41, # 6, p. 941 - 946
[5] Patent: WO2006/63863, 2006, A1, . Location in patent: Page/Page column 43-44; 1/2
[6] Journal of Medicinal Chemistry, 2013, vol. 56, # 24, p. 10016 - 10032
[7] Tetrahedron Letters, 2015, vol. 56, # 46, p. 6397 - 6401
[8] Patent: US2006/41005, 2006, A1, . Location in patent: Page/Page column 9-10
[9] Patent: WO2008/89390, 2008, A1, . Location in patent: Page/Page column 54
  • 43
  • [ 51934-41-9 ]
  • [ 151864-81-2 ]
YieldReaction ConditionsOperation in experiment
98% With tetrabutylammomium bromide; sodium hydrogencarbonate In ethyl acetate; N,N-dimethyl-formamide A.
3-(4-Ethoxycarbonylphenyl)-1-propanal
To a solution of 20 g (69.9 mmol) of ethyl 4-iodobenzoate, 0.47 g (2.1 mmol) of palladium acetate, 14.7 g (175 mmol) of sodium bicarbonate, and 22.5 g (70 mmol) of tetrabutylammonium bromide in 200 mL of dimethyl formamide were added, under nitrogen, 6.89 g (118.8 mmol) of allyl alcohol.
The reaction mixture was stirred at room temperature for 42 hours.
The dimethyl formamide was then removed by evaporation under reduced pressure and the residue was dissolved in 300 mL of ethyl acetate.
This was washed with water (3*50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
The residual solid was purified by column chromatography on silica gel, eluding with 7:3 hexane:ethyl acetate to give 13.3 g (98percent) of 3-(4-ethoxycarbonylphenyl)-1-propanal as a light yellow oil. 1 H NMR (CDCl3) δ 10.02 (1H, s), 8.18 (2H, d, J=7.3 Hz), 7 47 (2H, d, J=7.3 Hz), 4.56 (2H, q, J=6.5 Hz), 3,21 (2H, t, J=6.5 Hz), 3.02 (2H, t, J=6.5 Hz), 1,59 (3H, t, J=6.5 Hz), Taylor, E. C. et al., J. Org. Chem., 57, 3218 (1992); J. Org. Chem., 60, 6684 (1995).
Reference: [1] Patent: US6066732, 2000, A,
  • 44
  • [ 51934-41-9 ]
  • [ 275386-60-2 ]
Reference: [1] Macromolecules, 2005, vol. 38, # 15, p. 6367 - 6373
[2] Tetrahedron Letters, 2000, vol. 41, # 17, p. 3123 - 3126
  • 45
  • [ 51934-41-9 ]
  • [ 1066-54-2 ]
  • [ 275386-60-2 ]
Reference: [1] Chirality, 2015, vol. 27, # 8, p. 454 - 458
  • 46
  • [ 431-47-0 ]
  • [ 51934-41-9 ]
  • [ 898787-14-9 ]
Reference: [1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 6, p. 913 - 918
  • 47
  • [ 51934-41-9 ]
  • [ 2923-18-4 ]
  • [ 898787-14-9 ]
Reference: [1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 6, p. 913 - 918
  • 48
  • [ 431-47-0 ]
  • [ 51934-41-9 ]
  • [ 898787-14-9 ]
Reference: [1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 6, p. 913 - 918
  • 49
  • [ 51934-41-9 ]
  • [ 1393124-08-7 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 10, p. 3051 - 3058
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