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CAS No. : | 117-34-0 | MDL No. : | MFCD00004251 |
Formula : | C14H12O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PYHXGXCGESYPCW-UHFFFAOYSA-N |
M.W : | 212.24 g/mol | Pubchem ID : | 8333 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.07 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 62.47 |
TPSA : | 37.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.4 cm/s |
Log Po/w (iLOGP) : | 1.52 |
Log Po/w (XLOGP3) : | 3.09 |
Log Po/w (WLOGP) : | 2.9 |
Log Po/w (MLOGP) : | 3.15 |
Log Po/w (SILICOS-IT) : | 2.97 |
Consensus Log Po/w : | 2.72 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.56 |
Log S (ESOL) : | -3.46 |
Solubility : | 0.0737 mg/ml ; 0.000347 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.54 |
Solubility : | 0.0611 mg/ml ; 0.000288 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -4.34 |
Solubility : | 0.00963 mg/ml ; 0.0000454 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.02 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
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* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68 % ee | With 2,2-dimethylpropanoic anhydride; N-ethyl-N,N-diisopropylamine In diethyl ether at 20℃; for 12 h; | Test Example 5Production of Optically Active 2-Hydroxy Ester Using Various Types of Racemic 2-Hydroxy Ester (3) As shown in the above reaction scheme, to diethyl ether (0.2 M) containing 0.6 equivalents of pivalic acid anhydride and 0.5 equivalents of diphenylacetic acid were added 1.2 equivalents of diisopropyl ethylamine, 5percent by mole of (+)-benzotetramisole (BTM), and a solution containing 1 equivalent of a racemic 2-hydroxy ester in diethyl ether at room temperature in this order, and this reaction mixture was stirred at room temperature for 12 hrs. Thereafter, the reaction was stopped with a saturated aqueous sodium bicarbonate solution. After the organic layer was fractionated, the aqueous layer was extracted with diethyl ether three to five times. After the organic layers were admixed, the mixture was dried over anhydrous sodium sulfate. The solution was filtered and thereafter vacuum concentrated. Thus obtained mixture was fractionated on silica gel thin layer chromatography (developing solvent: hexane/ethyl acetate=3/1) to afford a corresponding diester and unreacted optically active 2-hydroxy ester. The results are shown in Table 5. TABLE 5 Yield [percent] [a] cc [percent] No.R5 R6 5a; 5b 5a; 5b s 29 Et n-Pr 47; 47 97; 89 217 30 Me Me 47; 23 97; 68 119 [a] Isolation yieldAs is seen from Table 5, prominently high enantiomeric excess ee and reaction velocity ratio s were exhibited also when a material other than the benzyl ester was used (Entries 29 and 30).The physical properties of the optically active hydroxy esters and the diesters in Table 5 are shown below.(Entry 29)Ethyl (S)-2-hydroxypentanoate1H NMR (CDCl3): δ4.19 (dq, J=14.0, 7.0 Hz, 1H, Eta), 4.18 (dq, J=14.0, 7.5 Hz, 1H, Eta), 2.96 (br d, J=3.5 Hz, 1H, OH), 1.75-1.65 (m, 1H, 3-H), 1.62-1.52 (m, 1H, 3-H), 1.48-1.30 (m, 2H, 4-H), 1.24 (dd, J=7.5, 7.0 Hz, 3H, Eta), 0.89 (t, J=7.3 Hz, 3H, 5-H);13C NMR (CDCl3): δ175.3, 70.2, 61.4, 36.4, 17.9, 14.1, 13.6.Ethyl (R)-2-(diphenylacetyloxy)pentanoateHPLC (CHIRALCEL AD-H, i-PrOH/hexane=1/50, flow rate=1.0 mL/min): tR=15.0 min (1.4percent), tR=17.5 min (98.6percent);IR (neat): 1745, 1496, 1454, 745, 701 cm-1;1H NMR (CDCl3): δ7.33-7.17 (m, 10H, Ph), 5.08 (s, 1H, 2'-H), 4.98 (dd, J=7.0, 6.0 Hz, 1H, 2-H), 4.12 (dq, J=14.0, 7.5 Hz, 3H, Eta), 4.11 (dq, J=14.0, 7.0 Hz, 3H, Eta), 1.78-1.71 (m, 2H, 3-H), 1.32-1.28 (m, 2H, 4-H), 1.16 (dd, J=7.5, 7.0 Hz, 3H, Eta), 0.81 (t, J=7.5 Hz, 3H, 5-H);13C NMR (CDCl3): δ172.1, 170.1, 138.4, 138.3, 128.7, 128.6, 128.4, 127.3, 127.2, 120.4, 72.9, 61.2, 56.8, 33.0, 18.3, 14.0, 13.5;HR MS: calcd for C21H24O4Na (M+Na+) 363.1567. found 363.1569.(Entry 30)Methyl (S)-lactate1H NMR (CDCl3): δ4.24 (q, J=7.0 Hz, 1H, 2-H), 3.72 (s, 3H, MeO), 3.16 (br s, 1H, OH), 1.36 (d, J=7.0 Hz, 3H, 3-H);13C NMR (CDCl3): δ176.0, 66.6, 52.3, 20.2.Methyl (R)-2-(diphenylacetyloxy)propanoateHPLC (CHIRALCEL AD-H, i-PrOH/hexane=1/50, flow rate=0.75 mL/min): tR=16.4 min (98.3percent), tR=19.7 min (1.7percent);IR (neat): 1744, 1496, 1454, 748, 699 cm-1;1H NMR (CDCl3): δ7.28-7.20 (m, 8H, Ph), 7.19-7.13 (m, 2H, Ph), 5.07 (q, J=7.0 Hz, 1H, 2-H), 5.03 (s, 1H, 2'-H), 3.60 (s, 3H, MeO), 1.37 (d, J=7.0 Hz, 3H, 3-H);13C NMR (CDCl3): δ171.9, 170.9, 138.3, 138.2, 128.7, 128.63, 128.55, 128.4, 127.3, 127.2, 69.2, 56.6, 52.2, 16.8;HR MS: calcd for C18H18O4Na (M+Na+) 321.1097. found 321.1091. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.7% | (1) Preparation of methyl 2,2-diphenylacetate To a 500 mL three-opening flask were added 2,2-diphenylacetic acid (20 g, 94 mmol) and 200 mL dichloromethane. After stirring, 1 mL DMF was added. To the mixture was slowly added oxalyl chloride (13.16 g, 104 mmol) dropwisely in an ice bath. The reaction was conducted at 25 C. After the completion of reaction, the mixture was evaporated under reduced pressure to remove oxalyl chloride. To the reaction flask were slowly added dichloromethane (100 mL) and anhydrous methanol (3.61 g, 113 mmol) dropwisely under cooling in an ice bath respectively. The reaction was conducted at 25 C. After the completion of reaction, the reaction solution was washed with a saturated aqueous NaCl solution. The organic phase was dried over sodium sulfate, and filtered by suction. The filtrate was evaporated to dryness to produce methyl 2,2-diphenylacetate (21 g) in a yield of 98.7%. | |
98.7% | With oxalyl dichloride; N,N-dimethyl-formamide; In dichloromethane; at 25℃;Cooling with ice; | (1) Preparation of methyl 2,2-diphenylacetate To a 500mL three-opening flask were added 2,2-diphenylacetic acid (20g, 94mmol) and 200mL dichloromethane. After stirring, 1mL DMF was added. To the mixture was slowly added oxalyl chloride (13.16g, 104mmol) dropwisely in an ice bath. The reaction was conducted at 25C. After the completion of reaction, the mixture was evaporated under reduced pressure to remove oxalyl chloride. To the reaction flask were slowly added dichloromethane (100mL) and anhydrous methanol (3.61g, 113mmol) dropwisely under cooling in an ice bath respectively. The reaction was conducted at 25C. After the completion of reaction, the reaction solution was washed with a saturated aqueous NaCl solution. The organic phase was dried over sodium sulfate, and filtered by suction. The filtrate was evaporated to dryness to produce methyl 2,2-diphenylacetate (21 g) in a yield of 98.7 %. |
93% | With sulfuric acid;Reflux; | Methyl 2,2-diphenylacetate To a stirred solution of 2,2-diphenylacetic acid (1 gram, 1 equiv) in dry MeOH (50 mL) was added sulfuric acid (0.4 mL) dropwise and heated to reflux. Stirring was then continued for 3 hours. The reaction mixture was then cooled and poured into saturated aqueous NaHCO3 and extracted with EtOAc. The combined organic fractions were dried over Na2SO4, filtered, and concentrated under reduced pressure to yield an oil (1.0 g, 93%) that was not further purified. |
84.37% | With sulfuric acid; at 80℃; for 2h; | A mixture of compound (AA) (280.00 g, 1.32 mol, 1.00 eq.) was dissolved in MeOH (1.4 L), and then H2SO4 (140.00 mL) was added. The mixture was stirred at 80 C. for 2 h and monitored by TLC (PE:EA=5:1), which showed no starting material after 2 h. The mixture was concentrated. The residue was washed with aq. NaHCO3 (2000 mL) and extracted with EA (1000 mL). The organic layer was concentrated to give compound (BB) (280 g, 84.37%). 1H NMR: (CDCl3, 400 MHz): delta7.38-7.29 (m, 10H), 5.07 (s, 1H), 3.78 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With thionyl chloride | 4.1 (1) (1) Diphenylacetic acid chloride 21.2 g (0.1 mol) of diphenylacetic acid and 75 ml (about 1 mol) of thionyl chloride are mixed cold. The reaction mixture is heated under reflux for 3 hours and is cooled, the excess thionyl chloride is evaporated and the acid chloride (crystallized at a low temperature, melting point < 50° C.) is collected. 22.9 g of acid chloride (yield about 99%) are thus obtained. |
96% | With thionyl chloride In benzene for 2h; Reflux; | |
90% | With thionyl chloride for 1h; Heating; |
86% | With thionyl chloride for 2h; Heating; | |
85% | With thionyl chloride In toluene for 7.5h; Heating / reflux; | A The preparation of diphenylketene. The preparation of diphenylketene was carried out according to the published procedure starting from diphenylacetic acid. [Taylor, E. C. , et al. , Org Synth CV 6,549.] A. Diphenylacetyl chloride.; A 500 mL, three-necked flask equipped with a dropping funnel and a reflux condenser carrying a calcium chloride drying tube was charged with diphenylacetic acid (50.0 g, 0.236 mol) and anhydrous toluene (150 mL). The mixture was heated under reflux, and thionyl chloride (132 g, 80.1 mL, 1.11 mol) was added dropwise over 30 minutes. Refluxing was continued for 7 additional hours and then the toluene and excess thionyl chloride were removed by distillation under reduced pressure. The residue was dissolved in 150 mL of refluxing, anhydrous hexane. The hot solution was treated with charcoal and filtered, and the filtrate was cooled to 0°C in a sealed flask. The product, which crystallizes as colorless plates was filtered, washed with a little cold hexane, dried at 25°C under vacuum giving diphenylacetyl chloride (46 g, 85%), m. p. 51-52°C. |
68% | With Amberlite IRA 93 (PCl5 form) In dichloromethane for 6h; Heating; | |
With thionyl chloride | ||
With phosphorus(V) chloride | ||
With phosphorus(V) chloride; trichlorophosphate | ||
With thionyl chloride | ||
With oxalyl dichloride In benzene for 3h; Ambient temperature; | ||
With thionyl chloride In dichloromethane for 12h; Heating; Yield given; | ||
With oxalyl dichloride In 1,4-dioxane for 3h; Heating; | ||
With thionyl chloride for 15h; | ||
With thionyl chloride at 90 - 100℃; for 3h; | ||
With thionyl chloride for 1h; Heating; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In benzene for 2h; Ambient temperature; | ||
With thionyl chloride In toluene for 4h; Heating; | ||
With thionyl chloride for 2h; Heating; | ||
With thionyl chloride for 2h; Heating; | ||
With oxalyl dichloride In dichloromethane at 0 - 20℃; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In benzene for 18h; | ||
With oxalyl dichloride | ||
With thionyl chloride In benzene Heating; | ||
With thionyl chloride for 0.75h; Heating; | ||
With thionyl chloride for 0.25h; Heating; | ||
With thionyl chloride In benzene for 4h; Heating; | ||
With thionyl chloride In dichloromethane for 1.5h; Heating; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane for 12h; | ||
With thionyl chloride In dichloromethane for 1.5h; Heating; | ||
100 % Spectr. | With trichloroacetonitrile; triphenylphosphine In chloroform-d1 at 20℃; for 0.25h; | |
With thionyl chloride for 2h; Heating; | ||
With thionyl chloride; N,N-dimethyl-formamide | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h; | ||
With thionyl chloride for 2h; Reflux; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; | ||
With thionyl chloride In chloroform | ||
With thionyl chloride at 20 - 50℃; for 1.5h; | ||
With trichloroacetonitrile; triphenylphosphine In acetonitrile at 20℃; Inert atmosphere; | ||
With thionyl chloride at 0℃; Reflux; | ||
With thionyl chloride for 3h; Reflux; | General procedure: Compound 10 was prepared by a procedure similar to that of Lu and co-workers, and Nagao and co-workers. A solution of octanoic acid (4.43g, 30.74mmol) and thionyl chloride (20mL) was heated under reflux for 3h. The excess thionyl chloride was removed in vacuo and the crude octanoyl chloride taken through to the next step without further purification. A solution of 2 (12.0g, 21.55mmol), triethylamine (4.6mL, 33.3mmol), dimethylaminopyridine (0.26g, 2.16mmol) and crude octanoyl chloride in dimethylformamide (150mL) was then stirred at room temperature for 3h. The mixture was then diluted with ethyl acetate (200mL) and washed with water (200mL). The separated aqueous phase was further extracted with ethyl acetate (2×100mL) and the combined organic phases washed with brine (4×100mL), dried over anhydrous magnesium sulfate, filtered and the solvent removed in vacuo. Purification by flash chromatography (hexane/ethyl acetate 2:1) afforded 10 as an off-white solid (9.92g, 14.66mmol, 68%). | |
With thionyl chloride at 80℃; for 6h; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In chloroform at 20℃; for 1h; Inert atmosphere; | ||
With thionyl chloride; N,N-dimethyl-formamide In toluene at 0℃; for 3h; Reflux; | ||
With thionyl chloride Reflux; | ||
With thionyl chloride Reflux; | ||
With thionyl chloride Reflux; | 5.1.1. N-(3-Bromopropyl)-3,5-dichlorobenzamide (10a) Compound 9a (191 mg, 1 mmol) was refluxed in excess of thionylchloride (3 mL) overnight. Excess of thionyl chloride was evaporatedand the residue was dissolved in CH2Cl2, 3-bromopropylamine hydrobromide (328 mg, 1.5 mmol was addedfollowed by triethylamine (TEA; 0.42 mL, 3 mmol). The reactionmixture was stirred at room temperature. After the reaction wascompleted, the reaction mixture was diluted with CH2Cl2 andsequentially washed with water, 1 N HCl and saturated NaHCO3.The organic layer was dried over MgSO4, filtered and concentrated.The obtained product was purified by column chromatographywith n-hexane/ethyl acetate (EtOAc) = 4:1 to obtain 10a, (236 mg,76%) as white solid. | |
With I,I-bischloroiodobenzene; triphenylphosphine In dichloromethane for 0.166667h; Reflux; Inert atmosphere; | ||
With thionyl chloride at 50 - 60℃; | ||
With phosphorus trichloride at 50 - 60℃; | In a 250 ml reaction flask, I (20.0 g) was added, stirred, phosphorus trichloride (100 ml) was added, heated to 50-60 ° C, the gas was absrobed from the lye, and reacted for 3-4 h. After completion of the reaction, the organic layer was separated to obtain brown liquid 2,2-diphenylacetyl chloride (formula II). | |
Multi-step reaction with 2 steps 1: magnesium(II) sulfate; sulfuric acid / dichloromethane / 20 °C / Inert atmosphere 2: thionyl chloride; lithium hydroxide monohydrate / 20 °C / Sealed tube | ||
With thionyl chloride In tetrahydrofuran; toluene; benzene Reflux; | 4.1.27. N-(2-Chloroethyl)-2,2-diphenylacetamide (18a) Compound 17a (530 mg, 2.49 mmol) was refluxed in excess of thionyl chloride (10 mL) in presence of benzene for overnight. Excess of thionyl chloride and benzene was evaporated and the residue was dissolved in CH2Cl2, 2-chloroethylamine hydrochloride(432 mg, 3.73 mmol) was added followed by triethylamine(TEA; 1 mL, 7.47 mmol). The reaction mixture was stirred at room temperature. After the reaction was completed, the reaction mixture was diluted with CH2Cl2 and sequentially washed with water,1 N HCl and saturated NaHCO3. The organic layer was dried overMgSO4, filtered and concentrated. The obtained product was purified by column chromatography with n-hexane: Ethyl acetate(EtOAc) = 4:1 to obtain 18a (386 mg, 60%) as light yellow liquid.Rf = 0.82 (n-hexane: EtOAc = 1:1). 1H NMR (300 MHz, CDCl3): d7.43-7.33 (m, 11H), 3.73-3.65 (m, 4H). | |
In dichloromethane at 20 - 80℃; for 1h; | ||
With thionyl chloride In benzine for 24h; Inert atmosphere; Reflux; | 5.8. General procedure for the synthesis of diphenylacetic acid chloride (18) A solution of diphenylacetic acid 17 (5 g, 23.56 mmol) in benzene (10 mL) was treated by the dropwise addition of SOCl2 (42 g, 0.35 mol, 26 mL) under nitrogen atmosphere. Then the reaction mixture was heated at reflux with stirring for 24 h, cooled to room temperature and stirred for another 24 h. Next, the excess of SOCl2 and benzene were removed under vacuum to obtained desired acid chloride 18 as a colorless oil, which solidified on standing. Diphenylacetic acid chloride (18) was further used without any purification. | |
Stage #1: 2,2-diphenylacetic acid With oxalyl dichloride In dichloromethane for 0.333333h; Inert atmosphere; Stage #2: With N,N-dimethyl-formamide In dichloromethane for 2h; Inert atmosphere; | ||
With thionyl chloride; N,N-dimethyl-formamide In dichloromethane at 55℃; for 5h; | ||
With thionyl chloride In dichloromethane for 6h; Reflux; | ||
With tungsten hexachloride In dichloromethane-d2 for 18h; Inert atmosphere; | ||
With thionyl chloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 0.5h; Inert atmosphere; | ||
With thionyl chloride at 90℃; | ||
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h; | ||
With chlorinating agent In dichloromethane at 0℃; | ||
With thionyl chloride at 25℃; for 0.5h; Inert atmosphere; | ||
With thionyl chloride In toluene at 55℃; for 0.5h; | ||
With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; for 4h; Inert atmosphere; | ||
With thionyl chloride In benzene for 12h; Reflux; | Synthesis of 1,2-13C-labeled diphenylacetyl chloride (8) General procedure: According to the literatures,6,7 a solution of 1,2-13C-labeled diphenylacetic acid (7) (7.15 g, 33.4 mmol) and thionyl chloride (5.0 mL, 70 mmol) in dry benzene (5.0 mL) was refluxed for 12 h, and then residual thionyl chloride was removed by distillation under reduced pressures. 1,2-13C-Labeled diphenylacetyl chloride (8) (6.71 g, 28.8 mmol) was obtained as a colorless solid by distillation using a glass tube oven and recrystallization in hexane. 8 was immediately used for the next stage. | |
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 1h; | 9.8; 10.1 [0145] 2,2-diphenylacetic acid (37 mg, 0.17 mmol) and DMF (1 drop) were added to dry dichloromethane (10 mL). After cooling to 0 °C, oxalyl chloride (27 mg, 0.21 mmol) was added, stirred at room temperature for 1 hour, and then concentrated under reduced pressure. The residue was dissolved in dichloromethane (2 mL) to obtain a 2,2-diphenylacetyl chloride solution. C283-8 (40 mg, 0.14 mmol) and triethylamine (28 mg, 0.28 mmol) were dissolved in dichloromethane (5 mL) and cooled to 0 °C. The previous 2,2-diphenylacetyl chloride solution was then slowly added. The reaction solution was allowed to react at room temperature for 5 hours. LC-MS indicated that the reaction of the starting materials was complete. Dichloromethane (30 mL) was added, washed with saturated brine (20 mL 3), dried over anhydrous sodium sulfate for 30 min and then filtered. The filtrate was concentrated under reduced pressure to obtain a crude compound. The crude product was subjected to separation by thin layer chromatography (petroleum ether:ethyl acetate=2:1) to obtain Compound C283-9 (30 mg, a colorless oily liquid, yield: 44%). MS m/z (ESI): 470.0 [M+H] +. | |
With thionyl chloride at 100℃; | ||
With thionyl chloride; N,N-dimethyl-formamide In dichloromethane at 85℃; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In the inert gas N2 atmosphere, after dehydration and deoxidation treatment to the reaction bottle after adding diphenyl acetic acid (105.8 mg, 0.5 mmol, gun for adding [...] borane (289 mul, 2 mmol), reacting at room temperature 12 hours, the reaction out of the glove box, in order to have three methoxybenzene (83.84 mg, 0.5 mmol) as the internal standard, CDCl3 for dissolving, stirring 10 minutes, sampling, with nuclear magnetic resonance. Calculated 1 H and the yield is 99%. The product of nuclear magnetic data: The residue is added to the sample in 1 g silica gel, in order to 3 ml methanol as a solvent, 50 C lower reaction 3 h, the borate further hydrolysis alcohol, after the reaction, extracted with ethyl acetate three times, the combined organic layer, dried with anhydrous sodium sulfate, the solvent is removed under reduced pressure, through the silica gel (100 - 200 mesh) column chromatography purification, ethyl acetate/hexane (1:5) mixture as the eluent, to obtain the pure primary alcohol, separation and the yield is 92%. | |
86% | With 1,1,3,3-Tetramethyldisiloxane; copper(II) bis(trifluoromethanesulfonate); In toluene; at 80℃; for 16h;sealed tube; | General procedure: In a sealed tube, 29 mg Cu(OTf)2 (0.08 mmol, 8 mol %) and 0.7 mL TMDS (537 mg, 4 mmol, 8 Si-H mol/mol substrate) were introduced to a solution of aliphatic carboxylic acid (1 mmol) in 1.5 mL toluene. After stirring 16 h at 80 C, the reaction mixture was cooled to room temperature and quenched with 4 mL H2O. The organic layer was extracted with CH2Cl2, dried with anhydrous MgSO4, and evaporated under reduced pressure. The crude was purified by silica gel column chromatography to obtain the alcohol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium hypochlorite; lithium hypochlorite In ethanol at 77℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With dmap; dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; for 15h;Inert atmosphere; | General procedure: A solution of diphenylacetic acid (212 mg, 1.0 mmol), N-methylaniline (128 mg, 1.2mmol), DCC (247 mg, 1.2 mmol), and DMAP (24 mg, 0.2 mmol) in CH2Cl2 (1.5 mL) was stirred at room temperature for 15 h. After aqueous extractive workup and column chromatographic purification process (hexanes/Et2O,5:1) 1a was obtained as a white solid, 226 mg (75%). Other 2,2,N-triarylacetamides were prepared similarly from corresponding N-arylaminesand 2,2-diarylacetic acids. Diphenylacetic acid, bis(4-chlorophenyl)acetic acid and 9-fluorenecarboxylic acid were purchased from commercial sources, and other diarylacetic acids were prepared by Friedel-Crafts reaction of arenes and corresponding mandelic acid derivatives according to the reported methods.3,4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58.8% | With dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; for 24h; | 3.4 g (16.4 mmol) of N,N'-dicyclohexylcarbodiimide (DCC) was added to a solution of 3.84 g (16.4 mmol) of diphenylacetic acid and 1.67 g (14.8 mmol) of 4-pyridylcarbinol in 50 mL of dichloromethane. The reaction mixture was stirred at room temperature for about 24 h. The urea precipitate was filtered off, and the filtrate was washed with (2 25 mL) NaHCO3 and (2 25 mL) water. The organic layer were collected and dried over MgSO4, and the solvent was evaporated yielding required compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium azide; TEA; triethylphosphine In dichloromethane; dimethyl sulfoxide at 0℃; for 30h; | |
88% | With sodium azide; triethylamine; triphenylphosphine In dichloromethane; dimethyl sulfoxide at 0 - 20℃; for 0.833333h; | |
Multi-step reaction with 2 steps 1: diethyl ether; NH3 / 230 °C / im geschlossenen Rohr 2: PCl5; POCl3 |
Multi-step reaction with 3 steps 1: thionyl chloride 2: ammonia 3: thionyl chloride / 90 - 105 °C | ||
Multi-step reaction with 2 steps 1.1: thionyl chloride / tetrahydrofuran / 1 h / 50 °C 1.2: 0.08 h / 0 °C 2.1: palladium diacetate; Selectfluor; acetonitrile / 18 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With (R)-(+)-2-phenyl-2,3-dihydrobenzo[d]imidazo[2,1-b]thiazole; 2,2-dimethylpropanoic anhydride; N-ethyl-N,N-diisopropylamine In diethyl ether at 20℃; for 12h; Inert atmosphere; Resolution of racemate; optical yield given as %ee; enantioselective reaction; | |
1: 82 % ee 2: 44% | With 2,2-dimethylpropanoic anhydride; N-ethyl-N,N-diisopropylamine In diethyl ether at 20℃; for 12h; | 2 Test Example 2Production of Optically Active 2-Hydroxy Ester Using Various Types of Carboxylic Acid Anhydride As shown in the above reaction scheme, to dichloromethane (0.2 M) containing 0.6 equivalents of carboxylic acid anhydride and 0.5 equivalents of diphenylacetic acid were added 1.2 equivalents of diisopropyl ethylamine, 5% by mole of (+)-benzotetramisole (BTM), and a solution containing 1 equivalent of racemic benzyl lactate in dichloromethane at room temperature in this order, and this reaction mixture was stirred at room temperature for 12 hrs. Thereafter, the reaction was stopped with a saturated aqueous sodium bicarbonate solution. After the organic layer was fractionated, the aqueous layer was extracted with diethyl ether three to five times. After the organic layer was mixed, the mixture was dried over anhydrous sodium sulfate. The solution was filtered and thereafter vacuum concentrated. Thus obtained mixture was fractionated on silica gel thin layer chromatography (developing solvent: hexane/ethyl acetate=3/1) to afford a corresponding diester and unreacted optically active benzyl lactate. The results are shown in Table 2. TABLE 2 No.R2 Yield [%] of 2a[a] 2a /2c[b] Yield [%] of 2b[a] ee (2a;2b) [%] s 8 Ph 46 87/13 43 92;84 64 94-Me0C6H4 35 80/20 48 95;62 70 10 t-Bu 44 98/2 55 94;68 62 11PhMe2C 27 98/2 43 95;75 92 12Ph2MoC 37 >99/<1 44 96;62 87 13Ph3C 11 >99/<1 75 97;12 7214[c] t-Bu 44 98/2 55 97;82 146 [a]Isolation yield[b]Determined by 1H NMR[c]Diethyl ether used in place of dichloromethaneAs is seen from Table 2, Test Example 2 in which diphenylacetic acid was used as the carboxylic acid exhibited a very high reaction velocity ratio s of no less than 62 for any of the carboxylic acid anhydrides of Entries 8 to 14 used. Also, when a bulky carboxylic acid anhydride such as pivalic acid anhydride was used, the amount of the by-product (compound 2c) was small (Entries 10 to 14), and particularly, when pivalic acid anhydride was used, a high yield was attained (Entries 10 and 14). Furthermore, when diethyl ether was used in place of dichloromethane, a prominently high reaction velocity ratio s was attained (Entry 14). |
1: 50 % ee 2: 33% | With 1-phenyl-1-cyclopentanecarboxylic acid anhydride; N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 12h; | 4 Test Example 4Production of Optically Active 2-Hydroxy Ester Using Various Types of Racemic 2-Hydroxy Ester (2) As shown in the above reaction scheme, to a solution containing 0.50 equivalents of diphenylacetic acid and 0.60 equivalents of 1-phenyl-1-cyclopentanecarboxylic acid anhydride in dichloromethane were sequentially added 1.2 equivalents of diisopropyl ethylamine, 5% by mole of (+)-benzotetramisole ((+)-BTM), and the racemic 2-hydroxy ester at room temperature. This reaction mixture was then allowed to react at room temperature for 12 hrs, whereby a corresponding optically active ester and an unreacted 2-hydroxy ester were obtained. The results are shown in Table 4. TABLE 4 Yield [%] [a] ee [%] No. R 4 4a; 4b 4a; 4b s 27 Me 33; 58 97; 50 107 28 Et 31; 49 94; 52 58 [a] Isolation yieldAs is seen from Table 4, also when 1-phenyl-1-cyclopentanecarboxylic acid anhydride and diphenylacetic acid were used in combination in place of diphenylacetic acid anhydride, prominently high enantiomeric excess ee and reaction velocity ratio s were attained (Entries 27 and 28).The production method and the physical properties of the optically active hydroxy esters and the diesters presented in Table 4 are shown below.(Entry 27)To a solution containing 1-phenyl-1-cyclopentanecarboxylic acid anhydride (48.3 mg, 0.133 mmol) and diphenylacetic acid (23.6 mg, 0.111 mmol) in dichloromethane was added diisopropyl ethylamine (46.4 μL, 0.266 mmol) at room temperature. After this reaction mixture was stirred for 10 min, (+)-benzotetramisole (2.8 mg, 0.0111 mmol) and racemic benzyl lactate (35.7 μL, 0.222 mmol) were added thereto at room temperature. After this reaction mixture was stirred at room temperature for 12 hrs, saturated sodium bicarbonate water was added at room temperature to stop the reaction. After the organic layer was fractionated, the aqueous layer was extracted with diethyl ether five times. After the organic layer was mixed, the mixture was dried over anhydrous sodium sulfate. The solution was filtered and thereafter vacuum concentrated. Thus obtained mixture was fractionated on silica gel thin layer chromatography (developing solvent: hexane/ethyl acetate=3/1), and a highly polar fraction was fractionated again on silica gel thin layer chromatography (developing solvent: benzene/ethyl acetate=9/1) to afford a corresponding diester (23.0 mg, 58%, 50% ee) and unreacted optically active benzyl lactate. Moreover, the poorly polar fraction was also fractionated on silica gel thin layer chromatography (developing solvent: hexane/diethyl ether=5/1) to afford a corresponding diester (7.6 mg, 33%, 97% ee) and unreacted optically active benzyl lactate.Benzyl (S)-lactate[α]D28=-10.0 (c 1.10, acetone);HPLC (CHIRALPAK OD-H, i-PrOH/hexane=1/50, flow rate=1.0 mL/min): tR=16.7 min (75.2%), tR=18.7 min (24.8%);1H NMR (CDCl3): δ7.42-7.31 (m, 5H, Ph), 5.22 (s, 2H, Bn), 4.33 (ddd, J=13.4, 6.9, 5.4 Hz, 1H, 2-H), 2.81 (d, J=5.4 Hz, 1H, OH), 1.44 (d, J=6.9 Hz, 3H, 3-H).Benzyl (R)-2-(2,2-diphenylacetyloxy)propanoate[α]D28=+34.6 (c 1.43, CHCl3);HPLC (CHIRALPAK OD-H, i-PrOH/hexane=2/3, flow rate=1.0 mL/min): tR=30.6 min (1.5%), tR=46.3 min (98.5%);1H NMR (CDCl3): δ7.41-7.20 (m, 15H, Ph), 5.24-5.13 (m, 3H, 2-H, Bn), 5.10 (s, 1H, 2'-H), 1.49 (d, J=7.2 Hz, 3H, 3-H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (R)-9-methyl-2-phenyl-9-hydro-2-imidazolino[1,2-a]benzimidazole; 2,2-dimethylpropanoic anhydride In diethyl ether at 20℃; for 12h; Resolution of racemate; optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (R)-9-methyl-2-phenyl-9-hydro-2-imidazolino[1,2-a]benzimidazole; 2,2-dimethylpropanoic anhydride In diethyl ether at 20℃; for 12h; Resolution of racemate; optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 84 % ee 2: 46% | With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 12h; | 2 Test Example 2Production of Optically Active 2-Hydroxy Ester Using Various Types of Carboxylic Acid Anhydride As shown in the above reaction scheme, to dichloromethane (0.2 M) containing 0.6 equivalents of carboxylic acid anhydride and 0.5 equivalents of diphenylacetic acid were added 1.2 equivalents of diisopropyl ethylamine, 5% by mole of (+)-benzotetramisole (BTM), and a solution containing 1 equivalent of racemic benzyl lactate in dichloromethane at room temperature in this order, and this reaction mixture was stirred at room temperature for 12 hrs. Thereafter, the reaction was stopped with a saturated aqueous sodium bicarbonate solution. After the organic layer was fractionated, the aqueous layer was extracted with diethyl ether three to five times. After the organic layer was mixed, the mixture was dried over anhydrous sodium sulfate. The solution was filtered and thereafter vacuum concentrated. Thus obtained mixture was fractionated on silica gel thin layer chromatography (developing solvent: hexane/ethyl acetate=3/1) to afford a corresponding diester and unreacted optically active benzyl lactate. The results are shown in Table 2. TABLE 2 No.R2 Yield [%] of 2a[a] 2a /2c[b] Yield [%] of 2b[a] ee (2a;2b) [%] s 8 Ph 46 87/13 43 92;84 64 94-Me0C6H4 35 80/20 48 95;62 70 10 t-Bu 44 98/2 55 94;68 62 11PhMe2C 27 98/2 43 95;75 92 12Ph2MoC 37 >99/<1 44 96;62 87 13Ph3C 11 >99/<1 75 97;12 7214[c] t-Bu 44 98/2 55 97;82 146 [a]Isolation yield[b]Determined by 1H NMR[c]Diethyl ether used in place of dichloromethaneAs is seen from Table 2, Test Example 2 in which diphenylacetic acid was used as the carboxylic acid exhibited a very high reaction velocity ratio s of no less than 62 for any of the carboxylic acid anhydrides of Entries 8 to 14 used. Also, when a bulky carboxylic acid anhydride such as pivalic acid anhydride was used, the amount of the by-product (compound 2c) was small (Entries 10 to 14), and particularly, when pivalic acid anhydride was used, a high yield was attained (Entries 10 and 14). Furthermore, when diethyl ether was used in place of dichloromethane, a prominently high reaction velocity ratio s was attained (Entry 14). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62 % ee 2: 35% | With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 12h; | 1 Test Example 1Production of Optically Active 2-Hydroxy Ester Using Various Types of Carboxylic Acid As shown in the above reaction scheme, to dichloromethane (0.2 M) containing 0.6 equivalents of p-methoxybenzoic acid anhydride (PMBA) and 0.5 equivalents of carboxylic acid were added 1.2 equivalents of diisopropyl ethylamine, 5% by mole of (+)-benzotetramisole (BTM), and a solution containing 1 equivalent of racemic benzyl lactate in dichloromethane at room temperature in this order, and this reaction mixture was stirred at room temperature for 12 hrs. Thereafter, the reaction was stopped with a saturated aqueous sodium bicarbonate solution. After the organic layer was fractionated, the aqueous layer was extracted with diethyl ether three to five times. It is to be noted that for Entries 6 and 7, the aqueous layer was extracted with dichloromethane. After the organic layer was mixed, the mixture was dried over anhydrous sodium sulfate. The solution was filtered and thereafter vacuum concentrated. Thus obtained mixture was fractionated on silica gel thin layer chromatography (developing solvent: hexane/ethyl acetate=3/1) to afford a corresponding diester and unreacted optically active benzyl lactate. The results are shown in Table 1.The enantiomeric excess ee was determined by an HPLC analytical method on a chiral column. Further, the reaction velocity ratio s was calculated based on the formula of: s=[ln(1-C) (ee of 1-product)]/[ln(1-C) (ee of 1+product)], according to a method of Kagan et al, (Top. Stereochem., 1988, 18, p. 249-330). TABLE 1 No.R1 Yield [%] of 1a[a] 1a /1c[b] Yield [%] of 1b[a] ee (1a;1b) [%] s 1Ph(CH2)2 33 86/14 54 80;42 14 2p-To1CH2 35 86/14 42 85;46 20 3 i-Pr 50 95/5 47 85;78 29 4 c-Hex 38 87/13 34 88;56 27 5Ph2CH 35 80/20 48 95;62 70 6(α-Np)2CH 8 84/16 86 94;6 35 7(β-Np)2CH 31 89/11 52 95;51 63 [a]Isolation yield[b]Determined by 1H NMRAs is seen from Table 1, when a carboxylic acid having a secondary carbon atom in the α-position like a carboxylic acid in which R1 is Ph(CH2)2 or p-TolCH2 was used, the reaction velocity ratio s was no greater than 20 in either case, which was not satisfactory (Entries 1 and 2). On the other hand, when a more bulky carboxylic acid having a tertiary carbon atom in the α-position was used, the reaction velocity ratio s was as high as no less than 27. Accordingly, optically active benzyl lactate was successfully obtained with high efficiency (Entries 3 to 7). In particular, when diphenylacetic acid was used as the carboxylic acid, all of the yield, the enantiomeric excess ee, and the reaction velocity ratio s were very high (Entry 5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 51% 2: 48% | With (R)-(+)-2-phenyl-2,3-dihydrobenzo[d]imidazo[2,1-b]thiazole; 2,2-dimethylpropanoic anhydride; N-ethyl-N,N-diisopropylamine In diethyl ether at 20℃; for 12h; Inert atmosphere; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With diphenyl diselenide; dihydrogen peroxide; In water; at 20℃; for 6h;Green chemistry; | General procedure: Diphenyl diselenide (3, 0.006 g; 0.02 mmol) was treated with H2O2 (30%·w/w, 0.1 mL, 1 mmol) andwater (0.2 mL) and stirred at room temperature at 800 rpm until the discoloration of the reaction mixture;then, the aldehyde 1 (1 mmol) was added. After 6 h, the aqueous mixture was extracted three times withEtOAc (3 × 20 mL). The collected organic layers were dried over Na2SO4 and the solvent evaporatedunder reduced pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With 4-methyl-morpholine; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In N,N-dimethyl-formamide; at 20.0℃; | Step 1: To a stirred solution of [17] (0.08g, 0.42mmol) in DMF (5.0ml) was added EDC (0.12g, 0.63 mmol), HOBT (0.08g, 0.63mmol) at room temperature. After an additional stirring for 5 minutes at same temperature, [16](0.08g, 0.42mmol) and NMM (0.14ml, 2.3mmol) was added. The reaction temperature was allowed to stir at room temperature for overnight. TLC showed complete consumption of starting material. Water (100 ml) was added and organic layer was extracted with ethyl acetate (2 x 100 ml). The combined organic layers were washed with water, brine and dried over sodium sulphate. The organic layer was concentrated to afford light brown sticky which was subjected to column chromatography with 1% MeOH/DCM as eluent to afford off white solid material[18] (0.1 lg, 68%). Analytical Data: [18] ESIMS: 385 [M++l ]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With dmap; dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; for 15h;Inert atmosphere; | General procedure: A solution of diphenylacetic acid (212 mg, 1.0 mmol), N-methylaniline (128 mg, 1.2mmol), DCC (247 mg, 1.2 mmol), and DMAP (24 mg, 0.2 mmol) in CH2Cl2 (1.5 mL) was stirred at room temperature for 15 h. After aqueous extractive workup and column chromatographic purification process (hexanes/Et2O,5:1) 1a was obtained as a white solid, 226 mg (75%). Other 2,2,N-triarylacetamides were prepared similarly from corresponding N-arylaminesand 2,2-diarylacetic acids. Diphenylacetic acid, bis(4-chlorophenyl)acetic acid and 9-fluorenecarboxylic acid were purchased from commercial sources, and other diarylacetic acids were prepared by Friedel-Crafts reaction of arenes and corresponding mandelic acid derivatives according to the reported methods.3,4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 15h; Inert atmosphere; | Typical procedure for the preparation of 1a General procedure: A solution of diphenylacetic acid (212 mg, 1.0 mmol), N-methylaniline (128 mg, 1.2mmol), DCC (247 mg, 1.2 mmol), and DMAP (24 mg, 0.2 mmol) in CH2Cl2 (1.5 mL) was stirred at room temperature for 15 h. After aqueous extractive workup and column chromatographic purification process (hexanes/Et2O,5:1) 1a was obtained as a white solid, 226 mg (75%). Other 2,2,N-triarylacetamides were prepared similarly from corresponding N-arylaminesand 2,2-diarylacetic acids. Diphenylacetic acid, bis(4-chlorophenyl)acetic acid and 9-fluorenecarboxylic acid were purchased from commercial sources, and other diarylacetic acids were prepared by Friedel-Crafts reaction of arenes and corresponding mandelic acid derivatives according to the reported methods.3,4 |
58% | Stage #1: 2,2-diphenylacetic acid With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0℃; for 0.5h; Stage #2: With dmap In dichloromethane at 20℃; for 0.166667h; Stage #3: 2-(N-methylamino)pyridine With triethylamine In dichloromethane at 20℃; for 1h; | General procedure for synthesis of N-methyl-2-amino pyridine amides General procedure: A. To a mixture of benzoic acid (50 mg, 0.41 mmol, 1 equiv), PPh3 (160 mg, 0.61 mmol, 1.5 equiv) and NBS (108.5 mg, 0.61 mmol, 1.5 equiv), CH2Cl2 (1.5 ml) was added and the reaction was stirred at 0 °C for 30 min. Thereaction was brought to room temperature and DMAP (10 mg, 0.08 mmol, 0.20 equiv) was added and stirred for 10 min. The mixture of N-methyl-2-amino pyridine (49 mg, 0.45 mmol, 1.1 equiv), Et3N (45.5 mg, 63 µl, 0.45 mmol, 1.1 equiv) and CH2Cl2 (0.5 ml) were added and the reaction was stirred for1 h at room temperature. The reaction mixture was diluted with EtOAc and washed with aqueous sodium bicarbonate solution. The bicarbonate washings were again extracted with EtOAc and the combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure.Column chromatography was performed using EtOAc/Petroleum ether (1:5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 15h; Inert atmosphere; | Typical procedure for the preparation of 1a General procedure: A solution of diphenylacetic acid (212 mg, 1.0 mmol), N-methylaniline (128 mg, 1.2mmol), DCC (247 mg, 1.2 mmol), and DMAP (24 mg, 0.2 mmol) in CH2Cl2 (1.5 mL) was stirred at room temperature for 15 h. After aqueous extractive workup and column chromatographic purification process (hexanes/Et2O,5:1) 1a was obtained as a white solid, 226 mg (75%). Other 2,2,N-triarylacetamides were prepared similarly from corresponding N-arylaminesand 2,2-diarylacetic acids. Diphenylacetic acid, bis(4-chlorophenyl)acetic acid and 9-fluorenecarboxylic acid were purchased from commercial sources, and other diarylacetic acids were prepared by Friedel-Crafts reaction of arenes and corresponding mandelic acid derivatives according to the reported methods.3,4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With boron trifluoride diethyl etherate; In toluene; at 20.0℃; for 0.5h; | Carboxylic acid (0.2 g, 1.64 mmol), tert-butoxypyridine (0.33 g, 2.21 mmol) and boron trifluoride diethyl etherate (0.31 g, 2.21 mmol) in dry PhCH3 (2 mL) were added to a 20-ml vial. The reaction mixture was then allowed to stir at room temperature for 30 min before quenching with anhydrous NaHCO3. The reaction mixture was diluted with ethyl acetate (30 mL), then washed with water (20 mL), followed by brine (20 mL). The organic layer was dried over anhydrous sodium sulfate and carefully concentrated under reduced pressure. The resulting residue was then purified by flash column chromatography on silica gel with 0:4 to 1:4 dichloromethane/hexane as eluent to yield the desired product 5a as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With dipotassium peroxodisulfate; silver nitrate; In ethanol; at 50℃; | Add 2,2-diphenylacetic acid (212 mg, 1 mmol), diethyl phosphite (276 mg, 2 mmol), potassium persulfate (540 mg, 2.0 mmol), silver nitrate (34 mg, 0.2 mmol) and ethanol (10 mL) at 50 oC;TLC follows the reaction to completion;The crude product obtained after the reaction was separated by column chromatography (dichloromethane: methanol = 98: 2) to obtain the target product (yield 89%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With trans-bis(acetonitrile)palladium(II) chloride; silver(I) acetate In 1,2-dichloro-ethane at 40℃; for 8h; | 15 Example 15 A method for preparing an aromatic vinyl silane compound includes the following steps: To a 25 mL reaction tube were added 0.1061 g of diphenylacetic acid, 0.22 mL of trimethylvinylsilane, 0.0130 g of bis (acetonitrile) palladium dichloride, and 0.2504 g of silver acetate, an additional 5 mL of dichloroethane was added. The reaction tube was moved to an oil bath at 40 ° C for 8 h. After flash column chromatography, the product was concentrated under reduced pressure with a yield of 62%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With magnesium(II) nitrate hexahydrate In octane at 130℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With benzotriazol-1-ol; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 48h; | General procedure: The respective carboxylic acid (1.0 eq.), TBTU (1.1 eq.), and HOBt were dissolved in dry DMF and DIPEA (4.0 eq.) was added while cooling with an ice-water bath. The corresponding amine (1.0 eq.) was added after 30 min and the solution was stirred for 2 d at r.t. Water and EtOAc were added and the aqueous phase was extracted three times with EtOAc and the combined organic phases were washed with 2 M HCl, saturated NaHCO3-solution, and saturated NaCl-solution three times each. The organic phase was dried with MgSO4 and the solvent was evaporated under reduced pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With Isobutyronitrile; copper(II) bis(trifluoromethanesulfonate); sodium phosphate; In dichloromethane; at 20℃; for 24h;Irradiation; Inert atmosphere; Sealed tube; | General procedure: An oven-dried 6-ml vial equipped witha stir bar was placed in a nitrogen-filled glovebox and charged with Cu(OTf)2 (180.8 mg, 2.5 equiv., 0.50 mmol), Na3PO4 (98.2 mg, 3.0 equiv., 0.60 mmol), the sulfonamide nucleophile (1.5-3.0 equiv.), carboxylic acid (1.0 equiv., 0.20 mmol), methylene chloride (2.0 ml, 0.10 M) and isobutyronitrile (100 μl, 5.5 equiv.,1.1 mmol). The vial was sealed with a screwcap bearing a Teflon septum, removed from the glovebox and placed on a stir plate. The vial was irradiated at 427 nm with two 40-W Kessil PR160 lamps at a distance of 10 cm with stirring at 800 r.p.m. A fan was used to maintain the vial at room temperature. After 24 h, the crude reaction mixture was diluted with 1.5 ml of EtOAc and adsorbed directly on diatomaceous earth (Celite). The product was purified by flash chromatography on silica gel, eluting with mixtures of ethyl acetate and hexanes. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | In methanol at 20℃; for 3h; |
Tags: 117-34-0 synthesis path| 117-34-0 SDS| 117-34-0 COA| 117-34-0 purity| 117-34-0 application| 117-34-0 NMR| 117-34-0 COA| 117-34-0 structure
[ 13491-13-9 ]
(R)-3-Methyl-2-phenylbutanoic acid
Similarity: 0.97
[ 3508-94-9 ]
alpha-Isopropylphenylacetic Acid
Similarity: 0.97
[ 13490-69-2 ]
(S)-3-Methyl-2-phenylbutanoic acid
Similarity: 0.97
[ 13491-13-9 ]
(R)-3-Methyl-2-phenylbutanoic acid
Similarity: 0.97
[ 3508-94-9 ]
alpha-Isopropylphenylacetic Acid
Similarity: 0.97
[ 13490-69-2 ]
(S)-3-Methyl-2-phenylbutanoic acid
Similarity: 0.97
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P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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