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CAS No. : | 137-40-6 | MDL No. : | MFCD00002759 |
Formula : | C3H5NaO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | JXKPEJDQGNYQSM-UHFFFAOYSA-M |
M.W : | 96.06 | Pubchem ID : | 2723816 |
Synonyms : |
|
Chemical Name : | Sodiumpropionate |
Num. heavy atoms : | 6 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.67 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 16.36 |
TPSA : | 40.13 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.65 cm/s |
Log Po/w (iLOGP) : | -7.68 |
Log Po/w (XLOGP3) : | 0.33 |
Log Po/w (WLOGP) : | -0.85 |
Log Po/w (MLOGP) : | 0.03 |
Log Po/w (SILICOS-IT) : | -0.22 |
Consensus Log Po/w : | -1.68 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.58 |
Solubility : | 25.4 mg/ml ; 0.265 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.74 |
Solubility : | 17.6 mg/ml ; 0.183 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | 0.09 |
Solubility : | 118.0 mg/ml ; 1.22 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H319 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
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bei der Destillation; |
Yield | Reaction Conditions | Operation in experiment |
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With strong acid cation-exchange resin, Purolite C160; In water; at 20 - 50℃; | When sodium propionate is used instead of sodium formate, potassium propionate can be produced. The switch time was 330 s. The number of switches was 80. During one switch 3.2 [I] sodium propionate (concentration 6.0 [MOL/L,] average flow rate 0.58 [I/MIN] and temperature 50 [C)] and 7. [0 I] potassium chloride (concentration 3.9 [MOL/L,] sodium content 2.5 mole-%, average flow rate 1.3 [I/MIN] and temperature [20C)] was fed to the smb-unit. In addition to that water was fed for washing. Sodium propionate was fed to the column 2 and potassium chloride to the column 14. The production outlet was from column 9 and regeneration outlet was from column 19. Figure 15 and 16 illustrate the resin and solution profiles. The product during one switch was 19.1 mol potassium propionate (sodium content 11 mole-%). The regeneration product content was sodium chloride 66 mole-% and potassium chloride 34 [MOLE-%.] |
Yield | Reaction Conditions | Operation in experiment |
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15% | In dimethyl sulfoxide; for 0.75h; | A sample of 60 mg sodium propionate was added to a solution of compound of Formula II-19 (5.3 mg) in DMSO (1 ml) and the mixture sonicated for 5 minutes, though the sodium propionate did not completely dissolve. After 45 minutes, the solution was filtered through a 0.45 mu syringe filter and purified directly using HPLC. Conditions for the purification involved a linear gradient if 10% acetonitrile/90% water to 90% acetonitrile/10% water over 17 minutes using an Ace 5mu C18 HPLC column of dimensions 22 mm id by 150 mm length. Under these conditions, compound of Formula II-22 eluted at 12.3 minutes to yield 0.7 mg compound (15% isolated yield). UV (Acetonitrile/H2O) 225 (sh), ESMS, m/z 352.2 (M+H); HRMS (ESI), m/z 352.1762 [M+H]+, Deltacalc=0.6 ppm, C18H26NO6; 1H NMR in DMSO-d6 (see FIG. 18). |
15% | In dimethyl sulfoxide; for 0.833333h; | A sample of 60 mg sodium propionate was added to a solution of compound of Formula 11-19 (5.3 rag) in DMSO (1 ml) and the mixture sonicated for 5 minutes, though the sodium propionate did not completely dissolve. After 45 minutes, the solution was filtered through a 0.45 mu syringe filter and purified directly using HPLC. Conditions for the purification involved a linear gradient if 10% acetonitrile/90% water to 90% acetonitrile/ 10% water over 17 minutes using an Ace 5 mu Cl 8 HPLC column of dimensions 22 mm id by 150 mm length. Under these conditions, compound of Formula 11-22 eluted at 12.3 minutes to yield 0.7 mg compound (15% isolated yield). UV (Acetonitrile/H2O) 225 (sh), ESMS, m/z 352.2 (M+H); HRMS (ESI), m/z 352.1762 [M+H]+, A081C= 0.6 ppm, Ci8H26NO6; 1H NMR in DMSO-d6 (see FIG. 26). |
15% | In dimethyl sulfoxide; for 0.0833333h; | sample of 60 mg sodium propionate was added to a solution of compound of Formula 11-19 (5.3 mg) in DMSO (1 mL) and the mixture sonicated for 5 minutes, though the sodium propionate did not completely dissolve. After 45 minutes, the solution was filtered through a 0.45 mum syringe filter and purified directly using HPLC. Conditions for the purification involved a linear gradient if 10% acetonitrile/90% water to 90% acetonitrile/10% water over 17 minutes using an Ace 5 mum Cl 8 HPLC column of dimensions 22 mm id by 150 mm length. Under these conditions, compound of Formula II- 22 eluted at 12.3 minutes to yield 0.7 mg compound (15% isolated yield). UV (Acetonitrile/H2O) 225 (sh), ESMS, m/z 352.2 (M+H); HRMS (ESI), m/z 352.1762 [M+H]+, deltaCaic= 0.6 ppm, C18H26NO6. <n="111"/>sodium propionate |
Yield | Reaction Conditions | Operation in experiment |
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at 150℃; for 6h; | Reference Example 17 30 g of 4-benzyloxy-3-methoxybenzaidehyde, 12 g of sodium propionate and 24 g of propionic anhydride were mixed and stirred at 150C for 6 hours. After the reaction mixture was allowed to cool to room temperature, water was added, and the mixture was extracted with ethyl acetate. The resulting organic layer was washed with 5% hydrochloric acid and then with an aqueous saturated sodium chloride solution twice, dried over magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was washed with toluene and hexane to obtain 28 g of 3-(3-methoxy-4-benzyloxyphenyl)-2-methylacrylic acid. 1H-NMR (CDCl3, TMS) delta (ppm): 7.74 (1H, br.s), 7. 29-7. 45 (5H, m), 6.99-7.04 (2H, m), 6.91 (1H, d, J = 8.9 Hz), 5.20 (2H, s), 3.91 (3H, s), 2.16 (3H, d, J = 1.3 Hz) |
Yield | Reaction Conditions | Operation in experiment |
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[2-METHVLSULFANVL-4-(5-METHYLSULFANYL-PYRIDIN-2-YL)-6-TRIFLUOROMETHVL-PYRIMIDINE] To a solution of 4, 4, [4-TRIFLUORO-1- (5-METHYLSULFANYL-PYRIDIN-2-YL)-BUTANE-1, 3-DIONE] (0.600g, 2. [28MMOL)] in glacial acetic acid (6mL) was added 2-methyl 2- thiopseudourea sulphate (0. [761G,] 2. [74MMOL)] and sodium acetate (0.224g, 2. [74MMOL).] The reaction was heated to [120C] under nitrogen for 21 hours. The reaction was allowed to cool before the addition of water [(10ML),] leading to precipitation of a solid. The reaction mixture was poured onto water [(10ML)] and stirred for 15 minutes at [22C.] The precipitate was filtered from the aqueous solution, washed with water, and [DRIED IN VACUO] to yield the title compound as a grey solid : MS [M/Z] 317 [(M+1).] |
Yield | Reaction Conditions | Operation in experiment |
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Example 6 Synthesis of Ru(OCOCH2CH3)2((S)-binap) [RuCl2(p-cymene)]2 (612 mg, 1 mmol) and (S)-BINAP (1.2 g, 2 mmol) were put into a flask, and air inside the flask was replaced with nitrogen. Then, toluene (12 ml) and methanol (3 ml) were added thereinto, and the mixture was stirred at 50 C. for 1 hour. Thereafter, CH3CH2CO2Na (576 mg, 6 mmol) was added thereinto, and the mixture was further stirred at the same temperature for 2 hours. The reaction liquid was washed with water several times, and concentrated to obtain 1.7 g of the title compound. 1H-NMR (CDCl3, delta ppm): 0.77 (6H, t, J=7.8 Hz), 1.97 (4H, q, J=7.5 Hz)), 6.42-7.72 (32H, m) |
Yield | Reaction Conditions | Operation in experiment |
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In N,N-dimethyl-formamide; at 150℃; for 8h; | Example 42; Synthesis of (4S)-trans-,cis-[2-(4-chlorophenyl)-2-bromomethyl-1,3-dioxolan-4-yl]methyl benzoate A mixture of (4S)-trans-,cis-2-(4-chlorophenyl)-2-bromomethyl-4-chloromethyl-1,3-dioxolane (6.36 g) synthesized in Example 1, sodium benzoate (2.88 g, 1.0 equivalent) and DMF (100 mL) was stirred with heating at 150C for 8 hr. After cooling, the reaction mixture was diluted with water (100 mL), and extracted 3 times with ethyl acetate (100 mL). The organic layer was washed with water, and the solvent was evaporated under reduced pressure to give (4S)-trans-,cis-[2-(4-chlorophenyl)-2-bromomethyl-1,3-dioxolan-4-yl]methyl benzoate (5.46 g, >99%ee, trans/cis=34/66). Here, the content percentage of (4S)-trans-,cis-[2-(4-chlorophenyl)-2-chloromethyl-1,3-dioxolan-4-yl]methyl benzoate, which was derived from the halogen-exchanged compound in Example 1, was also 1.3%.Examples 43 to 48 Synthesis of (4S)-trans-,cis-[2-(4-chlorophenyl)-2-bromomethyl-1,3-dioxolan-4-yl]methyl carboxylate In Examples 43 to 48, reactions were performed according to Example 42 and using various carboxylic acid salts. The results are shown in Table 11 together with Example 42. |
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With hydrogen; In methanol; at 20℃; for 1h; | Survey Reactions with Hydrogen[0057]Prior to conducting reactions using deuterium, a series of survey reactions were herein performed using hydrogen gas to determine the optimum reaction conditions that would maximize the yield of non-deuterated sodium acrylate (4), while minimizing the amount of sodium propiolate (2-Na) remaining and the amount of sodium propionate (5) produced. Experimental details are provided below.[0058]In a typical procedure, a 250-mL round bottom flask was charged with sodium propiolate (2-Na, 1.15 g, 12.5 mmol), the appropriate Lindlar catalyst (e.g., 200 mg, 5 wt % Pd(0) on CaCO3 with 3 wt % of PbCO3), hydroquinone (10 mg), and a Teflon-coated stir bar. The appropriate solvent or solvent mixture (40 mL) was added and the solution stirred to dissolve the propiolate. The desired amount of quinoline (0 wt %, 50 wt %, 250 wt %, or 500 wt % of the catalyst, depending on the experiment) was then added via syringe. The flask was sealed with a rubber septum, sealed with parafilm, and evacuated and N2 back-filled three times by means of a needle attached to a double-manifold vacuum line. A plastic 5-mL syringe barrel with the large end cut off was fitted with two He-quality latex balloons (one balloon inserted inside a second balloon), using rubber bands and parafilm. The balloon assembly was purged with nitrogen at least three times. For reactions involving NO nitrogen blanketing atmosphere, the reaction flask was evacuated one more time. The balloon assembly was evacuated, filled with ca. 600-800 mL of hydrogen gas (>2-fold excess), and the syringe barrel fitted with a needle that was then inserted into the septum of the reaction flask. The solution was stirred at room temperature for up to 24 hours, with a small amount (?0.2 mL) of solution removed periodically by syringe. Those aliquots were diluted with 0.4 mL of D2O for analysis by 1H and 13C NMR. For reactions involving nominally 1 atm nitrogen blanketing atmosphere, the syringe barrel of the evacuated/deflated balloon assembly was fitted with a needle that was inserted through the septum of the nitrogen-filled reaction flask. An amount of hydrogen corresponding to a total of 13.3±0.3 mmol (the uncertainty being due to the day-to-day variance in lab temperature and pressure) was syringed into the reaction flask through the septum, using a 100-mL gas-tight syringe equipped with a valve, upon which the balloon was observed to inflate. The solution was stirred at room temperature for about 5 hours. A small amount (?0.2 mL) of solution was removed by syringe and diluted with 0.4 mL of D2O for 1H and 13C NMR at reaction times of 1, 2, and 3 hours. After 5 hours of stirring, (the balloon was completely deflated, indicating that the hydrogen had been consumed), the solution was filtered to remove the catalyst, and washed (to remove quinoline) with 5 mL×3 of CH3OH. The combined washing and reaction solvent was removed by rotary evaporation, and the solid that remained was suspended in 50 mL of ether and stirred for 10 minutes. The solid was then filtered, washed with additional ether (10 mL×3), and dried under vacuum to afford generally 1.10 to 1.15 g of a grey solid. 13C{1H} NMR (no NOE, see above) was used to determine the final distribution of sodium propiolate (2-Na), sodium acrylate (4), and sodium propionate (5).[0059]It was previously reported that treatment of sodium propiolate in 0.1 M NaOH at 40 C. with hydrogen over Pt-black (L. D. Volkova, et al., React. Kinet. Catal. Lett. 1985, 29, 345-351) could produce sodium acrylate. On the basis of this work, the partial reduction of sodium propiolate using the Lindlar catalyst (200 mg per 1.15 g of 2-Na) was herein first investigated in 0.05 M NaOH. However, as shown in Table 1 below, after 24 hours of stirring with a ?2-fold excess of hydrogen, only unreacted sodium propiolate (2-Na) was observed in the NMR spectrum.Switching to a 1:1 mixture of 0.05 M NaOH:CH3OH also resulted in only unreacted 2-H after 24 hours, and no reaction was also observed when the solvent was deionized water (2 hours). However, when pure CH3OH was used as the solvent, in the presence of a ?2-fold excess of hydrogen, complete over-reduction to sodium propionate (5) was observed within one hour. In this case, the balloon was completely deflated and, due to the excessive consumption of hydrogen, the flask was under negative pressure. This reaction was then repeated with the addition of 1.0 g of quinoline (500% on the weight of the catalyst), which is known to retard the over-reduction reaction. After 1 hour, a distribution ratio of 21:75:4 of 2-Na:4:5 was observed.[0061]In those first experiments, the reaction flask was placed under partial vacuum (evacuated and nitrogen refilled three times, then evacuated again until the solvent bubbled), and a balloon containing the ca. 2-fold excess hydrogen gas was attached to the flask. To better control the reaction and prevent over-reduction, in subsequent reactions a gas t... |
Yield | Reaction Conditions | Operation in experiment |
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70% | In ethanol; | An aqueous solution (10mL) of Zn(NO3)2·6H2O (0.313g, 1.0mmol) was added to a solution of dpe (0.182g, 1.0mmol) in ethanol (10mL). Subsequently, an aqueous solution (10mL) of NaCOOCH2CH3 (0.201g, 2.0mmol) was added, followed by KClO4 (0.152g, 1.0mmol) under continuous stirring. Next, a few drops of 98% CH3CH2COOH were added, yielding a clear colorless solution, which was allowed to stand unperturbed for the slow evaporation of the solvent at room temperature. Colorless crystals of 2 were collected from the solution by filtration after several days. Yield ca. 70%. Elemental Anal. Calc. for C72H70Cl2N10O16Zn3 (1598.46): C, 54.10; H, 4.41; N, 8.76. Found: C, 53.72; H, 4.74; N, 9.07%. IR (cm-1): nuas(COO) 1569, nus(COO) 1417, delta(O-C-O) 643, nu(ClO4) 1104-1045. |
Yield | Reaction Conditions | Operation in experiment |
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64% | In N,N-dimethyl-formamide; at 20℃; for 14h; | General procedure: Under N2 atmosphere, diethyl malonate (2.0 g, 12.5 mmol) was dropwise added to a suspension of NaH (624 mg, 3.9 mmol) and dry ether (10 mL) at room temperature and stirred for 5 min. The suspension was evaporated under the pressure to afford sodium diethyl malonate and the salt was dissolved in DMF (100 mL). Compound 2 (2.0 g, 6.73 mmol) was added to the DMF solution at room temperature and stirred at same temperature for 3 h. The progress of the reaction was monitored by TLC (hexane/ethyl acetate=4:1). The DMF solution was extracted with CH2Cl2 (3×30 mL) and the combined organic extracts were washed with brine (2×30 mL), dried over Na2SO4, and concentrated on a rotary evaporator. Chromatography on silica gel, eluting with a 4:1 mixture of hexane and ethyl acetate, afforded 6-(1-oxo-2,9,9-trimethylcycloundeca-2,6,10-trienyl)methylmalonic acid diethyl ester, 8 as a colorless oil in 64% yield. (0031) IR (NaCl film): 1735.8, 1654.8 cm-1; 1H NMR (CDCl3): delta 1.09 (s, 3H, CH3 at C9), 1.20 (s, 3H, CH3 at C9), 1.27 (s, 6H, CH3 at OCH2CH3), 1.80 (s, 3H, CH3 at C2), 1.88 (br m, 1H, CH at C6?), 2.05-2.47 (m, 6H, CH2 at C4, C5, C8), 2.92 (br m, 1H, CH at C6?), 3.47 (t, 1H, J=7.6 Hz, CH at COCHCO), 4.19 (s, 4H, CH2 at OCH2CH3), 5.35 (d, 1H, J=8.3 Hz, 1H, CH at C7), 5.83 (d, 1H, J=16.5 Hz, CH at C10), 5.97 (m, 1H, CH at C3), 5.97 (d, 2H, J=16.5 Hz, CH at C11); 13C NMR (CDCl3): delta 11.9 (CH3 at C2), 14.0 (OCH2CH3), 24.1 (CH3 at C9), 24.4 (C4), 27.0 (CH2 at C6), 29.3 (CH3 at C9), 36.0 (C5), 37.6 (C9), 42.0 (C8), 50.6 (COCH2CO), 61.4 (OCH2CH3), 61.6 (OCH2CH3), 127.1 (C11), 128.9 (C7), 135.8 (C2), 138.3 (C6), 148.9 (C3), 160.3 (C10), 168.7 (OCO), 169.1 (OCO), 204.0 (C1); HRMS (EI): m/z calcd mass for C22H32O5 376.2250, found 376.2277. |
Yield | Reaction Conditions | Operation in experiment |
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1.7 g | With propionic acid anhydride; at 150℃; for 3h; | 2.18 g (14.1 mmol) of 4-fluoro-3-methoxybenzaldehyde (CAS [128495-46-5]), 2.45 g (14.1 mmol) of sodium propoxide (CAS [137-40-6]) and 1.84 g (14.1 mmol) of propionic anhydride (CAS [123-62-6]) were stirred together at 150 C. for 3h. During this time, the suspension, which was initially white, turned into a clear solution. The mixture was cooled,diluted with 2M aqueous sodium hydroxide solution and extracted 2x with diethyl ether. The aqueous phase was acidified with 6M hydrochloric acid (pH about 5) and extracted 3x with ethyl acetate. The combined organic phases were washed with sat. sodium chloride solution and dried with sodium sulphate. and the solvents were removed on a rotary evaporator. This gave 1.70 g (51% of theory) of the product as a yellow solid which was reacted further without further purification. |
Yield | Reaction Conditions | Operation in experiment |
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In methanol;Inert atmosphere; Schlenk technique; | General procedure: [NiCl(triphos)]BPh4 (0.57 g, 0.6 mmol) was dissolved in ca. 20 mL of dry tetrahydrofuran,then a solution containing NaO2CR {0.058 g (R = Et), 0.086 g (R = Ph), 0.6 mmol} inmethanol was added. The solution changed rapidly from yellow to red and was stirred overnight.All volatiles were then removed in vacuo to produce a red microcrystalline solid. Thedry solid was extracted into a minimum amount of CH2Cl2 leaving an insoluble white solid(NaCl). The mixture was filtered and the white residue washed with a small volume ofCH2Cl2 (ca. 2 mL). Ethanol (ca. 3-4 times volume of CH2Cl2) was layered on the red solution.After several days of slow diffusion the red microcrystalline product was removed byfiltration, washed with diethyl ether, and dried in vacuo. Although the complex appears tobe stable in solution, when isolated as a solid it darkens in color over the course of severalhours at room temperature. Consequently, we have been unable to obtain satisfactory elementalanalyses and have only characterized the compounds by IR spectroscopy (table 1)and NMR spectroscopy (below).[Ni(O2CEt)(triphos)]BPh4. 1H NMR: 1.17 (t, JHH = 6.4 Hz, 3H, CH3); 3.73 (q,JHH = 6.4 Hz, 2H, CH2CH3); 2.20-3.50 (br, 8H, CH2); 6.60-8.45 (m, 45H, Ph). 31P{1H}NMR: 99.5 (t, JPP = 55 Hz, PPh); 47.0 (d, JPP = 55 Hz, PPh2).[Ni(O2CPh)(triphos)]BPh4. 1H NMR: 1.07-2.85 (br, 8H, CH2); 6.44-8.59 (m, 50H, Ph).31P{1H} NMR: 100.1 (t, JPP = 54 Hz, PPh); 46.9 (d, JPP = 54 Hz, PPh2). |
Yield | Reaction Conditions | Operation in experiment |
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85% | In methanol; at 20℃; for 24h; | The title complex was prepared by reacting theprecursor cis-[RuCl2(dppe)2] (0.103 mmol; 100 mg) withan excess of sodium propionate (0.300 mmol; 28.8 mg) and0.150 mmol (24.4 mg) of NH4PF6 in methanol (20 mL) atroom temperature for 24 h. The final yellow solution wasconcentrated to ca. 3 mL and water was added for theprecipitation of a pale yellow solid. The solid was filteredoff, washed with water (3 5 mL) and diethyl ether(3 5 mL) and dried under reduce pressure.Yield: 97.9 mg (85%). Anal. Calcd for C55H53F6O2P5Ru: exptl(calc) C, 58.85 (59.20); H, 4.80 (4.79). 31P{1H} NMR(161.73 MHz): d(ppm) 57.4 (triplet, 2P, 2JP-P = 18 Hz); 58.6(triplet, 2P, 2JP-P = 18 Hz);-144.7 (septet, 1P, 1JP-F = 711 Hz).HRESIMS (MeOH): m/z 971.2051 [M-PF6]+ (calcd for[C55H53O2P4Ru], 971.2034). UV-Vis (CH2Cl2, 2.30 105 M):l/nm (e/M1 cm1) 255 (5.29 104), 349 (2.16 103). |
Yield | Reaction Conditions | Operation in experiment |
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at 150℃; for 3h; | Example 8A 2-Methyl-3-(4-nitrophenyl)acrylic acid 100 g (662 mmol) of 4-nitrobenzaldehyde, 114 g (1.19 mol) of sodium propionate (CAS [137-40-6]) and 86.1 g (662 mmol) of propionic anhydride (CAS [123-62-6]) were stirred together at 150 C. for 3 h. The warm mixture was diluted with water and cooled, and the precipitate formed was filtered off, washed with water and dried (vacuum drying cabinet, 40 C.). This gave 140 g of crude product as a pale yellow solid which was converted further without further purification. LCMS (method 2): Rt=0.99 min; m/z [ES-]=206 (M-H)- 1H-NMR (400 MHz, DMSO-d6): delta=2.01 (s, 3H), 7.62 (s, 1H), 7.70 (d, 2H), 8.23 (d, 2H), 12.8 (s, br, 1H). |
Yield | Reaction Conditions | Operation in experiment |
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With sodium iodide; In N,N-dimethyl acetamide; at 20 - 70℃; for 69h;Inert atmosphere; | Next, under a nitrogen atmosphere, a mixture of 30.0 g of the crude 4-bromo-2-bromomethyl-1-butene, 40.0 g of sodium propionate, 5.00 g of sodium iodide and 100 ml of N,N-dimethylacetamide was stirred at room temperature for 63 hours and then stirred at 70 C. for 6 hours. The reaction mixture was cooled to room temperature, subjected to addition of water, and extracted with n-hexane. The organic phase was subjected to common work-up of washing, drying and concentration to obtain 23.72 g of crude 3-propionyloxymethyl-3-butenyl propionate (72% GC). The crude product was distilled under reduced pressure to obtain 18.52 g of 3-propionyloxymethyl-3-butenyl propionate as the target compound (88% GC, yield 77%) containing 10% of 2-methylene-3-butenyl propionate generated by elimination of hydrogen bromide as a by-product in addition to the target compound.3-Propionyloxymethyl-3-butenyl propionate (0068) Colorless Oil (0069) Boiling point: 78-81 C./399 Pa (0070) IR (D-ATR): nu=2982, 2944, 1739, 1463, 1349, 1179, 1019, 910 cm-1. (0071) 1H-NMR (500 MHz, CDCl3): delta=1.11 (3H, t, J=7.5 Hz), 1.14 (3H, t, J=7.5 Hz), 2.30 (2H, q, J=7.5 Hz), 2.34 (2H, q, J=7.5 Hz), 2.38 (2H, t, J=7 Hz), 4.19 (2H, t, J=7 Hz), 4.54 (2H, s), 4.99 (1H, s-like), 5.11 (1H, s) ppm. (0072) 13C-NMR (125 MHz, CDCl3): delta=9.03 (2C), 27.49, 27.51, 32.38, 62.31, 66.58, 114.73, 140.22, 173.97, 174.28 ppm. (0073) GC-MS (EI, 70 eV): 41, 57 (base peak), 84, 111, 128, 140. (0074) As a result of the spectral analyses of the crude 3-propionyloxymethyl-3-butenyl propionate synthesized in Example 1, 2-methylene-3-butenyl propionate as the by-product generated by the elimination of hydrogen bromide was observed, but the isomerization of the exo-methylene at the 2-position into internal olefin, for example, the formation of 2-methyl-2-butene-1,4-diyl dipropionate, was not observed. It is evident from the results that the method in accordance with the present invention achieves high selectivity. |
Yield | Reaction Conditions | Operation in experiment |
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In N,N-dimethyl acetamide; at 90℃; for 4h;Inert atmosphere; | Under a nitrogen atmosphere, a mixture of 10.0 g of 7-methyl-3-methylene-7-octenyl iodide (90.1% GC) obtained in Example 6, 8.00 g of sodium propionate, and 50 ml of N,N-dimethylacetamide was stirred at 90 C. for 4 hours. The reaction mixture was cooled, then poured in water, and extracted with diethyl ether. The diethyl ether solution was subjected to the work-up of washing, drying and concentration to obtain a crude product. The crude product was a mixture of 7-methyl-3-methylene-1,7-octadiene (26% GC, yield 44%) and 7-methyl-3-methylene-7-octenyl propionate (65% GC, yield 70%). |
Yield | Reaction Conditions | Operation in experiment |
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1.94 g; 20.14 g | With sodium iodide; In N,N-dimethyl-formamide; at 20 - 110℃; for 22h;Inert atmosphere; | Under a nitrogen atmosphere, a mixture of 28.8 g of 7-methyl-3-methylene-7-octenyl chloride (78% GC) obtained in Example 1, 19.0 g of sodium propionate, 0.8 g of sodium iodide, and 300 ml of N,N-dimethylformamide was stirred at 80 to 110 C. for 8 hours and was further stirred at room temperature for 14 hours. The reaction mixture was poured in water and extracted with n-hexane. The hexane solution was subjected to the work-up of washing, drying and concentration to obtain a crude product. Next, the crude product was distilled under reduced pressure to obtain 1.94 g of 7-methyl-3-methylene-1,7-octadiene (99% GC, yield 11%) as a by-product through the elimination reaction and 20.14 g of 7-methyl-3-methylene-7-octenyl propionate (95% GC, yield 74%) as the target compound. 7-Methyl-3-methylene-1,7-octadiene (0103) Colorless Oil (0104) IR (D-ATR): v=3777, 2970, 2937, 1650, 1595, 1449, 1374, 991, 889 cm-1. (0105) 1H-NMR (500 MHz, CDCl3): delta=1.61-1.69 (2H, m), 1.73 (3H, s), 2.06 (2H, t, J=7.7 Hz), 2.21 (2H, t-like, J=8 Hz), 4.71 (2H, d-like, J=13 Hz), 5.01 (2H, d-like, J=8 Hz), 5.06 (1H, d-like, J=11 Hz), 5.24 (1H, d, J=18 Hz), 6.38 (1H, dd, J=10.7, 17.5 Hz) ppm. (0106) 13C-NMR (125 MHz, CDCl3): delta=22.37, 26.06, 30.90, 37.62, 109.96, 113.10, 115.64, 138.94, 145.72, 146.32 ppm. (0107) GC-MS (EI, 70 eV): 27, 41, 68, 79 (base peak), 93, 107, 121, 136 (M+). 7-Methyl-3-methylene-7-octenyl propionate (0108) Colorless Oil (0109) IR (D-ATR): v=3075, 2981, 2938, 1739, 1645, 1462, 1375, 1349, 1182, 1084, 889 cm-1. (0110) 1H-NMR (500 MHz, CDCl3): delta=1.12 (3H, t, J=7.6 Hz), 1.53-1.61 (2H, m), 1.71 (3H, s), 1.97-2.06 (4H, m), 2.31 (2H, q, J=7.6 Hz), 2.33 (2H, t-like, J=7 Hz), 4.17 (2H, t, J=7.1 Hz), 4.67 (1H, s-like), 4.70 (1H, s-like), 4.77 (1H, s-like), 4.81 (1H, s-like) ppm. (0111) 13C-NMR (125 MHz, CDCl3): delta=9.10, 22.32, 25.51, 27.56, 34.95, 35.86, 37.29, 62.73, 109.96, 111.18, 145.44, 145.60, 174.41 ppm. (0112) GC-MS (EI, 70 eV): 29, 41, 57 (base peak), 68, 79, 93, 107, 121, 136, 210 (M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With copper(II) bis(trifluoromethanesulfonate); In acetonitrile; at 25℃; for 16h;Sealed tube; | General procedure: Potassium (4-fluorophenyl)trifluoroborate (1) (101 mg, 0.5 mmol, 1 equiv) or potassium(4-biphenyl)trifluoroborate (130 mg, 0.5 mmol, 1 equiv), Cu(OTf)2 (722 mg, 2 mmol, 4equiv) and tetraalkylammonium or alkali salt (2 mmol, 4 equiv) were weighed into a 20mL vial equipped with a magnetic stir bar. CH3CN (6 mL) was added, and the vial wassealed with a Teflon-lined cap. The reaction mixture was allowed to stir at roomtemperature for 16 h. For products that were isolated, the reactions were diluted withdiethyl ether or pentane (10 mL), and this solution was washed with water (3 x 10 mL).The organic layer was dried over MgSO4, filtered, and concentrated under vacuum. Theproducts were purified by column chromatography on silica gel. For product yieldsdetermined by 19F NMR spectroscopy, the crude reaction mixture was diluted withCH3CN, 1,3,5-trifluorobenzene was added as an internal standard, and the reaction wasanalyzed by 19F NMR spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With propionic acid anhydride; at 150℃; for 3h; | 4-nitrobenzaldehyde 100 g (662 mmol), sodium propionate (CAS [137-40-6]) 114 g (1.19 mol) and propionic anhydride (CAS [123-62-6]) 86.1 g (662 mmol) with the at 150 was stirred for 3 hours. Dilute the mixture with water, warm, and cool, the precipitate formed was filtered, washed with water, dried (vacuum drying cabinet, 40 ). Thus it was obtained 140 g of a crude product as a light yellow solid, was obtained as a further without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N,N-dimethyl acetamide; sodium iodide; at 90 - 100℃; for 5h;Inert atmosphere; | General procedure: Example 1 Synthesis 1 of 1-(2-Propionyloxyethyl)Cyclopropyl Methanesulfonate which is the Compound Having Z=CH3 and R1=CH3CH2 in General Formula (2) (0078) As shown in the following reaction equation, 1-(2-propionyloxyethyl)cyclopropyl methanesulfonate is synthesized from 1-(2-chloroethyl)cyclopropyl methanesulfonate. (0079) Under a nitrogen atmosphere, a mixture of 13.0 g of 1-(2-chloroethyl)cyclopropyl methanesulfonate (90.3% GC), 12.6 g of sodium propionate, 2.0 g of sodium iodide and 70 ml of N,N-dimethylacetamide was stirred at 90 to 100 C. for 5 hours. The reaction mixture was cooled on ice, subjected to addition of water and extracted with ethyl acetate. The organic phase was separated and then subjected to common work-up of washing, drying and concentration to obtain 17.84 g of crude 1-(2-propionyloxyethyl)cyclopropyl methanesulfonate (66% GC, yield 84%), containing 6.5% GC of 1-vinylcyclopropyl methanesulfonate generated by elimination of hydrogen chloride as a by-product and 18.1% GC of N,N-dimethylacetamide in addition to the target compound. 1-(2-Propionyloxyethyl)cyclopropyl methanesulfonate (0080) Brown Oil (0081) IR (D-ATR): nu=3022, 2979, 2943, 1733, 1352, 1189, 1163, 933 cm-1. (0082) 1H-NMR (500 MHz, CDCl3): delta=0.73-0.77 (2H, m), 1.12 (3H, t, J=7 Hz), 1.26-1.30 (2H, m), 2.17 (2H, t, J=7 Hz), 2.32 (2H, q, J=7.5 Hz), 3.00 (3H, s), 4.72 (1H, s-like), 4.32 (2H, t, J=7.5 Hz) ppm. (0083) 13C-NMR (125 MHz, CDCl3): delta=8.98, 11.50 (2C), 27.47, 35.03, 39.71, 60.91, 63.48, 174.29 ppm. (0084) In the 13C-NMR spectrum, signals are overlapped due to the symmetry of the molecule. In the above, two methylene groups constituting the cyclopropyl ring are equivalent and give a signal assigned to two carbons. Hereinafter, the same is observed in the spectra of similar compounds. (0085) GC-MS (EI, 70 eV): 29, 42, 57 (base peak), 83. (0086) GC-MS (CI, isobutane): 141, 163, 237 [(M+H)+]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N,N-dimethyl acetamide; sodium iodide; at 90 - 100℃; for 5h;Inert atmosphere; | General procedure: Example 1 Synthesis 1 of 1-(2-Propionyloxyethyl)Cyclopropyl Methanesulfonate which is the Compound Having Z=CH3 and R1=CH3CH2 in General Formula (2) (0078) As shown in the following reaction equation, 1-(2-propionyloxyethyl)cyclopropyl methanesulfonate is synthesized from 1-(2-chloroethyl)cyclopropyl methanesulfonate. (0079) Under a nitrogen atmosphere, a mixture of 13.0 g of 1-(2-chloroethyl)cyclopropyl methanesulfonate (90.3% GC), 12.6 g of sodium propionate, 2.0 g of sodium iodide and 70 ml of N,N-dimethylacetamide was stirred at 90 to 100 C. for 5 hours. The reaction mixture was cooled on ice, subjected to addition of water and extracted with ethyl acetate. The organic phase was separated and then subjected to common work-up of washing, drying and concentration to obtain 17.84 g of crude 1-(2-propionyloxyethyl)cyclopropyl methanesulfonate (66% GC, yield 84%), containing 6.5% GC of 1-vinylcyclopropyl methanesulfonate generated by elimination of hydrogen chloride as a by-product and 18.1% GC of N,N-dimethylacetamide in addition to the target compound. 1-(2-Propionyloxyethyl)cyclopropyl methanesulfonate (0080) Brown Oil (0081) IR (D-ATR): nu=3022, 2979, 2943, 1733, 1352, 1189, 1163, 933 cm-1. (0082) 1H-NMR (500 MHz, CDCl3): delta=0.73-0.77 (2H, m), 1.12 (3H, t, J=7 Hz), 1.26-1.30 (2H, m), 2.17 (2H, t, J=7 Hz), 2.32 (2H, q, J=7.5 Hz), 3.00 (3H, s), 4.72 (1H, s-like), 4.32 (2H, t, J=7.5 Hz) ppm. (0083) 13C-NMR (125 MHz, CDCl3): delta=8.98, 11.50 (2C), 27.47, 35.03, 39.71, 60.91, 63.48, 174.29 ppm. (0084) In the 13C-NMR spectrum, signals are overlapped due to the symmetry of the molecule. In the above, two methylene groups constituting the cyclopropyl ring are equivalent and give a signal assigned to two carbons. Hereinafter, the same is observed in the spectra of similar compounds. (0085) GC-MS (EI, 70 eV): 29, 42, 57 (base peak), 83. (0086) GC-MS (CI, isobutane): 141, 163, 237 [(M+H)+]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N,N-dimethyl acetamide; sodium iodide; at 90 - 100℃; for 5h;Inert atmosphere; | Example 1 Synthesis 1 of 1-(2-Propionyloxyethyl)Cyclopropyl Methanesulfonate which is the Compound Having Z=CH3 and R1=CH3CH2 in General Formula (2) (0078) As shown in the following reaction equation, 1-(2-propionyloxyethyl)cyclopropyl methanesulfonate is synthesized from 1-(2-chloroethyl)cyclopropyl methanesulfonate. (0079) Under a nitrogen atmosphere, a mixture of 13.0 g of 1-(2-chloroethyl)cyclopropyl methanesulfonate (90.3% GC), 12.6 g of sodium propionate, 2.0 g of sodium iodide and 70 ml of N,N-dimethylacetamide was stirred at 90 to 100 C. for 5 hours. The reaction mixture was cooled on ice, subjected to addition of water and extracted with ethyl acetate. The organic phase was separated and then subjected to common work-up of washing, drying and concentration to obtain 17.84 g of crude 1-(2-propionyloxyethyl)cyclopropyl methanesulfonate (66% GC, yield 84%), containing 6.5% GC of 1-vinylcyclopropyl methanesulfonate generated by elimination of hydrogen chloride as a by-product and 18.1% GC of N,N-dimethylacetamide in addition to the target compound. 1-(2-Propionyloxyethyl)cyclopropyl methanesulfonate (0080) Brown Oil (0081) IR (D-ATR): nu=3022, 2979, 2943, 1733, 1352, 1189, 1163, 933 cm-1. (0082) 1H-NMR (500 MHz, CDCl3): delta=0.73-0.77 (2H, m), 1.12 (3H, t, J=7 Hz), 1.26-1.30 (2H, m), 2.17 (2H, t, J=7 Hz), 2.32 (2H, q, J=7.5 Hz), 3.00 (3H, s), 4.72 (1H, s-like), 4.32 (2H, t, J=7.5 Hz) ppm. (0083) 13C-NMR (125 MHz, CDCl3): delta=8.98, 11.50 (2C), 27.47, 35.03, 39.71, 60.91, 63.48, 174.29 ppm. (0084) In the 13C-NMR spectrum, signals are overlapped due to the symmetry of the molecule. In the above, two methylene groups constituting the cyclopropyl ring are equivalent and give a signal assigned to two carbons. Hereinafter, the same is observed in the spectra of similar compounds. (0085) GC-MS (EI, 70 eV): 29, 42, 57 (base peak), 83. (0086) GC-MS (CI, isobutane): 141, 163, 237 [(M+H)+]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; at 178℃; | A solution of 2,4-dihydroxybenzaldehyde (2.762 g, 20 mmol), propionic anhydride (7.808 g, 60 mmol), sodium propionate (3.842 g, 40 mmol)Triethylamine (2.023 g, 20 mmol) was added to a 100 ml round-bottomed flask under reflux at 178 C and monitored by TLC. After completion of the reaction, the reaction solution was poured into 50 ml of ice water, adjusted to pH 7 with saturated NaHCO3, filtered and the cake was recrystallized from acetone to give pure product VIII-2.VIII-2 (1.762 g, 10 mmol), NBS (1.958 g, 11 mmol),Benzoyl peroxide (242 mg, 1 mmol) was added to a 50 ml round-bottomed flask, 20 ml of carbon tetrachloride was added, refluxed at 80 C, and monitored by TLC. After the reaction was complete, the filtrate was concentrated under reduced pressure and the concentrate was extracted with dichloromethane (3 x 50 mL) and saturated brine. The combined organic phases were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrate was recrystallized from acetone to give Compound VII-2. 5 ml of an aqueous solution of sodium azide (975 mg, 15 mmol) was added with stirring, and the reaction was carried out at room temperature, followed by TLC follow-up monitoring, and the mixture was stirred at room temperature for 1 hour. After the reaction, acetone was distilled off. The concentrate was extracted with ethyl acetate (3 x 50 mL) and saturated brine. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure and concentrated to give compound V-2 . Yield 75% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With triethylamine; In propionic acid anhydride; for 12h;Reflux; | 3.0 g, 26.6 mmol) of 2,4-dihydroxybenzaldehyde,(4.5 g, 46.8 mmol) of sodium propionate and (7.5 mL, 58.5 mmol) of propionic anhydride were added to the reaction flask,(3 mL, 26.6 mmol) of triethylamine was added dropwise with stirring,After completion of the dropwise addition, the reaction was refluxed for 12 hours to stop heating,Recovery room temperature, the reaction solution into 100mL water, a powder precipitation, filter, solidThe product was separated by ethyl acetate / petroleum ether = 1: 2 column chromatography to obtain 7.7 g of pure white product in 92% yield. |
82% | With piperidine; propionic acid anhydride; at 140℃; for 6h; | A mixture of 2,4-dihydroxybenzaldehyde (1.5 g, 10.8 mmol), sodium propionate (2.25 g, 23.4 mmol), piperidine (150 muL, 1.5 mmol) and propionic anhydride (4 mL, 31.04 mmol) was refluxed at 140 C for 6 h and then poured into ice. Then a 0.1 mol/L solution of HCl was added in the aqueous mixture, which yielded a milky flocculent precipitate. The precipitate was filtered and treated under stirring with concentrated H2SO4 (3 mL) for 30 minutes. The obtained mixture was poured into ice again to afford brown residue, which was purified by column chromatography over silica gel eluting with petroleum ether/ethyl acetate (2:1) to afford 1 (1.5 g, 82% yield) as pale solid. 1H NMR (500 MHz, -DMSO-d6): delta 10.37 (s, 1H), 7.74 (d, 1H, J = 8.8 Hz), 7.45-7.39 (m, 1H), 6.76 (dd, 1H, J = 8.4, 2.2 Hz), 6.70 (d, 1H, J = 2.0 Hz,), 2.03 (s, 3H). HR-MS (ESI): calcd. for C10H8O3 ([M+H]+) 175.0401, found: 175.0403. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18.52 g | With sodium iodide; In N,N-dimethyl acetamide; at 20 - 70℃; for 69h;Inert atmosphere; | Furthermore, under the nitrogen atmosphere, will 30.0g crude product of 4-bromo-2-bromomethyl-1-butene, 40.0g the sodium propionate, 5.00g of the sodium iodide and 100 ml N of the, mixture of N-dimethyl acetamide stirring at room temperature for 63 hours, then the 70 C stirring 6 hours. Cooling the reaction mixture to room temperature, add water to, and using normal hexane extraction. The organic phase for the conventional washing, drying and concentrating the common work, get 23.72g crude product of 3-propionyloxymethyl-3-butenyl propionate (72% GC). The crude product is distilled under reduced pressure, to obtain 18.52g the target compound 3-propionyloxymethyl-3-butenyl propionate (88% GC, yield 77%), other than in addition to the same target compound, also comprises the elimination of hydrogen bromide as a by-product produced in the reaction to 10% of the 2-methylene-3-butenyl propionate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | for 0.25h; | GC4444 (1.6 g, 3.2 mmol) was added to a 125-mL Erlenmeyer flask containing 50 ml_ of Dl water. The mixture was stirred vigorously for 15-20 min to yield a light yellow solution. In a separate flask was prepared an aqueous solution of 6.15 g sodium propionate in 100 ml_ of Dl water. In a 250-mL Erlenmeyer flask combined the GC4444 and sodium propionate solutions. The resultant solution was stirred for 15 min and was transferred to a 0.25-L separatory funnel and extracted with 50 ml_ of dichloromethane. The organic layer was separated and the solvent removed using a rotavap. Methanol (25 mL) was used to co-evaporate residual dichloromethane to yield a light brown solid. This material was dried in vacuo at 40 C for 24h. [ 00260 ] There was obtained 1 .1 g of the isolated light tan solid corresponding to 60% yield based on GC4444. HPLC analysis showed a purity of 99.5% and the elemental analysis showed 1 .44% residual chloride expressed as total halogen content and consistent with the GC4747 FontWeight="Bold" FontSize="10" 0.5 H20 structure. Anal Calc'd: C, 57.82%; H, 8.32%; Mn, 9.45%; and N, 12.04%. Anal Found: C, 58.19%; H, 8.50%; Mn, 9.39%; N, 12.36%, and CI as total halogen content of 1.44%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In water; | GC4444 (1.6 g, 3.2 mmol) was added to a 125-mL Erlenmeyer flask containing 50 ml_ of Dl water. The mixture was stirred vigorously for 15-20 min to yield a light yellow solution. In a separate flask was prepared an aqueous solution of 6.15 g sodium propionate in 100 ml_ of Dl water. In a 250-mL Erlenmeyer flask combined the GC4444 and sodium propionate solutions. The resultant solution was stirred for 15 min and was transferred to a 0.25-L separatory funnel and extracted with 50 ml_ of dichloromethane. The organic layer was separated and the solvent removed using a rotavap. Methanol (25 mL) was used to co-evaporate residual dichloromethane to yield a light brown solid. This material was dried in vacuo at 40 C for 24h. [ 00260 ] There was obtained 1 .1 g of the isolated light tan solid corresponding to 60% yield based on GC4444. HPLC analysis showed a purity of 99.5% and the elemental analysis showed 1 .44% residual chloride expressed as total halogen content and consistent with the GC4747 FontWeight="Bold" FontSize="10" 0.5 H20 structure. Anal Calc'd: C, 57.82%; H, 8.32%; Mn, 9.45%; and N, 12.04%. Anal Found: C, 58.19%; H, 8.50%; Mn, 9.39%; N, 12.36%, and CI as total halogen content of 1.44%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In dichloromethane; water; at 40℃; | GC4419 (1 1 .0 g) was added to a 500-mL Erlenmeyer flask containing 200 mL of Dl water. The mixture was stirred vigorously for 15-20 min with warming to 40C for 10 min. The resulting light, brownish suspension was filtered using a 10-20 mu fritted funnel to afford a clear, light tan solution. In a separate flask was prepared an aqueous solution of 80 g sodium propionate in 200 ml_ of Dl water. In a 500-mL Erlenmeyer flask the GC4419 solution and 200 ml_ of the sodium propionate solution were combined. The resulting tan solution was stirred for 5 min. The light tan-yellow solution was transferred to a 1 -L separatory funnel and extracted with DCM (3 X 75 ml_). The three resulting DCM layers were combined, and transferred back into a separatory funnel and the resulting DCM solution was back-extracted with additional aqueous sodium propionate solution (3 x 70 ml_). The DCM layer was dried over MgS04 for 15 min (w/stirring), filtered using a 20-50 mu fritted funnel, and rendered dry (i.e., foam) using a rotavap. Methanol (100 ml_) was added and the resulting solution dried using a rotavap to remove residual DCM to yield a light tan-yellow solid. This material was dried in vacuo at 30C for 20 h. [ 00226 ] There was obtained 1 1 .45 g of the isolated yellowish solid corresponding to 94% yield based on GC4419. HPLC analysis showed a purity of 99.6% and the elemental analysis showed only 873 ppm residual chloride expressed as total halogen content and consistent with the [bis-Propionato(GC4419)] structure. Anal Calc'd: C, 58.05%; H, 8.12%; Mn, 9.83%; and N, 12.54%. Anal Found: C, 57.64% ; H, 8.05% ; Mn, 9.91 %; N, 12.51 %, and CI as total halogen content of 873 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; water; In acetonitrile; at 60℃; for 2h;Sealed tube; | A mixture of phenylacetylene (0. 1 mmol, 0.0102 g),Benzyl isonitrile (0.25 mmol, 0.0293 g),Sodium propionate (0.3 mmol, 0.0229 g),H2O (0.1 mmol, 0.0018 g)And Pd (dppf) Cl2 (0.01 mmol, 0.0018 g)Mixed in a 15 mL sealed tube,Add 2.0 mL of acetonitrile as solvent,Stirred at 60 & lt; 0 & gt; C for 2 hours;The residue was purified by flash silica gel column chromatography (ethyl acetate / petroleum ether = 1: 25) to give the acetamide compound (yellow solid), and the residue was purified by filtration under reduced pressure.4i 8.26 mg, the yield was 81% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.8% | at 50℃; for 2.33333h; | General procedure: 1), taking 16.8g (0.1mol) of dinitrobenzene and 8.2g (0.1mol) of sodium acetate, placed in 50mL stainless steel capping typeIn the grinding jar, after sealing, it was fixed on a Mixer Mill 400 hybrid mill, set the vibration frequency to 30 Hz, and grind at 10 C for 20 min.2) After the reaction is completed, it is washed with 150 mL of anhydrous methanol, filtered, and repeated three times. The filtrate is combined, and the methanol in the filtrate is distilled off under reduced pressure (vacuum degree: 40 mmHg), and the product is separated by column chromatography;The column chromatography is: loading 20-50 g of 200-300 mesh column chromatography silica gel in a glass chromatography column, and loading all the filtrate after steaming methanol to ethyl acetate: petroleum ether = 1:2 ( a mixture of the volume ratios as an eluent; all the eluates were collected; and the solvent (ie, ethyl acetate and petroleum ether) was distilled off under reduced pressure (vacuum degree: 40 mmHg) to give the product nitrophenol ethyl ester. 3.2 g, the yield was 17.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | GC4403 (3.0 g, 6.2 mmol) was added to a 250-mL Erlenmeyer flask containing 75 mL of Dl water. The mixture was stirred vigorously for 15-20 min to yield a light, brownish solution. In a separate flask was prepared an aqueous solution of 23.8 g sodium propionate in 75 mL of Dl water. In a 500-mL Erlenmeyer flask combined the GC4403 solution and 40 mL of the sodium propionate solution together. The resultant solution was stirred for 5 additional min and was transferred to a 0.5-L separatory funnel and extracted with 50 mL of dichloromethane. The organic layer was separated, transferred back into a separatory funnel and back-extracted with remaining aqueous sodium propionate (35 mL). The dichloromethane layer was separated and the solvent removed using a rotavap. Methanol (25 mL) was used to co-evaporate residual dichloromethane to yield a light brown solid. This material was dried in vacuo at 40 C over the weekend. There was obtained 2.7 g of the isolated light brown solidcorresponding to 78% yield based on GC4403. HPLC analysis showed a purity of 97.3 % (1.2% monoamine GC4520) and the elemental analysis showed 0.356% residual chloride expressed as total halogen content and consistent with the GC4748 structure. Anal Calc'd: C, 58.05%; H, 8.12%; Mn, 9.83%; and N, 12.54%. Anal Found: C, 58.00%;H, 8.45%; Mn, 9.57%; N, 12.53%, and CI as total halogen content of 0.356%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | GC4444 (1 .6 g, 3.2 mmol) was added to a 125-mL Erlenmeyer flask containing 50 mL of Dl water. The mixture was stirred vigorously for 15-20 min to yield a light yellow solution. In a separate flask was prepared an aqueous solution of 6.15 g sodium propionate in 100 mL of Dl water. In a 250-mL Erlenmeyer flask combined the GC4444 and sodium propionate solutions. The resultant solution was stirred for 15 min and was transferred to a 0.25-L separatory funnel and extracted with 50 mL of dichloromethane. The organic layer was separated and the solvent removed using a rotavap. Methanol (25 mL) was used to co-evaporate residual dichloromethane to yield a light brown solid. This material was dried in vacuo at 40 C for 24h. There was obtained 1 .1 g of the isolated light tan solid corresponding to 60% yield based on GC4444. HPLC analysis showed a purity of 99.5% and the elemental analysis showed 1 .44% residual chloride expressed as total halogen content and consistent with the GC4747. 0.5 H2O structure. Anal Calc'd: C, 57.82%; H, 8.32%; Mn, 9.45%; and N, 12.04%. Anal Found: C, 58.19%; H, 8.50%; Mn, 9.39%; N, 12.36%, and CI as total halogen content of 1.44%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | GC4419 (1 1 .0 g) was added to a 500-mL Erlenmeyer flask containing 200 mL of Dl water. The mixture was stirred vigorously for 15-20 min with warming to 40C for 10 min. The resulting light, brownish suspension was filtered using a 10-20 mu fritted funnel to afford a clear, light tan solution. In a separate flask was prepared an aqueous solution of 80 g sodium propionate in 200 mL of Dl water. In a 500-mL Erlenmeyer flask the GC4419 solution and 200 mL of the sodium propionate solution were combined. The resulting tan solution was stirred for 5 min. The light tan-yellow solution was transferred to a 1 -L separatory funnel and extracted with DCM (3 X 75 mL). The three resulting DCM layers were combined, and transferred back into a separatory funnel and the resulting DCM solution was back-extracted with additional aqueous sodium propionate solution (3 x 70 mL). The DCM layer was dried over MgS04for 15 min (w/stirring), filtered using a 20-50 mu fritted funnel, and rendered dry (i.e., foam) using a rotavap. Methanol (100 mL) was added and the resulting solution dried using a rotavap to remove residual DCM to yield a light tan-yellow solid. This material was dried in vacuo at 30C for 20 h. There was obtained 1 1 .45 g of the isolated yellowish solidcorresponding to 94% yield based on GC4419. HPLC analysis showed a purity of 99.6% and the elemental analysis showed only 873 ppm residual chloride expressed as total halogen content and consistent with the [bis-Propionato(GC4419)] structure. Anal Calc'd: C, 58.05%; H, 8.12%; Mn, 9.83%; and N, 12.54%. Anal Found: C, 57.64% ; H, 8.05% ; Mn, 9.91 %; N, 12.51 %, and CI as total halogen content of 873 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.1% | 4.77 g (10 mmol) of N1-hexadecyl-N3-(2-piperidinylethyl)imidazole hydrochloride was dissolved in 100 mL of ethanol.The reaction was carried out by adding 0.40 g (10 mmol) of sodium hydroxide under stirring for 40 minutes.Then 1.15 g (12 mmol) of sodium propionate was added, and the reaction was stirred at room temperature for 12 hours.After completion of the reaction, the insoluble matter was removed by filtration, and 0.38 g (4 mmol) of sodium propionate was again added thereto to carry out a reaction at room temperature for 6 hours.To exchange unreacted N1-hexadecyl-N3-(2-piperidinylethyl)imidazole hydrochloride.This operation was repeated until sodium propionate was added and stirred without precipitation.Filtration, concentration of the filtrate, addition of diethyl ether to precipitate sodium propionate, filtration,The filtrate is evaporated to remove the solvent to obtain a milky white solid product.N1-hexadecyl-N3-(2-piperidylethyl)imidazole propionate 4.21 g, yield 88.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.5% | In dimethyl sulfoxide at 60 - 70℃; for 2h; | 2 Example 2 120.5g of compound 2 and 192g of sodium propionate, 220ml of dimethyl sulfoxide were stirred and mixed and heated up, the temperature was controlled at 60 to 70°C and the reaction was incubated for two hours, cooled to room temperature, added 250ml of water, 365ml of dichloromethane, and stirred until the solution was clarified. The layers were separated, the organic layer was washed once with 250 ml of water, and the solvent was concentrated under negative pressure to obtain 149.5 g of compound 3-2 with a molar yield of 94.5% and a purity of 99.1%. |
Tags: 137-40-6 synthesis path| 137-40-6 SDS| 137-40-6 COA| 137-40-6 purity| 137-40-6 application| 137-40-6 NMR| 137-40-6 COA| 137-40-6 structure
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
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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