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Chemical Structure| 61240-20-8

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Product Details of [ 61240-20-8 ]

CAS No. :61240-20-8
Formula : C28H28BrO3P
M.W : 523.40
SMILES Code : COC1=C(OC)C(OC)=CC(C[P+](C2=CC=CC=C2)(C3=CC=CC=C3)C4=CC=CC=C4)=C1.[Br-]
MDL No. :MFCD03452736

Safety of [ 61240-20-8 ]

Application In Synthesis of [ 61240-20-8 ]

* 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 [ 61240-20-8 ]

[ 61240-20-8 ] Synthesis Path-Downstream   1~6

  • 1
  • [ 54439-75-7 ]
  • [ 61240-20-8 ]
  • [ 134029-52-0 ]
  • [ 134054-80-1 ]
  • 2
  • [ 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,
  • 3
  • [ 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.
  • 4
  • [ 473917-15-6 ]
  • [ 61240-20-8 ]
  • (Z)-3'-fluoro-4'-trifluoromethoxy-3,4,5-trimethoxystilbene [ No CAS ]
  • (E)-3'-fluoro-4'-trifluoromethoxy-3,4,5-trimethoxystilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
57%; 21% General procedure: A typical procedure is described for the synthesis of (Z) and (E)-4?-trifluoromethoxy-3,4,5-trimethoxystilbene (Z-2 and E-2). All other fluoro-analogs of CA-4/CA-1 were synthesized in the same manner. 3,4,5-Trimethoxybenzylphosphonium bromide ( 17) (500mg, 0.96mmol) was dissolved in THF (15mL, 0.067M) and cooled to -78C for 2h. Then, n-BuLi (2.5M in hexane, 0.40mL, 0.96mmol, 1.0 eq) was added to this solution. The reaction mixture turned red. After 1h at -78C, 4-trifluoromethoxybenzaldehyde (16) (240mg, 1.26mmol, 1.3 eq) was added dropwise. The reaction mixture turned from red into orange to yellow. After stirring overnight, the reaction was quenched by addition of water, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator. The residue was subjected to column chromatography on silica gel (hexanes:ethyl acetate 9:1) to afford Z-2 as a clear oil (177mg, 52% yield), which became a white solid afterwards, and E-2 as a white solid (78mg, 23% yield).
  • 5
  • [ 61240-20-8 ]
  • [ 31680-08-7 ]
  • 1,2,3-trimethoxy-5-(4-methoxy-3-nitrostyryl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
68.49% Under nitrogen conditions, 3,4,5-trimethoxy-triphenylbenzyl bromide phosphonium salt (3.18g) was dissolved in anhydrous tetrahydrofuran (30mL), potassium tert-butoxide (2.48g) was added and placed together Stir in an ice-water bath for 30 minutes, then slowly add <strong>[31680-08-7]4-methoxy-3-nitrobenzaldehyde</strong> (1.21g) in tetrahydrofuran (15mL) dropwise. After the addition is complete, slowly warm to room temperature and keep it at room temperature. After stirring for 12 hours, TLC monitors that the reaction of the raw materials is complete.Quenched with water, extracted with ethyl acetate (10mL×3), collected the organic phase, washed with saturated sodium chloride (10mL×3), dried, filtered, and removed the organic solvent to obtain a brownish-yellow oily liquid, which was added 3 times The volume of absolute ethanol was stirred at room temperature for 1 h, and a yellow solid was precipitated out, which was filtered to obtain 1.58 g of the fourth intermediate (9) with a yield of 68.49%.
46% Under nitrogen protection, 3,4,5-trimethoxybenzyl bromide triphenylphosphine salt (4.42 g, 8.5 mmol) was suspended in anhydrous tetrahydrofuran (50 mL), cooled to -20C, and slowly added dropwise with stirring. N-butyllithium solution (8 mL, 2.5M) was added and gradually dissolved, and stirring was continued for 3 hours. <strong>[31680-08-7]3-Nitro-4-methoxybenzaldehyde</strong> (1.5 g, 8.3 mmol) was dissolved in 10 mL of anhydrous tetrahydrofuran. The solution was added dropwise to the reaction solution through a dropping funnel. After the addition was complete, the reaction was warmed to room temperature over 5 hours and the reaction was stirred overnight. The reaction was completed by TLC, 50 mL of quenching reaction was added and the solution was separated. Extract the organic phase again with 50 mL of ethyl acetate, combine the organic phases, and continue washing with water 2-3 times. Dry the organic phase with anhydrous sodium sulfate and vortex to obtain an oil. Crystallize with anhydrous ethanol to obtain the product 3′-nitro-3. 4,4',5-tetramethoxystilbene (1.6 g, 46%).
46% Under nitrogen, 3,4,5-trimethoxybenzylbromotriphenylphosphonate (4.42 g, 8.5 mmol) was suspended in anhydrous tetrahydrofuran (50 ml). the mixture was cooled to -20 C., and n-butyl lithium solution (8 ml, 2.5 m) was added dropwise slowly. After adding, the reactant was keep stirring for 3 h. A tetrahydrofuran (10 mL) solution of 3-nitro-4-methoxy benzaldehyde (1.5 g, 8.3 mmol) was added to the reaction solution through a drop funnel. After adding, the reaction was keep for 5 h, the reactant was raised to room temperature and reacted overnight. While TLC test showed that the reaction was complete, water (50 ml) was added to quench reaction and the organic solution was separated. The water layer was exacted by ethyl acetate (50 ml). The organic phase was combined and washed with water for 2 or 3 time, and was dried with anhydrous sodium sulfate. The oil was obtained by rotary evaporation. The residue was crystallized with anhydrous ethanol to obtain a solid of 3'-nitro-3,4,4', 5-tetramethoxystilbene (1.6 g, 46%).1H-NMR (500 MHz, CDCl3) δ8.03 (s, 1H), 7.68 (d, J=5 Hz, 1H), 7.11 (d, J=10 Hz, 1H), 7.00 (m, 2H), 6.75 (s, 2H), 4.01 (s, 3H), 3.94 (s, 6H), 3.90 (s, 3H).
Example 22 (Z / E) -3,4,5-Trimethoxy-4'-methoxy-3'-aminostilbene Under nitrogen protection, Into a 250 ml three-necked flask, trimethoxyphenylmethylenetriphenylphosphonium bromide (17.3 g, 33.12 mmol) was added, Dry tetrahydrofuran (20 ml), Cool to -78 C, N-Butyllithium solution (24 ml) was slowly added dropwise to the system, After adding dropwise and stirring for 1 hour, a solution of 3-nitro-4-methoxybenzaldehyde (6 g, 33.12 mmol) in tetrahydrofuran (12 ml) was slowly added and the temperature was raised to room temperature. The reaction was completed by TLC. Saturated brine was added to the aqueous layer and the organic phase was washed with saturated brine. Dried over anhydrous sodium sulfate, concentrated to give the crude product.

  • 6
  • [ 61240-20-8 ]
  • [ 109466-87-7 ]
  • (Z)-3,4,5-trimethoxy-2'-nitro-4'-(trifluoromethyl)stilbene [ No CAS ]
  • (E)-3,4,5-trimethoxy-2'-nitro-4'-(trifluoromethyl)stilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
420 mg; 490 mg Weigh 3,4,5-trimethoxybenzyl bromide triphenylphosphine salt 3 (1.50 g, 2.86 mmol)Placed in a 50 mL three-necked flask equipped with a thermometer and dried.Dissolve it by adding 10 mL of anhydrous tetrahydrofuran.Then, the reaction flask was placed in a cooling cycle device cooled to -78 C in advance.After the temperature inside the bottle is cooled to -78 C,Slowly drip 0.9 mL of n-butyllithium in tetrahydrofuran (2.5 M), and add dropwise.The reaction system was kept at -78 C and stirring was continued for 1 hour.Then slowly add <strong>[109466-87-7]4-(trifluoromethyl)-2-nitrobenzaldehyde</strong> 14 (668 mg, 3.05 mmol)Tetrahydrofuran solution (2.5mL), drip in about 5 minutes,Then, the reaction apparatus was taken out from the cooling circulation apparatus, and the temperature was gradually raised to room temperature, and the reaction was continued for 2 hours.After the reaction is completed, the reaction is quenched with water, washed with water, and washed with a saturated sodium chloride solution.The organic layer was combined, dried over anhydrous sodium sulfate, concentrated and purified by column chromatography (PE: EA=100:1).Obtaining compound 17,They are yellow oil, Z compound A3-1 420mg,ESI-HRMS (m/z): calculated for C18H16F3NO5 (M+H)+: 384.3232, found: 384.3239.Yellow solid E compound A3-2 490mg, ESI-HRMS(m/z):Calculated for C18H16F3NO5(M+H)+: 384.3232, found: 384.3256, Witting reaction yield 57%, Z/E ratio 1:1.
 

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