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[ CAS No. 119-61-9 ] {[proInfo.proName]}

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Chemical Structure| 119-61-9
Chemical Structure| 119-61-9
Structure of 119-61-9 * Storage: {[proInfo.prStorage]}
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Product Details of [ 119-61-9 ]

CAS No. :119-61-9 MDL No. :MFCD00003076
Formula : C13H10O Boiling Point : -
Linear Structure Formula :- InChI Key :RWCCWEUUXYIKHB-UHFFFAOYSA-N
M.W :182.22 Pubchem ID :3102
Synonyms :
Benzophenone

Calculated chemistry of [ 119-61-9 ]

Physicochemical Properties

Num. heavy atoms : 14
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.0
Num. rotatable bonds : 2
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 56.32
TPSA : 17.07 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.15 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.15
Log Po/w (XLOGP3) : 3.18
Log Po/w (WLOGP) : 2.92
Log Po/w (MLOGP) : 3.0
Log Po/w (SILICOS-IT) : 3.44
Consensus Log Po/w : 2.94

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.48
Solubility : 0.061 mg/ml ; 0.000335 mol/l
Class : Soluble
Log S (Ali) : -3.21
Solubility : 0.112 mg/ml ; 0.000617 mol/l
Class : Soluble
Log S (SILICOS-IT) : -4.86
Solubility : 0.0025 mg/ml ; 0.0000137 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.11

Safety of [ 119-61-9 ]

Signal Word:Danger Class:9
Precautionary Statements:P501-P273-P260-P270-P202-P201-P264-P280-P391-P308+P313-P337+P313-P305+P351+P338-P301+P312+P330-P405 UN#:3077
Hazard Statements:H302-H319-H373-H350-H411 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 119-61-9 ]

* 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 [ 119-61-9 ]
  • Downstream synthetic route of [ 119-61-9 ]

[ 119-61-9 ] Synthesis Path-Upstream   1~68

  • 1
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  • [ 119-61-9 ]
  • [ 67-72-1 ]
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  • [ 983-79-9 ]
Reference: [1] Tetrahedron Letters, 1988, vol. 29, # 48, p. 6287 - 6290
  • 2
  • [ 80500-16-9 ]
  • [ 2038-03-1 ]
  • [ 119-61-9 ]
Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 3, p. 730 - 736
  • 3
  • [ 14691-88-4 ]
  • [ 908093-98-1 ]
  • [ 36768-62-4 ]
  • [ 119-61-9 ]
Reference: [1] Journal of Organic Chemistry, 1984, vol. 49, # 26, p. 5214 - 5217
[2] Journal of Organic Chemistry, 1984, vol. 49, # 26, p. 5214 - 5217
  • 4
  • [ 80500-17-0 ]
  • [ 123-00-2 ]
  • [ 119-61-9 ]
Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 3, p. 730 - 736
  • 5
  • [ 80500-20-5 ]
  • [ 2706-56-1 ]
  • [ 119-61-9 ]
Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 3, p. 730 - 736
  • 6
  • [ 115975-19-4 ]
  • [ 612-59-9 ]
  • [ 119-61-9 ]
  • [ 67-72-1 ]
  • [ 983-79-9 ]
Reference: [1] Tetrahedron Letters, 1988, vol. 29, # 48, p. 6287 - 6290
  • 7
  • [ 120569-14-4 ]
  • [ 1532-91-8 ]
  • [ 119-61-9 ]
  • [ 67-72-1 ]
  • [ 983-79-9 ]
Reference: [1] Tetrahedron Letters, 1988, vol. 29, # 48, p. 6287 - 6290
  • 8
  • [ 120569-15-5 ]
  • [ 1448-87-9 ]
  • [ 119-61-9 ]
  • [ 67-72-1 ]
  • [ 983-79-9 ]
Reference: [1] Tetrahedron Letters, 1988, vol. 29, # 48, p. 6287 - 6290
  • 9
  • [ 119-61-9 ]
  • [ 18514-85-7 ]
  • [ 18514-84-6 ]
Reference: [1] Journal of the Chemical Society, 1945, p. 512,519
  • 10
  • [ 75997-02-3 ]
  • [ 19155-24-9 ]
  • [ 119-61-9 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1980, p. 1700 - 1705
  • 11
  • [ 119-61-9 ]
  • [ 841-77-0 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 4, p. 1822 - 1826
[2] Tetrahedron Letters, 2013, vol. 54, # 28, p. 3688 - 3693
[3] Journal of Enzyme Inhibition and Medicinal Chemistry, 2014, vol. 29, # 2, p. 205 - 214
[4] Synthetic Communications, 2014, vol. 44, # 5, p. 600 - 609
[5] Medicinal Chemistry Research, 2014, vol. 23, # 6, p. 3207 - 3219
[6] Analytical Chemistry, 2014, vol. 86, # 17, p. 8693 - 8699
[7] Journal of Chemistry, 2016, vol. 2016,
  • 12
  • [ 119-61-9 ]
  • [ 61613-22-7 ]
  • [ 20474-15-1 ]
YieldReaction ConditionsOperation in experiment
53%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h;
Stage #2: at 20℃; for 12 h;
After dissolving 10 g of 2-bromo-N-phenylphenylamine in 100 ml of tetrahydrofuran, the reaction temperature was lowered to -78 ° C,Slowly add 20 ml of 2.5 M butyllithium and stir for 1 h. 11 g of benzophenone was dissolved in 100 ml of tetrahydrofuran and slowlyAfter dropping, the temperature was increased to room temperature and stirred for 12 h. After the reaction has ended, distilled water and methylene chloride will be usedRow extraction and drying by anhydrous magnesium sulfate followed by filtration under reduced pressure gave the solid which was dissolved in 100 ml of acetic acid, 7 ml of sulfuric acid was added dropwise and the mixture was reflux-stirred. After the reaction was completed, the mixture was extracted with distilled water and methylene chlorideThe resulting solid was purified by column chromatography to give Intermediate B-1 (7.1 g, yield 53percent).
53%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h;
Stage #2: at 20℃; for 12 h;
Dissolve 2-bromo-N-phenylaniline 10g in 100ml After THF (tetrahydrofuran), the reaction temperature is lowered to -78 °C,20 ml of 2.5 M BuLi (butyllithium) was slowly added dropwise and stirred for 1 hour.Benzophenone 11g is dissolved in 100ml THF (tetrahydrofuran)After slowly adding dropwise, the temperature was raised to room temperature and stirred for 12 hours.After the reaction is over,A solid obtained by extracting with distilled water and MC (dichloromethane) and removing water using anhydrous magnesium sulfate and then filtering under reduced pressure is directly dissolved in 100 ml of acetic acid (Acetic acid) without further purification.7 ml of sulfuric acid was added dropwise and stirred under reflux. After the reaction is over,Use distilled water and MC (dichloromethane)The extraction was carried out and column purification of the resulting solid gave 7.1 g of I2. (Yield 53percent)
Reference: [1] Patent: CN107400085, 2017, A, . Location in patent: Paragraph 0048; 0049
[2] Patent: CN104471022, 2018, B, . Location in patent: Paragraph 0085-0087
  • 13
  • [ 119-61-9 ]
  • [ 84099-58-1 ]
  • [ 464-72-2 ]
  • [ 16806-93-2 ]
Reference: [1] Chemistry Letters, 2008, vol. 37, # 8, p. 822 - 823
  • 14
  • [ 38875-53-5 ]
  • [ 119-61-9 ]
  • [ 65147-89-9 ]
Reference: [1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1980, vol. 19, # 10, p. 863 - 865
  • 15
  • [ 119-61-9 ]
  • [ 750512-44-8 ]
  • [ 298-57-7 ]
Reference: [1] Synthetic Communications, 2014, vol. 44, # 5, p. 600 - 609
  • 16
  • [ 119-61-9 ]
  • [ 14470-28-1 ]
Reference: [1] Journal of Organic Chemistry, 1991, vol. 56, # 26, p. 7320 - 7322
[2] Journal of the American Chemical Society, 1944, vol. 66, p. 415
[3] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 19, p. 6252 - 6255
[4] Patent: US2014/5196, 2014, A1,
[5] Advanced Synthesis and Catalysis, 2014, vol. 356, # 18, p. 3755 - 3760
  • 17
  • [ 81194-62-9 ]
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Reference: [1] Journal of Organic Chemistry, 1986, vol. 51, # 11, p. 2131 - 2134
  • 18
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  • [ 111-77-3 ]
Reference: [1] Journal of Organic Chemistry, 1986, vol. 51, # 11, p. 2131 - 2134
  • 19
  • [ 52417-36-4 ]
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  • [ 758-16-7 ]
Reference: [1] Helvetica Chimica Acta, 1980, vol. 63, # 1, p. 102 - 116
  • 20
  • [ 152530-75-1 ]
  • [ 119-61-9 ]
  • [ 1501-27-5 ]
  • [ 52903-53-4 ]
Reference: [1] Journal of Organic Chemistry, 1993, vol. 58, # 23, p. 6442 - 6450
  • 21
  • [ 101858-70-2 ]
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  • [ 5617-32-3 ]
Reference: [1] Journal of Organic Chemistry, 1986, vol. 51, # 11, p. 2131 - 2134
  • 22
  • [ 119-61-9 ]
  • [ 105-56-6 ]
  • [ 5232-99-5 ]
Reference: [1] Synthetic Communications, 2008, vol. 38, # 17, p. 2967 - 2982
[2] Journal of Organic Chemistry, 1950, vol. 15, p. 381,386, 389
[3] Journal of the Indian Chemical Society, 1953, vol. 30, p. 443,445
[4] Journal of the American Chemical Society, 1941, vol. 63, p. 3455
[5] RSC Advances, 2013, vol. 3, # 13, p. 4311 - 4320
  • 23
  • [ 119-61-9 ]
  • [ 631-61-8 ]
  • [ 64-19-7 ]
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  • [ 71-43-2 ]
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Reference: [1] Journal of the American Chemical Society, 1941, vol. 63, p. 3455
  • 24
  • [ 119-61-9 ]
  • [ 59239-90-6 ]
  • [ 477-75-8 ]
  • [ 4423-41-0 ]
  • [ 77924-80-2 ]
Reference: [1] Journal of Organic Chemistry, 1981, vol. 46, # 16, p. 3357 - 3359
  • 25
  • [ 119-61-9 ]
  • [ 6011-14-9 ]
  • [ 70591-20-7 ]
Reference: [1] Synthetic Communications, 1995, vol. 25, # 3, p. 369 - 378
[2] Synthetic Communications, 1999, vol. 29, # 9, p. 1561 - 1569
  • 26
  • [ 119-61-9 ]
  • [ 623-33-6 ]
  • [ 69555-14-2 ]
YieldReaction ConditionsOperation in experiment
91%
Stage #1: With toluene-4-sulfonic acid In toluene at 110 - 115℃; for 4 h;
Stage #2: With N-ethyl-N,N-diisopropylamine In toluene for 1 h;
Example 1 : Preparation of benzophenone glycine imine ethyl ester. In a 1 litre glass reactor equipped with a distillation section and a Dean and Stark separator, 182g (1 mole) of benzophenone, 70.1g (0.5 mole) of glycine ethyl ester hydrochloride, 4.75g (0.05 mole) of paratoluenesulfonic acid and 249g of toluene were loaded. The mixture was heated at 110-115°C at atmospheric pressure to give a good reflux in toluene. 97g (1.05 mole) of N,N-diisopropyl N-ethyl amine was added by pump over 4 hours. During the reaction, water was formed and was distilled off as water-toluene azeotrop. Water was decanted in the Dean and Stark seprator and toluene was returned to the reactor. Reaction was pursued for 1 hour after the end of the amine addition and completion of the reaction was monitored by liquid chromatography. When reaction was complete, the reaction mixture was cooled down to 20°C. The mixture was then washed with 335g of water and the 2 liquid phases were separated by decantation. The bottom aqueous phase containing all N,N-diisopropyl N-ethyl amine hydrochloride was kept for treatment by aqueous sodium hydroxide to recover N,N-diisopropyl N-ethyl amine for recycle. The upper toluen phase containing benzophenone glycine imine ethyl ester and the excess benzophenone was concentrated during which operation water was removed as an azeotrope with toluene. The dry solution, of benzophenone glycine imine ethyl ester in toluene was assayed by liquid chromatography : a 91 percent yield of benzophenone glycine imine ethyl ester was obtained with respect to glycine ethyl ester hydrochloride.
48%
Stage #1: With potassium carbonate In water for 0.25 h;
Stage #2: With boron trifluoride diethyl etherate In xylene for 5 h; Reflux
2.1
Preparation of ethyl N-(diphenylmethylene)glycinate
Ethyl glycinate hydrochloride (37 g, 0.27 mol) was dissolved in a solution of K2CO3 (74.4 g, 0.54 mol) in water (186 ml).
The solution was stirred for 15 min and then extracted with dichloromethane (10*150 ml).
The organic phases obtained in this manner were combined, dried over MgSO4 and freed from solvent under reduced pressure (500 mbar) (yield ~50percent).
The residue (9.5 g, 0.092 mol) was, together with benzophenone (14.03 g, 0.077 mol) dissolved in xylene (76 ml).
After addition of a few drops of BF3*Et20, the reaction mixture was stirred under reflux conditions on a water separator for 5 h.
After cooling of the reaction mixture to room temperature, the solvent was removed under reduced pressure.
From the residue obtained, ethyl N-(diphenylmethylene)glycinate was isolated by distillation (80° C. at 5.5*10-2 mbar) in a yield of 48percent.
30%
Stage #1: With toluene-4-sulfonic acid In toluene at 115℃; Dean-Stark
Stage #2: With N-ethyl-N,N-diisopropylamine In toluene for 18.75 h;
Step 3: To a 500 mL three neck RB flask equipped with a distillation and a Dean-Stark separator, benzophenone (20 g, 109.8 mmol), glycine ethyl ester Hydrochloride (15.32 g, 109.8mmol), p-toluenesulfonic acid (0.522 g, 2.745 mmol) and 400 mL of toluene were added. The mixture was heated at 115 C with stirring to get a good reflux in toluene. Finally N, Ndiisopropyl ethyl amine (14.4 mL, 82.35 mmole) was added using a dropping funnel over 45 mm. During the reaction, water was formed which was decanted from the Dean-Stark separator and toluene were returned to the reactor. The reaction was monitored by TLC, and it took about18 h for 50percent completion. The reaction mixture was cooled down to room temperature, and extracted (3 x 100 mL) with ethyl acetate, collected organic layer and washed organic layer once with saturated NaCI solution. The organic layer separated, dried over Na2504, and distilled off the volatiles to get crude material, which was flash chromatographed to get 9.0 g (30percent isolated) ofEthyl-2-(diphenylmethyleneamino) acetate as a white solid, which was confirmedbyH1NMR.
Reference: [1] Patent: EP1422220, 2004, A1, . Location in patent: Page 5
[2] Patent: CN104557684, 2017, B, . Location in patent: Paragraph 0021-0026; 0027; 0028; 0029; 0030-0033
[3] Tetrahedron Letters, 2005, vol. 46, # 16, p. 2795 - 2797
[4] Patent: US2010/173777, 2010, A1, . Location in patent: Page/Page column 23
[5] Patent: WO2016/27285, 2016, A2, . Location in patent: Page/Page column 50; 51
[6] Patent: US2010/190794, 2010, A1, . Location in patent: Page/Page column 59
[7] Organic Letters, 2012, vol. 14, # 2, p. 552 - 555
[8] Angewandte Chemie - International Edition, 2013, vol. 52, # 49, p. 12942 - 12945[9] Angew. Chem., 2013, vol. 125, # 49, p. 13180 - 13183,4
[10] Patent: CN104788361, 2017, B, . Location in patent: Paragraph 0054-0056
  • 27
  • [ 119-61-9 ]
  • [ 459-73-4 ]
  • [ 69555-14-2 ]
YieldReaction ConditionsOperation in experiment
98.1% With pyrrolidine In N,N-dimethyl-formamide at 50℃; Molecular sieve Tetrahydropyrrole 0.85 g (12 mmol),Molecular sieve 100g,Glycine ethyl ester 10.3g (100mmol)And benzophenone 27.3g (150mmol)Added to the reaction vessel,200ml N,N-dimethylformamide as the reaction solvent,Raise the temperature to 50°C for 2 to 3 hours.The reaction solution was cooled to room temperature, poured into water, extracted with dichloromethane, and concentrated under reduced pressure.Column chromatography afforded glycine ethyl benzophenone imine 26.2g, a yield of 98.1percent, purity 99.25percent.
Reference: [1] Patent: CN107954886, 2018, A, . Location in patent: Paragraph 0027; 0032-0050
[2] Transition Metal Chemistry, 2010, vol. 35, # 8, p. 949 - 957
  • 28
  • [ 119-61-9 ]
  • [ 51-79-6 ]
  • [ 69555-14-2 ]
YieldReaction ConditionsOperation in experiment
93% With toluene-4-sulfonic acid; N-ethyl-N,N-diisopropylamine In tolueneReflux; Inert atmosphere 139.6 g of glycine ethyl ester, 400 g of benzophenone, 9.5 g of p-toluenesulfonic acid (PTS) and 400 ml of toluene were added to the reaction flask, and the temperature was raised to reflux, and diisopropylethylamine was slowly added to the reaction system. After diisopropylethylamine was added dropwise, the reaction was continued for 2 hours. The reaction solution was cooled to room temperature, 300 ml of water and 200 ml of toluene were added, stirred, and the layers were allowed to stand. The toluene layer was washed once with brine. The toluene layer was concentrated to dryness to give 490 g of liquid benzophenone glycine imide ethyl ester in 93percent yield.
Reference: [1] Patent: CN106467471, 2017, A, . Location in patent: Paragraph 0064; 0065; 0066; 0067
  • 29
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  • [ 6456-74-2 ]
Reference: [1] European Journal of Organic Chemistry, 2017, vol. 2017, # 34, p. 5154 - 5162
  • 30
  • [ 91-01-0 ]
  • [ 613-45-6 ]
  • [ 119-61-9 ]
  • [ 7314-44-5 ]
Reference: [1] Chemical Communications, 2018, vol. 54, # 50, p. 6883 - 6886
  • 31
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  • [ 3060-50-2 ]
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  • [ 267225-27-4 ]
  • [ 42538-40-9 ]
YieldReaction ConditionsOperation in experiment
46 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 32
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  • [ 23429-44-9 ]
Reference: [1] Journal of Organic Chemistry, 1991, vol. 56, # 26, p. 7320 - 7322
  • 33
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  • [ 10359-08-7 ]
  • [ 51513-29-2 ]
  • [ 2345-56-4 ]
Reference: [1] Synthetic Communications, 2004, vol. 34, # 24, p. 4545 - 4556
  • 34
  • [ 119-61-9 ]
  • [ 589-15-1 ]
  • [ 18648-66-3 ]
YieldReaction ConditionsOperation in experiment
90%
Stage #1: at 150℃; for 24 h; Inert atmosphere
Stage #2: With potassium <i>tert</i>-butylate In tetrahydrofuran for 24 h;
40.00 g of p-bromobenzyl bromide (0.16 mol) and 83.6 mL of triethyl phosphite (0.48 mol) were added to a solution of 500 mlThree bottles,Magnetic stirring and argon, oil bath heated at 150 ° C for 24 hours, cooled to room temperature,Get Ye Lide reagent.To the three-necked flask was added 450 ml of tetrahydrofuran (THF), 21.87 g of benzophenone (0.12 mol) and 40.39 g of potassium tert-butoxide (t-BuOK, 0.36 mol) were added and the mixture was stirred for 24 h. After the reaction was stopped, The solution was poured into water and extracted with a large amount of white precipitate. The precipitate was collected by extraction with a funnel, washed three times with ethanol and dried in a vacuum at 60C for 24 h to give Tri-Br as a white intermediate.
Reference: [1] Patent: CN104341311, 2016, B, . Location in patent: Paragraph 0028; 0029; 0030
[2] Chinese Journal of Chemistry, 2015, vol. 33, # 8, p. 939 - 947
  • 35
  • [ 119-61-9 ]
  • [ 38186-51-5 ]
  • [ 18648-66-3 ]
YieldReaction ConditionsOperation in experiment
72%
Stage #1: at 0℃; Inert atmosphere
Stage #2: With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 2 h; Inert atmosphere
A solution of benzophenone (1.82g, 10 mmol) and diethyl 4-bromobenzylphosphonate (3.1 g, 10 mmol) in anhydrous THF (40 mL) was stirred under argon atmosphere at 0 ºC. Potassium tert-butoxide (1.1 g, 10 mmol) was added quickly and the mixture was stirred for 2 h at room temperature. The reaction mixture was poured into ethanol and a solid precipitated out. The precipitate was filtered and washed with ethanol (3×10 mL) to afford product 6 as a white powder (2.41g, 72percent). Mp 52−54 ºC; IR (KBr, cm-1): 3032, 1610, 1484; 1H NMR (300 MHz, CDCl3): δ 7.25−7.18 (m, 3H), 7.16–7.06 (m, 5H), 7.05−6.94 (m, 4H), 6.92−6.82 (m, 3H); MS (EI): m/z 335, 337 (M+, M++2, 95, 100percent).
72% With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 2 h; Inert atmosphere A solution of benzophenone (1.82 g, 10 mmol) and diethyl 4-bromobenzylphosphonate (3.1 g, 10 mmol) in anhydrous THF (40 mL) was stirred under argon atmosphere at 0°C. Potassium tert-butoxide (1.1 g, 10 mmol) was added quickly and the mixture was stirred for 2 h at room temperature. The reaction mixture was poured into ethanol (10 mL) and a solid precipitated out. The precipitate was filtered and washed with ethanol (310 mL) to afford 1 as a white powder (2.41 g, 72percent). Mp 52-54 °C; IR (KBr, cm-1): 3032, 1610, 1484; 1H NMR (300 MHz, CDCl3): δ 7.25-7.18 (m, 3H), 7.16-7.06 (m, 5H), 7.05-6.94 (m, 4H), 6.92-6.82 (m, 3H); LCMS(EI): m/z 335 (MH+, 100percent).
Reference: [1] Journal of the American Chemical Society, 2000, vol. 122, # 24, p. 5695 - 5709
[2] Tetrahedron Letters, 2012, vol. 53, # 50, p. 6838 - 6842
[3] Dyes and Pigments, 2013, vol. 99, # 3, p. 740 - 747
[4] Patent: WO2009/51390, 2009, A2, . Location in patent: Page/Page column 64-65; 70-72
[5] Journal of Materials Chemistry, 2012, vol. 22, # 35, p. 18505 - 18513
[6] Chemistry - An Asian Journal, 2011, vol. 6, # 6, p. 1470 - 1478
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Reference: [1] Tetrahedron Letters, 2011, vol. 52, # 12, p. 1329 - 1333
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  • [ 362-59-4 ]
Reference: [1] Journal of Organic Chemistry, 2003, vol. 68, # 13, p. 5236 - 5243
  • 38
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  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 1132-68-9 ]
  • [ 18125-46-7 ]
YieldReaction ConditionsOperation in experiment
57 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 39
  • [ 119-61-9 ]
  • [ 61326-44-1 ]
Reference: [1] Journal of Nanoscience and Nanotechnology, 2016, vol. 16, # 3, p. 3102 - 3105
[2] Chemistry - A European Journal, 2017, vol. 23, # 35, p. 8390 - 8394
[3] Patent: CN107141250, 2017, A,
[4] Angewandte Chemie - International Edition, 2018, vol. 57, # 3, p. 729 - 733[5] Angew. Chem., 2018, vol. 130, # 3, p. 737 - 741,5
[6] Journal of the American Chemical Society, 2017, vol. 139, # 50, p. 18142 - 18145
[7] Angewandte Chemie - International Edition, 2018, vol. 57, # 20, p. 5750 - 5753[8] Angew. Chem., 2018, vol. 130, # 20, p. 5852 - 5855,4
[9] Journal of Materials Chemistry A, 2018, vol. 6, # 43, p. 21542 - 21549
  • 40
  • [ 119-61-9 ]
  • [ 90-90-4 ]
  • [ 34699-28-0 ]
Reference: [1] Chemistry - An Asian Journal, 2013, vol. 8, # 10, p. 2363 - 2369
[2] Analytical Chemistry, 2017, vol. 89, # 23, p. 12698 - 12704
[3] Journal of Materials Chemistry C, 2017, vol. 6, # 1, p. 19 - 28
  • 41
  • [ 119-61-9 ]
  • [ 90-90-4 ]
  • [ 34699-28-0 ]
Reference: [1] Journal of Materials Chemistry, 2007, vol. 17, # 44, p. 4670 - 4678
  • 42
  • [ 119-61-9 ]
  • [ 90-90-4 ]
  • [ 34699-28-0 ]
  • [ 632-51-9 ]
Reference: [1] Journal of Organic Chemistry, 2006, vol. 71, # 26, p. 9873 - 9876
  • 43
  • [ 119-61-9 ]
  • [ 27329-60-8 ]
Reference: [1] Advanced Synthesis and Catalysis, 2012, vol. 354, # 14-15, p. 2659 - 2664
  • 44
  • [ 5962-91-4 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 27527-05-5 ]
  • [ 58717-02-5 ]
YieldReaction ConditionsOperation in experiment
52 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 45
  • [ 3027-05-2 ]
  • [ 3060-50-2 ]
  • [ 2043-61-0 ]
  • [ 119-61-9 ]
  • [ 27527-05-5 ]
  • [ 58717-02-5 ]
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 46
  • [ 5962-91-4 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 27527-05-5 ]
  • [ 58717-02-5 ]
YieldReaction ConditionsOperation in experiment
52 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 47
  • [ 3027-05-2 ]
  • [ 3060-50-2 ]
  • [ 2043-61-0 ]
  • [ 119-61-9 ]
  • [ 27527-05-5 ]
  • [ 58717-02-5 ]
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 48
  • [ 119-61-9 ]
  • [ 68-12-2 ]
  • [ 2019-71-8 ]
Reference: [1] Organic and Biomolecular Chemistry, 2016, vol. 14, # 41, p. 9823 - 9835
  • 49
  • [ 28030-16-2 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 6230-11-1 ]
  • [ 39878-65-4 ]
YieldReaction ConditionsOperation in experiment
57 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 50
  • [ 7647-01-0 ]
  • [ 7500-79-0 ]
  • [ 119-61-9 ]
  • [ 4229-44-1 ]
Reference: [1] Chemische Berichte, 1918, vol. 51, p. 934
[2] Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1914, vol. &lt;5&gt; 23 II, p. 349
  • 51
  • [ 119-61-9 ]
  • [ 6456-74-2 ]
  • [ 81477-94-3 ]
YieldReaction ConditionsOperation in experiment
40% With boron trifluoride diethyl etherate In toluene at 130℃; for 8 h; To a solution of benzophenone (3g, 16.4 mmol) and glycine tertbutylester (1.8 g, 13.7 mmol) in anhydrous toluene (18 mL) wasadded boron trifluoride diethyl etherate (0.12 mL), and the mixturewas refluxed at 130 C for 8 h. After removal of the solvent in vacuo, the residue was dissolved in EtOAc (100 mL), and washedwith H2O (2 30 mL) and brine (2 30 mL), and dried (anhydrousNa2SO4). The crude product was purified by flash column chromatography(eluting with hexane/EtOAc, 20:1) to afford N-(diphenylamine)glycine tert-butyl ester (3) (1.4 g, 40percent yield) aswhite solid. M.p. 112–113 C; 1H NMR (300 MHz, CDCl3): d 1.46(s, 9H), 4.12 (s, 2H), 7.17-7.20 (m, 2H), 7.30-7.48 (m, 6H), 7.65-7.68 (m, 2H); 13C NMR (75 MHz, CDCl3): d 28.2, 56.4, 81.2, 128.1,128.9, 130.5, 139.5, 170.0, 171.6; HRMS (ESI, positive): Calcd. forC19H21NO2Na [M+Na]+ 318.1465; observed: 318.1463.
28.5 g With boron trifluoride diethyl etherate In tolueneReflux 1. Benzophenone (50 g) and glycine tert-butyl ester (30 g) were dissolved in 300 ml toluene and 2 ml of boron trifluoride etherate was added as a catalyst. The reaction mixture was refluxed for overnight. The solvent was removed on vacuum to give a crude product of as a white solid. The solid material obtained after evaporation was crystallized twice in hexane/diethyl ether (20:1 .v/v) to give a pure product of 2 (28.5 g) as a white solid.10085] 1H NMR (300 MHz, CDC13) 7.6-7.7 (m, 2H), 7.4-7.5 (m, 3H), 7.3-7.4 (m, 3H), 7.1-7.2 (m, 2H), 4.1-4.2 (m,2H), 1.4-1.5 (m, 9H).
Reference: [1] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 9, p. 2320 - 2330
[2] Patent: US2011/21527, 2011, A1, . Location in patent: Page/Page column 23
[3] Patent: US2014/135356, 2014, A1, . Location in patent: Paragraph 0083; 0084; 0085
  • 52
  • [ 119-61-9 ]
  • [ 5680-79-5 ]
  • [ 81167-39-7 ]
Reference: [1] European Journal of Organic Chemistry, 2017, vol. 2017, # 3, p. 695 - 703
[2] Patent: WO2010/123792, 2010, A1, . Location in patent: Page/Page column 11-13
[3] Revue Roumaine de Chimie, 2010, vol. 55, # 10, p. 689 - 695
[4] Angewandte Chemie - International Edition, 2013, vol. 52, # 49, p. 12942 - 12945[5] Angew. Chem., 2013, vol. 125, # 49, p. 13180 - 13183,4
[6] Journal of Materials Chemistry C, 2018, vol. 6, # 5, p. 1071 - 1082
  • 53
  • [ 1458-63-5 ]
  • [ 119-61-9 ]
  • [ 3254-89-5 ]
Reference: [1] Patent: CN106749101, 2017, A, . Location in patent: Paragraph 0039; 0040
  • 54
  • [ 119-61-9 ]
  • [ 98732-63-9 ]
  • [ 18629-11-3 ]
  • [ 5319-67-5 ]
Reference: [1] Phosphorus and Sulfur and the Related Elements, 1987, vol. 29, p. 233 - 238
  • 55
  • [ 119-61-9 ]
  • [ 5267-34-5 ]
Reference: [1] Patent: US2010/190771, 2010, A1, . Location in patent: Page/Page column 27-28
[2] Patent: EP2511283, 2012, A1,
[3] Patent: US2013/45942, 2013, A1,
[4] Journal of Chemical Research, 2018, vol. 42, # 4, p. 181 - 183
  • 56
  • [ 34906-87-1 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 57224-50-7 ]
  • [ 88319-43-1 ]
YieldReaction ConditionsOperation in experiment
62 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 57
  • [ 3027-05-2 ]
  • [ 630-19-3 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 57224-50-7 ]
  • [ 88319-43-1 ]
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 58
  • [ 38335-22-7 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 1991-87-3 ]
YieldReaction ConditionsOperation in experiment
53 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 59
  • [ 34906-87-1 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 57224-50-7 ]
  • [ 88319-43-1 ]
YieldReaction ConditionsOperation in experiment
62 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 60
  • [ 3027-05-2 ]
  • [ 630-19-3 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 57224-50-7 ]
  • [ 88319-43-1 ]
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
  • 61
  • [ 119-61-9 ]
  • [ 96-34-4 ]
  • [ 178306-47-3 ]
Reference: [1] Patent: US2011/263854, 2011, A1, . Location in patent: Page/Page column 7-8
  • 62
  • [ 119-61-9 ]
  • [ 178306-47-3 ]
Reference: [1] Patent: WO2012/17441, 2012, A1,
[2] Organic Process Research and Development, 2001, vol. 5, # 1, p. 16 - 22
[3] Patent: KR2016/39907, 2016, A,
[4] Patent: JP2017/128528, 2017, A,
[5] Organic Process Research and Development, 2018, vol. 22, # 9, p. 1200 - 1207
  • 63
  • [ 119-61-9 ]
  • [ 124-41-4 ]
  • [ 96-34-4 ]
  • [ 178306-51-9 ]
YieldReaction ConditionsOperation in experiment
80%
Stage #1: at -10 - 40℃; for 1 h;
Stage #2: With toluene-4-sulfonic acid In methanol at 20℃; for 1 h;
Stage #3: at 97℃;
91.11 g (0.5 mol) of benzophenone and 45.92 g (0.85 mol) of sodium methoxide were added,Was suspended in 150 ml of methyl t-butyl ether (MTB) at room temperature. After cooling to -10 ° C.,92.24 g (0.85 mol) of methyl chloroacetate,In such a way that the internal temperature rose to 40 ° C. while the outside was cooled in a bath at -10 ° C.next,The mixture was stirred for 1 hour at naturally occurring temperature without cooling.250 ml of water was added,After stirring for a while,The aqueous phase was separated.The MTB phase was washed with 250 ml of an aqueous dilute sodium chloride solution.After changing the solvent to methanol (250 ml)A solution of 1 g of p-toluenesulfonic acid in 10 ml of methanol was added at room temperature.The mixture was stirred at naturally occurring temperature for 1 hour,Followed by heating under reflux.While methanol was distilled off,400 g of 10percent strength sodium hydroxide solution was added dropwise,Finally 60 ml of water was added.This methanol was added drop-Until the bottom temperature reached 97 ° C,And distilled.After cooling to 55 ° C., 190 ml of MTB was added and the mixture was acidified to pH 2 with about 77 ml of concentrated hydrochloric acid.After cooling to room temperature, the aqueous phase was distilled off, and the organic phase was concentrated by distilling 60 ml of MTB.The product was crystallized by adding 500 ml of heptane and gradually cooled to room temperature.The crude crystalline solid was filtered off with suction, washed with heptane and dried in a vacuum oven at 40 ° C. to constant weight.Yield: 108.9 g (80percent), HPLC> 99.5percent area.
Reference: [1] Patent: JP5700378, 2015, B2, . Location in patent: Paragraph 0070
  • 64
  • [ 119-61-9 ]
  • [ 178306-51-9 ]
Reference: [1] Patent: US2011/263854, 2011, A1,
[2] Patent: WO2012/17441, 2012, A1,
[3] Organic Process Research and Development, 2001, vol. 5, # 1, p. 16 - 22
[4] Patent: KR2016/39907, 2016, A,
[5] Patent: JP2017/128528, 2017, A,
  • 65
  • [ 119-61-9 ]
  • [ 178306-52-0 ]
Reference: [1] Patent: US2011/263854, 2011, A1,
[2] Patent: WO2012/17441, 2012, A1,
[3] Patent: KR2016/39907, 2016, A,
[4] Patent: JP2017/128528, 2017, A,
  • 66
  • [ 119-61-9 ]
  • [ 13361-34-7 ]
  • [ 6197-30-4 ]
YieldReaction ConditionsOperation in experiment
76.3% With ammonium acetate; acetic acid In water at 85 - 90℃; for 16 h; A 1000 mL four neck round bottom flask, equipped with a mechanical stirrer, a thermometer and a condenser, was charged with 2-ethylhexyl cyanoacetate (347 g, 1.76 gmol), benzophenone (200 g, 1.1 gmol) , recovered acetic acid (168.3 g containing 2percent water, 2.75 gmol) and ammonium acetate (3 lg, 0.4 gmol). The stirred reaction mass was then heated to 85-90°C. Azeotrope of acetic acid/water mixture was distilled off oyer a period of 16 h. under reduced pressure from 400-420 mm of Hg A till the Gas chromatographic analysis showed no further decrease in benzophenone concentration in reaction mass. The loss of acetic acid was continuously adjusted by adding the corresponding recovered acetic acid. The acetic acid was then recovered under reduced pressure (30-60 mm of Hg A). The HPLC analysis of reaction mass showed BPCA content of 0.19percent. The crude reaction mixture was cooled and washed twice with 300 g portion of water and subsequently distilled to yield pale yellow colored viscous liquid (303 g, Yield 76.3percent) which was found to be of 99.48percent purity by Gas chromatographic analysis.
66.18% With propionic acid In n-heptane at 110℃; for 5 h; Into a 500ml four-neck round-bottom flask, equipped with a mechanical stirrer, a thermometer and a condenser is charged with 62.2 g (0.32mol) of 2-Ethylhexyl cyanoacetate (EHCA) and 81.Og (0.45 mol) of Benzophenone (BP) (molar ratio EHCA:BP = 0.71 : 1) and 27.7g (0.36 mol) of ammonium acetate and 81.0g (1.1 mol) of propionic acid and 81.0g of heptane. The mixture is heated under stirring. When the temperature reach H O0C, a mixture of propionic acid, water, heptane is distilled off over a period of 5 hours at normal pressure. Heptane phase is returned back to the flask. Then the reactant is cooled to 900C, and 100 ml of hot water is added to the reaction mixture. The mixture is kept at 85°C for 10 minutes, and then transferred to a funnel for separation. To a flask equipped with a column 256.Og of crude 2-ethylhexyl 2-cyano-3,3- diphenylacrylate solution is added. Rectification is carried out at 1 mbar. 2-Ethylhexyl 2-cyano- <n="9"/>3,3-diphenylacrylate is distilled out at 2100C (vapor). After distillation, light yellow 2-ethylhexyl 2-cyano-3,3-diphenylacrylate is obtained. Reaction yields are as indicated in table 1 and assume recycle of unreacted benzophenone and 2-EHCA.The experiment is repeated by adjusting the amount of 2-EHCA in order to give the molar ratios as indicated in the table 1 below.
Reference: [1] Patent: WO2014/178061, 2014, A2, . Location in patent: Page/Page column 9; 10
[2] Patent: WO2008/89920, 2008, A1, . Location in patent: Page/Page column 7-8
  • 67
  • [ 119-61-9 ]
  • [ 13361-34-7 ]
  • [ 731-48-6 ]
  • [ 6197-30-4 ]
YieldReaction ConditionsOperation in experiment
0.42 - 0.7 %Chromat. With propionic acid In n-heptane at 95 - 110℃; for 6 h; Heating / reflux A 2000ml reactor is charged with 3 U g of 2-ethylhexyl cyanoacetate, 70 g of ammoniumacetate, 404 g of benzophenones, 405 g of propionic acid and 405 g of n-heptane. The mixture is heated to about 950C under stirring at reduced pressure (about 700 mbar in order to maintain the reaction at reflux). When the temperature reached 950C a mixture of heptane, water and propionic acid is distilled off azeotropically over a period of 6h wherein the organic phase is recharged back in the reactor. During this time every hour 25 g of additional ammonium acetate is added stepwise (5 portions, 1 per hour). After the reaction is finished heptane and propionic acid are distilled off at reduced vacuum (up to 20 mbar while keeping the temperature below about 95°C). When no more distillate is observed, 500g of water is added and the mixture is stirred for 10 min at 75°C. After adding 340 g of n-heptane the organic phase is collected and the washing procedure is repeated. After evaporation of the solvent at reduced pressure (temperature is maintained below 95°C) the crude product (comprising about 0.04 percent of 2-cyano-3,3-diphenyl-2-propenamide) is collected followed by distillation using a wiped thin film evaporator. A second distillation yielded 388 g of light yellow octocrylene comprising about 0.38 percent of 2-cyano-3,3-diphenyl- 2-propenamide (determined via HPLC). The reaction is repeated at normal pressure and a temperature of about HO0C (reflux temperature) resulting after purification in an amount of 0.7 percent of 2-cyano-3,3- diphenyl- 2-propenamide
Reference: [1] Patent: WO2008/89920, 2008, A1, . Location in patent: Page/Page column 9
  • 68
  • [ 120240-65-5 ]
  • [ 3060-50-2 ]
  • [ 119-61-9 ]
  • [ 267225-27-4 ]
  • [ 42538-40-9 ]
YieldReaction ConditionsOperation in experiment
46 % ee With C39H33N3O2*2ClH In methanol; water at 20℃; for 72 h; General procedure: To a 5 mL vial equipped with a magnetic stirrer bar were added 3-cyclohexyl-2-oxopropanoic acid (1j) (0.0510 g, 0.30 mmol), 2,2-diphenylglycine (2) (0.0681 g, 0.30 mmol), chiral pyridoxamine 6g (0.0195 g, 0.030 mmol), and MeOH-H2O (8:2) (3.0 mL). The mixture was stirred at 20 °C for 3 days. The reaction mixture was transferred to a 25 mL round-bottom flask and MeOH was added until all the solid was dissolved. Then silica gel (0.50 g) was added. After removal of the solvent in vacuo at 20 °C, the resulting residue was submitted to column chromatography on silica gel (EtOH/ethyl acetate/25-28percent ammonia solution =100:58:16) to give compound 3j (0.0401 g, 78percent yield, 52percent ee) as a white solid. The enantiomeric excesses of 3b-k were deteremined by HPLC analysis after being converted to N-benzoyl methyl esters by treatment with thionyl chloride in methanol and subsequent reaction benzoyl chloride.7 The enantiomeric excess of 3a was deteremined by HPLC analysis after being converted to its methyl ester by treatment with CH2N2 in methanol.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 41, p. 4612 - 4615
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