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Chemical Structure| 162705-13-7

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Product Details of [ 162705-13-7 ]

CAS No. :162705-13-7
Formula : C18H19NO6
M.W : 345.35
SMILES Code : O=[N+](C1=CC(/C=C\C2=CC(OC)=C(OC)C(OC)=C2)=CC=C1OC)[O-]

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Application In Synthesis of [ 162705-13-7 ]

* 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.

  • Downstream synthetic route of [ 162705-13-7 ]

[ 162705-13-7 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 61240-20-8 ]
  • [ 31680-08-7 ]
  • [ 162705-13-7 ]
YieldReaction ConditionsOperation in experiment
39% NaH (1.54 g, 64.2 mmol) was added into an oven-dried round-bottom reaction flask. AnhydrousCH2Cl2 (100 mL) and 3,4,5-trimethoxybenzyltriphenylphosphonium bromide (6.94 g, 13.3mmol) were added to the reaction flask, and the reaction mixture was stirred for 1 h. The reactionmixture was cooled to -15 C, and <strong>[31680-08-7]4-methoxy-3-nitrobenzaldehyde</strong> (2.01 g 11.1 mmol) wasadded to the reaction flask. The reaction mixture was stirred for 20 h while warming to ambienttemperature under N2. Water (100 mL) was slowly added to the reaction, and the product wasextracted with CH2Cl2 (3 × 100 mL). The organic phase was rinsed with brine, dried withNa2SO4, and concentrated under reduced pressure, and the residue was purified by flash columnchromatography using a pre-packed 100 g silica column [solvent A: EtOAc; solvent B: hexanes;gradient: 10%A / 90%B (1 CV), 10%A / 90%B → 70%A / 30%B (10 CV), 70%A / 30%B (5CV); flow rate: 100 mL/min; monitored at 254 and 280 nm] affording 3' CA4-nitro 46 (1.51 g,S24.34 mmol, 39% yield) as a yellow solid.
1.3 g To a solution of compound 4 (4.5 g, 8.6 mmol) in dry CH2Cl2 (100 mL),NaH (1.7 g, 43.1 mmol) was added at 0 C and the mixture stirred at the sametemperature for 0.5 h, and then the compound 5 (1.6 g, 8.6 mmol) in dry CH2Cl2 (20 mL) wasadded to dropwise in reaction. The mixture reaction stirred at room temperaturefor overnight and monitored by TLC. After completion of reaction, the mixturereaction was quenched with ice water, washed with water (200 mL). The organiclayer was dried over anhydrous Na2SO4 and concentratedunder vacuum. The residue was purified on a silica gel column eluted withpetroleum ether/ethyl acetate (20:1= V:V) to give the desired product 6 (1.3 g, yield 43.7%) asa yellow solid. 1HNMR (300 MHz, CDCl3) δ 7.79 (d, J = 11.6 Hz, 1H), 7.43 (d, J= 8.7 Hz, 1H), 6.94 (d, J = 8.7 Hz, 1H), 6.58 (d, J = 12.1 Hz,1H), 6.47 - 6.42(m, 3H), 3.93 (s, 3H), 3.85 (s, 3H), 3.71 (s, 6H). HR-MS (m/z) (ESI): calcd for C18H19NO6 [M+H]+: 346.1291; found: 346.1275.
1.51 g NaH (1.54 g, 64.2 mmol) was added into an oven-dried round-bottom reaction flask. Anhydrous CH2C12 (100 ml) and 3,4,5-trimethoxybenzyltriphenylphosphonium bromide (6.94 g, 13.3 mmol) were added to the reaction flask, and the reaction mixture was stirred for 1 h. The reaction mixture was cooled to -15 C., and <strong>[31680-08-7]4-methoxy-3-nitrobenzaldehyde</strong> (2.01 g 11.1 mmol) was added to the reaction flask. The reaction mixture was stirred for 20 h while warming to ambient temperature under N2. Water (100 mL) was slowly added to the reaction, and the product was extracted with CH2C12 (3×100 mL). The organic phase was rinsed with brine, dried with Na2SO4, and concentrated under reduced pressure, and the residue was purified by flash column chromatography using a pre-packed 100 g silica column [solvent A: EtOAc; solvent B: hexanes; gradient: 10% A/90% B (1 CV), 10% A/90% B→70% A/30% B (10 CV), 70% A /30% B (5 CV); flow rate: 100 mL/min; monitored at 254 and 280 nm affording 3′ CA4-nitro (1.51 g,
  • 2
  • [ 61240-20-8 ]
  • [ 31680-08-7 ]
  • [ 162705-13-7 ]
  • [ 206649-07-2 ]
YieldReaction ConditionsOperation in experiment
34%; 50% A mixture of 3,4,5-trimethoxybenzyltriphenylphosphoniumbromide [22] (1.57 g, 3 mmol), powdered potassiumcarbonate (1.38 g, 10 mmol) and 18-crown-6 (0.01 g,0.04 mmol) in dichloromethane (20 mL) was stirred at roomtemperature for 10 min. Then, <strong>[31680-08-7]4-methoxy-3-nitrobenzaldehyde</strong>(0.54 g, 3 mmol) was added and the reaction mixturewas refluxed for 6 h (monitored by TLC). The inorganicsalts were filtered after cooling and the filtrate was concentratedunder reduced pressure to give a mixture of isomers1, 2 and triphenylphosphine oxide. Recrystallization ofthe crude reaction mixture from ethanol afforded pure Estilbene1 (0.40 g, 38 % yield). Column chromatography ofthe mother liquors (petroleum ether/acetone, 15:1 v/v) gaveZ-isomer 2 (0.35 g, 34 % yield) and 1 (0.12 g, 12 % yield). (E)-5-(4-Methoxy-3-nitrostyryl)-1,2,3-trimethoxybenzene(1)Orange crystals. Rf = 0.52. Mp: 151-153 C. 1H NMR(CDCl3, 300 MHz): δ 3.87 (s, 3H, OCH3), 3.91 (s, 6H,OCH3), 3.98 (s, 3H, OCH3), 6.72 (s, 2H, ArH), 6.91 (d, 1H,J = 16.3 Hz, = CH), 6.99 (d, 1H, J = 16.3 Hz, = CH),7.08 (d, 1H, J = 8.7 Hz, ArH), 7.64 (dd, 1H, J = 1.6 Hz,J = 8.7 Hz, ArH), 7.99 (d, 1H, J = 1.6 Hz, ArH). 13CNMR (CDCl3, 75 MHz): δ 55.9; 56.5; 60.8; 103.5; 113.6;122.9; 124.9; 129.3; 130.1; 131.6; 132.1; 138.1; 139.6;151.9; 153.3.(Z)-5-(4-Methoxy-3-nitrostyryl)-1,2,3-trimethoxybenzene(2)Yellow crystals. Rf = 0.58. Mp: 122-123 C. Lit. Mp:123-124 C [12]. 1H NMR (CDCl3, 300 MHz): δ 3.70 (s,6H, OCH3), 3.84 (s, 3H, OCH3), 3.92 (s, 3H, OCH3),6.41-6.46 (m, 3H, ArH, = CH), 6.57 (d, 1H,J = 12.1 Hz, = CH), 6.94 (d, 1H, J = 8.7 Hz, ArH), 7.42(dd, 1H, J = 2.2 Hz, J = 8.7 Hz, ArH), 7.78 (d, 1H,J = 2.2 Hz, ArH). 13C NMR (CDCl3, 75 MHz): δ 55.9;56.5; 60.9; 105.8; 113.1; 125.9; 126.8; 129.7; 131.3; 131.7;134.6; 137.7; 139.4; 151.6; 153.8.
Step (i) :A solution of sodium methoxide (5.66 kg, 29.34 mol) is run into a mixture, at a temperature of 5-10 C., comprising toluene (91.1 litres), trimethoxybenzylphosphonium bromide (15.35 kg, 29.33 mol) and <strong>[31680-08-7]4-methoxy-3-nitrobenzaldehyde</strong> (5.06 kg, 27.93 mol). At the end of the reaction, 0.32 litre (5.59 mol) of acetic acid is run in. After the medium has been maintained at 20 C., it is filtered. The cake is washed with toluene (11.1 litres). The filtrates are washed several times with water (20.2 litres) and then concentrated under vacuum. Isopropyl alcohol (87.6 litres) is then introduced and the medium is concentrated and then cooled. The suspension is then filtered at 10 C. The isolated product is dried under vacuum (6.46 kg, 52.2%). The purity of the isolated product is of the order of 78% with respect to (Z) and 22% with respect to (E).
With sodium hydride; In dichloromethane; at 0 - 20℃; General procedure: To a stirred solution of nitrobenzaldehydes (10, 11, 19, 1 mmol) and 3,4,5-trimethoxybenzyl triphenylphosphonium bromide (9, 1.1 mmol) in anhydrous dichloromethane, sodium hydride (4 mmol) was added at 0 C. The reaction mixture was stirred at room temperature for 18 h and monitored by TLC. After completion of the reaction appropriate amount of water, until foaming stopped, was added at 0 C. The organic layer was separated and the aqueous layer was extracted with chloroform. The combined organic layers were washed with brine solution, dried over anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure to get crude compounds, nitro Z-and E-stilbenes isomeric mixture. The isomers were separated by using column chromatographyto give pure Z-stilbenes.
 

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