Home Cart 0 Sign in  
X

[ CAS No. 3762-25-2 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
3d Animation Molecule Structure of 3762-25-2
Chemical Structure| 3762-25-2
Chemical Structure| 3762-25-2
Structure of 3762-25-2 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Quality Control of [ 3762-25-2 ]

Related Doc. of [ 3762-25-2 ]

Alternatived Products of [ 3762-25-2 ]

Product Details of [ 3762-25-2 ]

CAS No. :3762-25-2 MDL No. :MFCD00041385
Formula : C12H19O3P Boiling Point : -
Linear Structure Formula :- InChI Key :QKGBKPZAXXBLJE-UHFFFAOYSA-N
M.W : 242.25 Pubchem ID :3050
Synonyms :

Safety of [ 3762-25-2 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 3762-25-2 ]

* 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 [ 3762-25-2 ]

[ 3762-25-2 ] Synthesis Path-Downstream   1~52

  • 2
  • [ 104-82-5 ]
  • [ 122-52-1 ]
  • [ 3762-25-2 ]
YieldReaction ConditionsOperation in experiment
at 200℃;
at 150℃; for 15h;
for 8h; Heating;
for 4h; Reflux; 3.2 2. Synthesis of 4-(4-methylphenyl)vinylphenylbenzyl sulfide Take the reaction product of p-methylbenzyl chloride and an excess of triethyl phosphite (2.91 g, 12 mmol) in a three-necked flask.After adding NaH (1.23 g, 50 mmol) and 100 mL of DMF, it was found that a gas was generated, and then 4-benzyl mercaptobenzaldehyde (2.25 g, 10 mmol) was added, and the reaction was stirred at room temperature for 12 h, and the reaction was completed by thin-plate chromatography. The system was poured into 10 volumes of distilled water, and the precipitate was collected by filtration, and the solid was collected by recrystallization from ethanol, and stored in a vacuum oven at 40 ° C, yield 64.4%.
In tetrahydrofuran for 4h; Reflux;
for 4h; Reflux;

  • 3
  • [ 67-36-7 ]
  • [ 3762-25-2 ]
  • [ 156871-48-6 ]
YieldReaction ConditionsOperation in experiment
91% With sodium hydride In 1,2-dimethoxyethane for 96h; Ambient temperature;
  • 4
  • [ 3762-25-2 ]
  • [ 104-87-0 ]
  • 4,4'-dimethylstilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With sodium hydride In 1,2-dimethoxyethane for 10h; Ambient temperature;
With sodium ethanolate In N,N-dimethyl-formamide
  • 5
  • [ 3762-25-2 ]
  • [ 459-57-4 ]
  • [ 39769-27-2 ]
YieldReaction ConditionsOperation in experiment
81% With sodium hydride In 1,2-dimethoxyethane for 10h; Ambient temperature;
  • 6
  • [ 3762-25-2 ]
  • [ 538-51-2 ]
  • diethyl ester of (erythro)-2-phenylamino-2-phenyl-1-(4-methylphenyl)-ethanephosphonic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With lithium amide In diethyl ether at -33℃; for 6h;
  • 7
  • [ 3762-25-2 ]
  • [ 538-51-2 ]
  • diethyl ester of (threo)-2-phenylamino-2-phenyl-1-(4-methylphenyl)-ethanephosphonic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With sodium amide In N,N,N,N,N,N-hexamethylphosphoric triamide at 10℃; for 1.25h;
  • 8
  • [ 3762-25-2 ]
  • [ 123-11-5 ]
  • (E)-4'-methoxy-4-methylstilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With sodium hydride In 1,2-dimethoxyethane for 10h; Ambient temperature;
75% With sodium hydride In 1,2-dimethoxyethane at 70℃; for 0.5h;
75% With sodium hydride In N,N-dimethyl-formamide at 70℃; for 0.5h;
  • 10
  • [ 3762-25-2 ]
  • [ 3446-89-7 ]
  • [ 156871-46-4 ]
YieldReaction ConditionsOperation in experiment
86% With sodium hydride In 1,2-dimethoxyethane for 10h; Ambient temperature;
  • 11
  • [ 104-81-4 ]
  • [ 122-52-1 ]
  • [ 3762-25-2 ]
YieldReaction ConditionsOperation in experiment
100% at 140℃;
94% for 20h; Reflux; Inert atmosphere;
90% at 140℃; for 0.0833333h; Microwave irradiation;
82% at 200℃; for 1h;
72% for 3h; Heating;
at 150℃;
In 1,4-dioxane for 20h; Inert atmosphere; Reflux;
at 140℃; for 1h; Inert atmosphere; Microwave irradiation; No. A10-152: Ethyl N-[1-(n-propyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate Triethyl phosphite (2.00 g, 12.04 mmol) and 4-methylbenzyl bromide (15.65 mmol) were added to a microwave vessel which had been dried by heating and then stirred together in the microwave under nitrogen at a temperature of 140° C. for 1 h. After complete conversion, the resulting crude product was purified by column chromatography (heptane/ethyl acetate gradient), distilled POCl3 (4.43 mmol) was then added to a partial amount of the resulting purified intermediate (4.43 mmol) and the mixture was stirred under argon at a temperature of 60° C. for 1.5 h. After complete conversion, the reaction mixture was concentrated carefully and the ethyl (4-methylbenzyl)phosphonochloridate obtained was, without further purification, directly reacted in the next step. In a round-bottom flask which had been dried by heating, under argon, 6-amino-1-propyl-3,4-dihydroquinolin-2(1H)-one (904 mg, 4.43 mmol) was dissolved in abs. tetrahydrofuran (2 ml) and slowly added dropwise under argon to a solution, cooled to -20° C., of ethyl (4-ethylbenzyl)phosphonochloridate (1030 mg, 4.43 mmol) in abs. tetrahydrofuran (8 ml) in a round-bottom flask which had been dried beforehand by heating. The resulting reaction mixture was stirred at -20° C. for 10 minutes, triethylamine (1.23 ml, 8.86 mmol) was then added and the mixture was subsequently stirred at room temperature for 2 h. The reaction mixture was then filtered, the filter cake was washed with tetrahydrofuran and the filtrate was concentrated under reduced pressure. Column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient) gave ethyl N-[1-(n-propylmethyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate (224 mg, 12% of theory) as a colorless solid. 1H-NMR (600 MHz, CDCl3 δ, ppm) 7.16-03 (m, 4H), 6.87 (m, 1H), 6.81 (m, 1H), 6.72 (m, 1H), 5.00 (br. m, 1H, NH), 4.24-4.17 (m, 1H), 4.08-4.00 (m, 1H), 3.90-3.84 (m, 2H), 3.27/3.02 (d, 2H), 2.83-2.78 (m, 2H), 2.63-2.59 (m, 2H), 2.30 (s, 3H), 1.71-1.63 (m, 2H), 1.33 (t, 3H), 0.96 (t, 3H).
at 140℃; for 1h; Microwave irradiation; Inert atmosphere; 4.2.3.12 Ethyl N-[1-(n-propyl)-2-oxo-1,2,3,4-tetrahydro-quinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate 13l. General procedure: Triethyl phosphite (2.00g, 12.04mmol) and 4-methylbenzyl bromide (15.65mmol) were added to a microwave vessel which had been dried by heating and then stirred together in the microwave under nitrogen at a temperature of 140°C for 1h. After complete conversion, the resulting crude product was purified by column chromatography (heptane/ethyl acetate gradient), distilled POCl3 (4.43mmol) was then added to a partial amount of the resulting purified intermediate (4.43mmol) and the mixture was stirred under argon at a temperature of 60°C for 1.5h. After complete conversion, the reaction mixture was concentrated carefully and the ethyl (4-methylbenzyl)phosphonochloridate obtained was, without further purification, directly reacted in the next step. In a round-bottom flask which had been dried by heating, under argon, 6-amino-1-propyl-3,4-dihydroquinolin-2(1H)-one (904mg, 4.43mmol) was dissolved in abs. tetrahydrofuran (2ml) and slowly added dropwise under argon to a solution, cooled to -20°C, of ethyl (4-ethylbenzyl)phosphonochloridate (1030mg, 4.43mmol) in abs. tetrahydrofuran (8ml) in a round-bottom flask which had been dried beforehand by heating. The resulting reaction mixture was stirred at -20°C for 10min, triethylamine (1.23ml, 8.86mmol) was then added and the mixture was subsequently stirred at room temperature for 2h. The reaction mixture was then filtered, the filter cake was washed with tetrahydrofuran and the filtrate was concentrated under reduced pressure. Column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient) gave ethyl N-[1-(n-propylmethyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate 13l (224mg, 12% of theory) as a colourless solid. 1H NMR (600MHz, CDCl3 δ, ppm) 7.16-03 (m, 4H), 6.87 (m, 1H), 6.81 (m, 1H), 6.72 (m, 1H), 5.00 (br. m, 1H, NH), 4.24-4.17 (m, 1H), 4.08-4.00 (m, 1H), 3.90-3.84 (m, 2H), 3.27/3.02 (d, 2H), 2.83-2.78 (m, 2H), 2.63-2.59 (m, 2H), 2.30 (s, 3H), 1.71-1.63 (m, 2H), 1.33 (t, 3H), 0.96 (t, 3H); LCMS (ESI, m/z): [M]+ 400.2; logp 2.44.

  • 12
  • [ 3762-25-2 ]
  • [ 93-02-7 ]
  • 1,4-dimethoxy-2-[2-(4-methylphenyl)ethenyl]benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With sodium methylate In methanol; N,N-dimethyl-formamide for 4h; Ambient temperature;
  • 13
  • [ 3762-25-2 ]
  • [ 77123-58-1 ]
  • 1-[(E)-2-(4-methylphenyl)ethenyl]-2-[2-(trimethylsilyl)ethynyl]benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium hydride In tetrahydrofuran at 26℃; for 12h;
  • 14
  • [ 3762-25-2 ]
  • [ 151692-46-5 ]
  • trimethyl-[6-(2-<i>p</i>-tolyl-vinyl)-benzo[1,3]dioxol-5-ylethynyl]-silane [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium hydride In tetrahydrofuran at 26℃; for 12h;
  • 15
  • [ 3762-25-2 ]
  • [ 177937-97-2 ]
  • [5-methoxy-2-(2-<i>p</i>-tolyl-vinyl)-phenylethynyl]-trimethyl-silane [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium hydride In tetrahydrofuran at 26℃; for 12h;
  • 16
  • [ 3762-25-2 ]
  • [ 86-81-7 ]
  • [ 141172-18-1 ]
YieldReaction ConditionsOperation in experiment
90% With potassium <i>tert</i>-butylate
72% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hydride In tetrahydrofuran Stage #2: 3,4,5-trimethoxy-benzaldehyde In tetrahydrofuran at 20 - 60℃;
  • 17
  • [ 3762-25-2 ]
  • [ 129529-07-3 ]
YieldReaction ConditionsOperation in experiment
With trichlorophosphate at 60℃; for 3h;
With trichlorophosphate at 60℃; for 1.5h; Inert atmosphere; No. A10-152: Ethyl N-[1-(n-propyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate Triethyl phosphite (2.00 g, 12.04 mmol) and 4-methylbenzyl bromide (15.65 mmol) were added to a microwave vessel which had been dried by heating and then stirred together in the microwave under nitrogen at a temperature of 140° C. for 1 h. After complete conversion, the resulting crude product was purified by column chromatography (heptane/ethyl acetate gradient), distilled POCl3 (4.43 mmol) was then added to a partial amount of the resulting purified intermediate (4.43 mmol) and the mixture was stirred under argon at a temperature of 60° C. for 1.5 h. After complete conversion, the reaction mixture was concentrated carefully and the ethyl (4-methylbenzyl)phosphonochloridate obtained was, without further purification, directly reacted in the next step. In a round-bottom flask which had been dried by heating, under argon, 6-amino-1-propyl-3,4-dihydroquinolin-2(1H)-one (904 mg, 4.43 mmol) was dissolved in abs. tetrahydrofuran (2 ml) and slowly added dropwise under argon to a solution, cooled to -20° C., of ethyl (4-ethylbenzyl)phosphonochloridate (1030 mg, 4.43 mmol) in abs. tetrahydrofuran (8 ml) in a round-bottom flask which had been dried beforehand by heating. The resulting reaction mixture was stirred at -20° C. for 10 minutes, triethylamine (1.23 ml, 8.86 mmol) was then added and the mixture was subsequently stirred at room temperature for 2 h. The reaction mixture was then filtered, the filter cake was washed with tetrahydrofuran and the filtrate was concentrated under reduced pressure. Column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient) gave ethyl N-[1-(n-propylmethyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate (224 mg, 12% of theory) as a colorless solid. 1H-NMR (600 MHz, CDCl3 δ, ppm) 7.16-03 (m, 4H), 6.87 (m, 1H), 6.81 (m, 1H), 6.72 (m, 1H), 5.00 (br. m, 1H, NH), 4.24-4.17 (m, 1H), 4.08-4.00 (m, 1H), 3.90-3.84 (m, 2H), 3.27/3.02 (d, 2H), 2.83-2.78 (m, 2H), 2.63-2.59 (m, 2H), 2.30 (s, 3H), 1.71-1.63 (m, 2H), 1.33 (t, 3H), 0.96 (t, 3H).
Multi-step reaction with 2 steps 1: sodium hydroxide / ethanol / 12 h / 85 °C 2: thionyl chloride / 12 h / 80 °C / Inert atmosphere
With trichlorophosphate at 60℃; for 1.5h; Inert atmosphere; 4.2.3.7 Methyl N-[1-(cyclopropylmethyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)phosphonamidate 13g. General procedure: 3,4-Dihydroquinolin-2(1H)-one (770mg, 3.83mmol) was added to conc. acetic acid (5ml), and fuming nitric acid (0.21ml, 5.06mmol) was then added carefully. The resulting reaction mixture was stirred at room temperature for 2h and then diluted with ice-water. The aqueous phase was then repeatedly extracted with ethyl acetate. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient), 6-nitro-3,4-dihydroquinolin-2(1H)-one (500mg, 68% of theory) was isolated as a colorless solid. 6-Nitro-3,4-dihydroquinolin-2(1H)-one (500mg, 2.60mmol) was dissolved under argon in abs. N,N-dimethylformamide and admixed with fine potassium carbonate powder (1.08mg, 7.81mmol). After stirring at room temperature for 5min, chloromethylcyclopropane (306mg, 3.38mmol) and potassium iodide (6mg, 0.04mmol) were added. The resulting reaction mixture was stirred at 120°C for 2h and, after cooling to room temperature, water and ethyl acetate were added. The aqueous phase was then repeatedly extracted with ethyl acetate. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient), 1-(cyclopropylmethyl)-6-nitro-3,4-dihydroquinolin-2(1H)-one (600mg, 94% of theory) was isolated as a colorless solid. 1H NMR (400MHz, CDCl3 δ, ppm) 8.17 (dd, 1H), 8.08 (d, 1H), 7.22 (d, 1H), 3.91 (d, 2H), 3.04 (m, 2H), 2.73 (m, 2H), 1.12 (m, 1H), 0.55 (m, 2H), 0.45 (m, 2H). In the next step, 1-(cyclopropylmethyl)-6-nitro-3,4-dihydroquinolin-2(1H)-one (600mg, 2.44mmol) was added together with tin(II) chloride dihydrate (2.19g, 9.75mmol) to abs. ethanol and the mixture was stirred under argon at a temperature of 80°C for 5h. After cooling to room temperature, the reaction mixture was poured into ice-water and then adjusted to pH 12 with aqueous NaOH. The aqueous phase was then repeatedly extracted with ethyl acetate. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient), 6-amino-1-(cyclopropylmethyl)-3,4-dihydroquinolin-2(1H)-one (481mg, 91% of theory) was isolated as a colorless solid. 1H NMR (400MHz, CDCl3 δ, ppm) 6.94 (d, 1H), 6.58 (dd, 1H), 6.53 (d, 1H), 3.83 (d, 3H), 2.81 (m, 2H), 2.61 (m, 2H), 1.12 (m, 1H), 0.47 (m, 2H), 0.39 (m, 2H). Trimethyl phosphite (1 equiv, 8.07mmol) and 4-methylbenzyl bromide (1 equiv, 8.07mmol) were added to a multi-necked flask which had been dried by heating and then stirred together under continuous nitrogen flow at a temperature of 100°C for 10h. After complete conversion, without further purification, distilled POCl3 (1 equiv) was added to the resulting crude product and the mixture was stirred under argon at a temperature of 60°C for 1.5h. After complete conversion, the methyl (4-methylbenzyl)phosphono-chloridate obtained was, without further purification, directly reacted in the next step. In a round-bottom flask which had been dried by heating, under argon, 6-amino-1-cyclopropylmethyl-3,4-dihydroquinolin-2(1H)-one (960mg, 4.57mmol) was dissolved in abs. tetrahydrofuran (2ml) and slowly added dropwise under argon to a solution, cooled to -20°C, of methyl (4-methylbenzyl)-phosphonochloridate (1000mg, 4.57mmol) in abs. tetrahydrofuran (10ml) in a round-bottom flask which had been dried beforehand by heating. The resulting reaction mixture was stirred at -20°C for 10min, triethylamine (1.27ml, 9.15mmol) was then added and the mixture was subsequently stirred at room temperature for 2h. The reaction mixture was then filtered, the filter cake was washed with tetrahydrofuran and the filtrate was concentrated under reduced pressure. By column chromatography purification of the crude product obtained (ethyl acetate/heptane gradient), methyl N-[1-(cyclopropylmethyl)-2-oxo-1,2,3,4-tetrahydroquinolin-6-yl]-P-(4-methylbenzyl)-phos-phonamidate 13g (209mg, 10% of theory) was isolated as a colorless solid. 1H NMR (400MHz, CDCl3 δ, ppm) 7.09-7.04 (m, 4H), 7.02 (m, 1H), 6.83 (m, 1H), 6.73 (m, 1H), 5.01 (br. s, 1H, NH), 3.84 (d, 2H), 3.76 / 3.53 (d, 3H), 3.25/3.00 (d, 2H), 2.87-2.82 (m, 2H), 2.65-2.61 (m, 2H), 2.32/2.30 (s, 3H), 1.13 (m, 1H), 0.53-0.48 (m, 2H), 0.45-0.41 (m, 2H); 13C NMR (150MHz, CDCl3 δ, ppm) 170.3, 141.4, 138.9, 134.3, 133.8, 130.0, 129.4, 129.2, 128.4, 128.2, 123.8, 117.0, 116.1, 53.7, 48.2, 32.9, 28.8, 25.2, 23.6, 21.5, 7.6, 7.2; LCMS (ESI, m/z): [M]+ 398.2; HRMS (ESI, m/z): calcd. for C22H27N2O3P, 398.4351 [M]+; found 398.4338.

  • 18
  • [ 3762-25-2 ]
  • [ 106-95-6 ]
  • [ 884489-18-3 ]
YieldReaction ConditionsOperation in experiment
33% Stage #1: diethyl 4-methylbenzylphosphonate With n-butyllithium In tetrahydrofuran at -70 - -50℃; Stage #2: allyl bromide In tetrahydrofuran at -70℃;
33% Stage #1: diethyl 4-methylbenzylphosphonate With n-butyllithium In tetrahydrofuran; hexane at -70 - -50℃; for 0.25h; Stage #2: allyl bromide In tetrahydrofuran; hexane for 2h; Heating;
  • 19
  • [ 42906-19-4 ]
  • [ 3762-25-2 ]
  • 4-methyl-4'-[N,N-bis(4-methylphenyl)amino]stilbene [ No CAS ]
  • 20
  • [ 19163-21-4 ]
  • [ 3762-25-2 ]
  • 2-(4-METHYLPHENYL)-1-(5-PHENYLTHIENE-2-YL)ETHENE [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium methylate In N,N-dimethyl-formamide 1 SYNTHESIS OF 2-(4-METHYLPHENYL)-1-(5-PHENYLTHIENE-2-YL)ETHENE To a stirred solution of 1.52 gram (0.008 mole) of 2-formyl-5-phenylthiophene and 2.0 grams (0.00820 mole) of diethyl 4-methylbenzylphosphonate in 40 mL of N,N-dimethylformamide was added 0.53 gram (0.0098 mole) of sodium methoxide. The reaction mixture was stirred at room temperature for approximately 18 hours and then was quenched with 50 mL of an aqueous solution saturated with ammonium chloride. A precipitate formed and was collected by filtration. The filter cake was washed with water. The washed solid was purified by column chromatography on silica gel, eluding with chloroform:n-hexane (10:90) yielded 1.1 gram of 2-(4-methylphenyl)-1-(5-phenylthien-2-yl)ethene as a solid, m.p. 159°-160° C.
  • 21
  • [ 3762-25-2 ]
  • [ 105-07-7 ]
  • 4-[(E)-2-(4-Methylphenyl)ethen-1-yl]benzonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
56% With potassium hydroxide In N,N-dimethyl-formamide
54% With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 16h; (E)-4-(4-Methylstyryl)benzonitrile12 To a stirred solution of diethyl 4-methylbenzylphosphonate (2.5 mL, 11.0mmol) and 4-formylbenzonitrile (1.48 g, 11.0mmol) in THF (50 mL) at 0 °C was addedportionwisepotassium tert-butoxide (1.51 g, 13.3mmol) and the resulting yellow solution stirred at room temperature for 16 h. Water (100 mL) was added and the resulting precipitate was collected by filtration, washed with water, and dried by vacuum oven to afford the title compound (1.31 g, 54%) as a yellow powder.1H NMR (300 MHz, Chloroform-d) δ 7.64 (d,J= 8.6 Hz, 2H), 7.58 (d,J= 8.5 Hz, 2H), 7.55-7.30 (m, 2H), 7.28-7.14 (m, 3H), 7.05 (d,J= 16.4 Hz, 1H), 2.40 (s, 3H). LC-MS: (High pH)tR1.44 min, no mass ion, 100% purity;
  • 22
  • [ 186534-02-1 ]
  • [ 3762-25-2 ]
  • [ 1000672-80-9 ]
  • 23
  • [ 4181-05-9 ]
  • [ 3762-25-2 ]
  • N,N-diphenyl-4-[2-(4-methylphenyl)ethenyl]benzenamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 8.16667h;
  • 24
  • [ 3762-25-2 ]
  • [ 100-52-7 ]
  • E-1-methyl-4-styryl-benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; Cooling with ice; 2.3 (E)-4-Methyl stilbene (4MSTB) (E)-4-Methyl stilbene was synthesized via the Wittig-Horner reaction using 4-methyltoluene(diethylphosphonate) and benzaldehyde (Scheme 1) [24]. To synthesize 4-methyltoluene(diethylphosphonate), 4-methylbenzyl chloride (15.0g, 107mmol) and triethyl phosphite (70.9g, 427mmol) were stirred in a 250ml flask and heated to 160°C for 24h. The remaining triethyl phosphite was removed by vacuum distillation at 80°C under 0.2mmHg to afford a colorless liquid (27.1g, 100%). 4-Methyltoluene(diethylphosphonate) (27.1g, 112mmol) and benzaldehyde (11.9g, 112mmol) in dry THF (60ml) were stirred in a 250ml round bottom flask cooled in an ice bath. tBuOK (1.0M in THF, 120ml) was then added drop wise. The solution formed was stirred at room temperature for an additional 24h after which it was poured into water (500ml). The product was precipitated from the solution, filtered and washed with water and vacuum dried overnight to yield (E)-4-methyl stilbene (white crystalline solid, 18.7g, 86%). 1H NMR (CDCl3, 500MHz) δ ppm: 7.52-7.08 (m, 11H), 2.37 (s, 3H) (FigureS1). Melting point: 117-118°C (lit [30]: 118-120°C).
80% With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; Inert atmosphere;
  • 25
  • [ 5765-65-1 ]
  • [ 3762-25-2 ]
  • [ 1582788-26-8 ]
YieldReaction ConditionsOperation in experiment
98% Stage #1: diethyl 4-methylbenzylphosphonate With bis(2,2,6,6-tetramethyl-1-piperidyl)zinc In toluene at 20℃; for 1h; Stage #2: 4-(benzoyloxy)morpholine With [2,2]bipyridinyl; copper dichloride In tetrahydrofuran; toluene at 20℃;
  • 26
  • [ 104-82-5 ]
  • [ 3762-25-2 ]
YieldReaction ConditionsOperation in experiment
100% With triethyl phosphite at 160℃; for 24h; 2.3 (E)-4-Methyl stilbene (4MSTB) (E)-4-Methyl stilbene was synthesized via the Wittig-Horner reaction using 4-methyltoluene(diethylphosphonate) and benzaldehyde (Scheme 1) [24]. To synthesize 4-methyltoluene(diethylphosphonate), 4-methylbenzyl chloride (15.0g, 107mmol) and triethyl phosphite (70.9g, 427mmol) were stirred in a 250ml flask and heated to 160°C for 24h. The remaining triethyl phosphite was removed by vacuum distillation at 80°C under 0.2mmHg to afford a colorless liquid (27.1g, 100%). 4-Methyltoluene(diethylphosphonate) (27.1g, 112mmol) and benzaldehyde (11.9g, 112mmol) in dry THF (60ml) were stirred in a 250ml round bottom flask cooled in an ice bath. tBuOK (1.0M in THF, 120ml) was then added drop wise. The solution formed was stirred at room temperature for an additional 24h after which it was poured into water (500ml). The product was precipitated from the solution, filtered and washed with water and vacuum dried overnight to yield (E)-4-methyl stilbene (white crystalline solid, 18.7g, 86%). 1H NMR (CDCl3, 500MHz) δ ppm: 7.52-7.08 (m, 11H), 2.37 (s, 3H) (FigureS1). Melting point: 117-118°C (lit [30]: 118-120°C).
  • 27
  • [ 26260-02-6 ]
  • [ 3762-25-2 ]
  • [ 1308866-21-8 ]
YieldReaction ConditionsOperation in experiment
93% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 0.166667h; Inert atmosphere; Stage #2: 2-iodobenzaldehyde In tetrahydrofuran at 20℃; for 12h; Inert atmosphere;
  • 28
  • [ 18742-02-4 ]
  • [ 3762-25-2 ]
  • diethyl 3-(1,3-dioxolan-2-yl)-1-(p-tolyl)propylphosphonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% Stage #1: diethyl 4-methylbenzylphosphonate With n-butyllithium In hexane; toluene at -78℃; for 1h; Inert atmosphere; Stage #2: 2-bromo-2-(2-ethyl)dioxolane In hexane; toluene at -78 - 20℃; Inert atmosphere;
  • 29
  • 4,4'-(2-phenylethene-1,1-diyl)bis(N,N-diphenylaniline) [ No CAS ]
  • [ 3762-25-2 ]
  • 4,4'-(2-(4-methylphenyl)ethene-1,1-diyl)bis(N,N-bis(4-methylphenyl)aniline) [ No CAS ]
YieldReaction ConditionsOperation in experiment
40% With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;
  • 30
  • [ 3762-25-2 ]
  • 4',4'',4''',4''''-germanetetrayltetrakis(biphenyl-4',4-diyl)tetrakis(phenylmethanone) [ No CAS ]
  • tetrakis(4'-(1-phenyl-2-p-tolylvinyl)biphenyl-4-yl)germane [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: 4',4'',4''',4''''-germanetetrayltetrakis(biphenyl-4',4-diyl)tetrakis(phenylmethanone) In tetrahydrofuran for 72h; Inert atmosphere; Reflux; 27 Insert the potassium tert-butoxide in a round bottom flask, 0.92 g (8.19mmol) using a vacuum pump for 30 minutes airAfter removal of the injected argon gas. Then, after using the syringe 300 ml THF was added a diethyl-4-Insert the methylbenzylphosphonate 1.22 ml (5.46mmol) was stirred for 1 hour. Then put the following, the compound prepared in Example 25 1.0 g (0.91mmol) was refluxed for 72 hours. After the reaction, it was added to 1% aqueous solution of HCl after cooling to room temperature, and diluted with chloroform. Then, after removing the fine moisture particles and the organic layer washed with water and saturated NaCl aqueous solution, with MgSO, and evaporated under reduced pressure to remove the solvent. Then, using a Column chromatography of the 55% to whiteFormula 35 to give a compound represented by (tetrakis (4 '(1-phenyl-2-p-tolylvinyl) biphenyl-4-yl) germane).
55% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: 4',4'',4''',4''''-germanetetrayltetrakis(biphenyl-4',4-diyl)tetrakis(phenylmethanone) In tetrahydrofuran for 72h; Inert atmosphere; Reflux; 27 0.92 g (8.19 mmol) of potassium tert-butoxide was added to a round-bottomed flask, and air was removed for 30 minutes using a vacuum pump. Then, argon gas was introduced.Then, 300 ml of THF was added using a syringe, 1.22 ml (5.46 mmol) of diethyl-4-methylbenzylphosphonate was added, and the mixture was stirred for 1 hour. Then 1.0 g (0.91 mmol) of the compound prepared in Example 25 was added and the mixture was refluxed for 72 hours.After the reaction, 1% aqueous HCl solution was added, the mixture was cooled to room temperature, and then diluted with chloroform. Then, the organic layer was washed with water and a saturated aqueous solution of NaCl, and water was removed with MgSO4, followed by distillation under reduced pressure to remove the solvent.Then, using column chromatography, 55% of white compound represented by formula 35 Tetrakis (4 '- (1-phenyl-2-p-tolylvinyl) biphenyl-4-yl) germane) was obtained.
  • 31
  • [ 3762-25-2 ]
  • 4,4',4'',4'''-germanetetrayltetrakis(benzene-4,1-diyl)tetrakis(phenylmethanone) [ No CAS ]
  • C84H68Ge [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: 4,4',4'',4'''-germanetetrayltetrakis(benzene-4,1-diyl)tetrakis(phenylmethanone) In tetrahydrofuran for 72h; Inert atmosphere; Reflux; 4 Insert the potassium tert-butoxide in a round bottom flask, 1.27 g (11.29mmol) using a vacuum pump for 30 minutes airAfter removal of the injected argon gas. Then, put back by using a syringe 300 ml THF was added to 1.57 ml (7.52mmol) of diethyl-4-methylbenzyl phosphonate was stirred for 1 hour. Then, into the compounds 1.0 g (1.25 mmol) prepared in Example 2 was refluxed for 72 hours. After the reaction, it was added to 1% aqueous solution of HCl after cooling to room temperature, and diluted with chloroform. Then, washing with water and a saturated aqueous NaCl solution, and then distilled under reduced pressure to remove the fine moisture MgSO and the solvent was removed. Then, using a Column chromatography to obtain a compound represented by the following formula (11) of the 67% white.
67% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: 4,4',4'',4'''-germanetetrayltetrakis(benzene-4,1-diyl)tetrakis(phenylmethanone) In tetrahydrofuran for 72h; Reflux; Inert atmosphere; 4 To a round bottom flask was added 1.27 g (11.29 mmol) of potassium tert-butoxide, air was removed for 30 minutes by using a vacuum pump, and then argon gas was injected.Then, 300 ml of THF was added using a syringe diethyl-4-methylbenzyl phosphonate (1.57 ml, 7.52 mmol) and stirred for 1 hour. Then 1.0 g (1.25 mmol) of the compound prepared in Example 2 was added, and the mixture was refluxed for 72 hours.After the reaction, 1% aqueous HCl solution was added, the mixture was cooled to room temperature, and then diluted with chloroform. It was then washed with water and saturated aqueous NaCl solution and dried over MgSO4 with fine waterAnd the solvent was distilled off under reduced pressure.Then, by column chromatography, 67% of a white compound represented by the following formula (11) was obtained.
  • 32
  • [ 3762-25-2 ]
  • [ 676244-31-8 ]
  • 1,4-di{3-[2-(4-methylphenyl)ethenyl]indol-1-yl}butane [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.333333h; Inert atmosphere; Stage #2: 1,1'-butane-1,4-diylbis-1H-indole-3-carbaldehyde In tetrahydrofuran at 20℃; for 3h; Alkaline conditions; 2.2. Materials 1,4-Di{3-[2-(4-methylphenyl)ethenyl]indol-1-yl}butane (4) was prepared by the reaction of the di-aldehyde 2 with an excess of diethyl 4-methylbenzylphosphonate. Potassium tert-butoxide (2.52 g, 26 mmol) and 20 ml of dry THF were placed in a flask at room temperature under nitrogen atmosphere. Diethyl 4-methylbenzylphosphonate (2.47 ml, 11 mmol) were added dropwise to the solution at 0°C under nitrogen. The reaction mixture was stirred for 20 min. Then 1.5 g (4.4 mmol) of di-aldehyde 2 was added to the reaction mixture. The resulting solution was stirred at room temperature under the basic conditions for 3 h, by which time the starting compound 2 reacted completely. Then the mixture was poured into ice water and extracted with chloroform. Organic fraction was dried by Na2SO4 and the solvent was removed by evaporation. The product was purified by column chromatography with silica gel using ethyl acetate/hexane (vol. ratio 1:5) as an eluent. Yield: 0.44 (22%) of white crystals. M.p.: 176°C (DSC). MS (APCI+, 20 V): 520,3 ([M]+, 100%), 521,3 ([M+H]+, 46%). 1H NMR spectrum (CDCl3, d, ppm): 7.97 (d, 2H, J = 7.2 Hz, Ar), 7.38 (d, 4H, J = 8.0 Hz, Ar), 7.27-7.17 (m, 8H, Ar), 7.16-7.01 (m, 8H, Ar and 2 x CH=CH), 4.04-3.93 (m, 4H, N-CH2-CH2-CH2-CH2-N), 2.34 (s, 6H, 2 CH3),1.87-1.75 (m, 4H, N-CH2-CH2-CH2-CH2-N). 13C NMR spectrum (CDCl3, d, ppm): 21.11, 26.94, 27.40, 45.74, 109.34, 118.81, 119.03, 120.50, 121.46, 121.58, 126.81, 128.29, 129.32, 135.16,135.32, 135.78, 140.76, 140.88. Elemental analysis for C38H36N2% Calc.: C 87.65, H 6.97, N 5.38; % Found: C 87.69, H 6.92, N 5.34.
  • 33
  • [ 3762-25-2 ]
  • C78H56N2O4 [ No CAS ]
  • N1,N1,N2,N2-tetrakis(4'-(1-phenyl-2-p-tolylvinyl)biphenyl-4-yl)ethane-1,2-diamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: C78H56N2O4 In tetrahydrofuran for 72h; Reflux; 21 0.47 g (4.15 mmol) of potassium tert-butoxide was added to a round bottom flask, and the Air was removed for 30 minutes using a vacuum pump.After removing the flask, argon gas was introduced. Then, 300 ml of THF was added using a syringe, and diethyl-0.67 g (2.76 mmol) of 4-tert-buthylbenzyl phosphonate was added, and the mixture was stirred for 1 hour. Then, in Example 19Was added 0.5 g (0.46 mmol) of the compound prepared in Reference Example 1 and refluxed for 72 hours. After the reaction, 1% aqueous HCl solution was added,After cooling down, it was diluted with chloroform. The organic layer was then washed with water and saturated aqueous NaCl solutionMgSO4? After removing fine water, the solvent was distilled off under reduced pressure. Then, using column chromatographyF 50%Of bright yellow formula 27 N1, N1, N2, N2-tetrakis (4 '- (1-phenyl-2-p-tolylvinyl) biphenyl-Yl) ethane-1,2-diamine was obtained.
  • 34
  • [ 3762-25-2 ]
  • N,N,N′,N'-tetrakis(4-benzoylphenyl)ethylenediamine [ No CAS ]
  • N,N,N′,N′-tetrakis(4-(1-phenyl-2-(4-tolyl)vinyl)phenyl) ethylenediamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
54% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran for 1h; Inert atmosphere; Stage #2: N,N,N′,N'-tetrakis(4-benzoylphenyl)ethylenediamine In tetrahydrofuran for 72h; Reflux; 3 0.56 g (4.99 mmol) of potassium tert-butoxide was added to a round bottom flask, and the Air was removed for 30 minutes using a vacuum pump,.After removing the flask, argon gas was introduced. Then 300 ml of THF was added using a syringe,Diethyl-4-tert-buthyl benzyl phosphonate (0.93 g, 3.84 mmol), and the mixture was stirred for 1 hour. Then, in Example 10.5 g (0.64 mmol) of the compound prepared in Reference Example 1 was added and refluxed for 72 hours. After the reaction, 1% aqueous HCl solution was added,After cooling down, it was diluted with chloroform. The organic layer was then washed with water and saturated aqueous NaCl solutionMgSO4? After removing fine water, the solvent was distilled off under reduced pressure. Then, using column chromatographyW 54% of light yellow(N, N, N ', N'-tetrakis (4- (1-phenyl-2- (4-Tolyl) vinyl) phenyl) ethylenediamine)Was obtained.
54% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: N,N,N′,N'-tetrakis(4-benzoylphenyl)ethylenediamine In tetrahydrofuran for 72h; Inert atmosphere; Reflux; 2.2.2. General procedure for the preparation of 3(a-e) General procedure: To tert-BuOK (1290 mg, 11.5 mmol) in a two-necked round bottomflask under nitrogen was added THF (100.0 mL) and diethyl-4-methylbenzylphosphonate (1.18 g, 3.84 mmol). After stirring the resultingsolution for at rt for 1 h, 2 (500 mg, 0.64 mmol) was added, and thereaction mixture heated at reflux for 72 h. After this time, the mixturewas cooled to rt, diluted with chloroform (300.0 mL), washed with 1%aqueous HCl, water, and brine, and dried over MgSO4. Following filtration,the resulting solution was concentrated under reduced pressureto afford the crude product. Purification was by column chromatography.
  • 35
  • [ 34036-07-2 ]
  • [ 3762-25-2 ]
  • (E)-1,2-difluoro-4-(4-methylstyryl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hydride In tetrahydrofuran at 0 - 5℃; for 0.5h; Stage #2: 3,4 difluorobenzaldehyde In tetrahydrofuran at 0 - 20℃; for 20h; 5.2.2. General procedure for synthesis of stilbenes General procedure: The appropriately substituted phosphonate ester (10 mmol) was dissolved in dry tetrahydrofuran (20 ml) and stirred at 0-5 °C. Sodium hydride (25 mmol) was added to the solution slowly and after thirty minutes the appropriate freshly distilled aldehyde(10 mmol) in tetrahydrofuran (30 ml) was added dropwise. The mixture was allowed to stir at room temperature overnight. In order to increase the yield, compounds 35, 37 and 40 were heated under reflux for 3-4 h. The mixture was cooled and quenched with ice water (10 ml) and poured onto ice. Dilute hydrochloric acid(1 M) was added until acidic and the solution was extracted with ethyl acetate (4 50 ml). The combined organic layers were washed with saturated salt and dried over magnesium sulfate. Filtration and evaporation of the ethyl acetate afforded crude stilbene products as oils or solids. The solids were crystallized from 95% ethanol to afford crystalline stilbenes. The oils were chromatographed on silica gel using methylene chloride to give pure products.
  • 36
  • [ 1550-35-2 ]
  • [ 3762-25-2 ]
  • (E)-2,4-difluoro-1-(4-methylstyryl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
32% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hydride In tetrahydrofuran at 0 - 5℃; for 0.5h; Stage #2: 2,4-difluorobenzaldehyde In tetrahydrofuran at 0 - 20℃; for 20h; 5.2.2. General procedure for synthesis of stilbenes General procedure: The appropriately substituted phosphonate ester (10 mmol) was dissolved in dry tetrahydrofuran (20 ml) and stirred at 0-5 °C. Sodium hydride (25 mmol) was added to the solution slowly and after thirty minutes the appropriate freshly distilled aldehyde(10 mmol) in tetrahydrofuran (30 ml) was added dropwise. The mixture was allowed to stir at room temperature overnight. In order to increase the yield, compounds 35, 37 and 40 were heated under reflux for 3-4 h. The mixture was cooled and quenched with ice water (10 ml) and poured onto ice. Dilute hydrochloric acid(1 M) was added until acidic and the solution was extracted with ethyl acetate (4 50 ml). The combined organic layers were washed with saturated salt and dried over magnesium sulfate. Filtration and evaporation of the ethyl acetate afforded crude stilbene products as oils or solids. The solids were crystallized from 95% ethanol to afford crystalline stilbenes. The oils were chromatographed on silica gel using methylene chloride to give pure products.
  • 37
  • [ 122-52-1 ]
  • [ 3762-25-2 ]
YieldReaction ConditionsOperation in experiment
In neat (no solvent) at 130℃; for 20h; 5.2.1. General procedure for synthesis of phosphonate esters General procedure: Benzyl chloride or benzyl bromide derivatives (1 eq) were added to triethyl phosphite (1.5 eq) and heated to 130 °C for 20 h. After cooling, the resulting crude product was distilled in vacuo to remove excess triethyl phosphite and ethyl chloride or ethyl bromide. Purification by filtration through a pad of silica gel (70% ethyl acetate/30% hexanes) gave the phosphonate ester products as colorless oils.
at 140℃; for 12h;
  • 38
  • [ 34036-07-2 ]
  • [ 3762-25-2 ]
  • 3,4-difluoro-4’-methyl-stilbene [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With sodium hydroxide at 45℃; for 2.5h; 15 A batch of stilbene type compound was prepared by using the following reaction conditions in substantially the same manner as in Example 2, and the reaction conditions and the results are shown in Table 1.
  • 39
  • [ 3762-25-2 ]
  • 10-(2-ethylhexyl)-3,7-diformylphenoxazine [ No CAS ]
  • 3,7-di[2-(4-methylphenyl)ethenyl]-10-(2-ethylhexyl)phenoxazine [ No CAS ]
YieldReaction ConditionsOperation in experiment
33% Stage #1: diethyl 4-methylbenzylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.333333h; Inert atmosphere; Stage #2: 10-(2-ethylhexyl)-3,7-diformylphenoxazine In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; 2.2. Materials 3,7-Di-[2-(4-methylphenyl)ethenyl]-10-(2-ethylhexyl)phenoxazine(5) was prepared by the reaction of the di-aldehyde 3 with anexcess of diethyl 4-methylbenzylphosphonate. Potassium tertbutoxide(0.58 g, 6 mmol) and dry THF (20 mL) were placed in aflask at room temperature under nitrogen atmosphere. Diethyl 4-methylbenzylphosphonate (1.14 mL, 4.7 mmol) was added dropwiseto the solution at 0 °C under nitrogen. The reaction mixturewas stirred for 20 min and di-aldehyde 3 (0.36 g, 1.0 mmol) wasadded to the reaction mixture. The resulting solution was stirred atroom temperature under the basic conditions for 3 h, by which timethe starting compound 3 reacted completely. Then the mixturewaspoured into ice water and extracted with chloroform. Organicfraction was dried by Na2SO4 and the solvent was removed byevaporation. The product was purified by column chromatographywith silica gel using ethyl acetate/hexane (vol. ratio 1:5) as aneluent. Yield: 0.15 (33%) of yellow crystals. M.p.: 183 °C (DSC). MS(APCI+, 20 V): 528.33 ([M+H]+, 100%). 1H NMR (400 MHz, DMSO, δ,ppm): 7.43 (d, J 7.4 Hz, 4H, Ar), 7.16 (d, J 7.3 Hz, 4H, Ar), 6.97 (d,J 15.7 Hz, 8H, Ar, CHCH), 6.72 (d, J 8.1 Hz, 2H), 3.55 (d,J 6.2 Hz, 2H, CH2), 2.30 (s, 6H, CH3), 1.88-1.76 (m, 1H, CH),1.43-1.16 (m, 8H, CH2), 0.88 (t, J 7.1 Hz, 3H, CH3), 0.82 (t, J 7.1 Hz,3H, CH3). 13C NMR spectrum (CDCl3, δ, ppm): 11.69, 14.14, 23.14,24.32, 26.36, 29.47, 32.36, 37.23, 63.16, 114.56, 118.45, 120.36,124.45, 126.36, 126.56, 129.46, 128.08, 132.25, 137.23, 137.61, 142.77.Elemental analysis for C38H41NO % Calc.: C 86.48, H 7.83, N 2.65; %Found: C 86.19, H 7.89, N 2.63.
  • 40
  • [ 3762-25-2 ]
  • [ 18869-29-9 ]
YieldReaction ConditionsOperation in experiment
88% Stage #1: diethyl 4-methylbenzylphosphonate With sodium t-butanolate In N,N-dimethyl-formamide at 25℃; for 0.0833333h; Inert atmosphere; Stage #2: With oxygen In N,N-dimethyl-formamide at 25℃; for 8h; stereoselective reaction;
  • 41
  • [ 59046-72-9 ]
  • [ 3762-25-2 ]
  • [ 80663-55-4 ]
YieldReaction ConditionsOperation in experiment
77% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: o-(phenylethynyl)benzaldehyde In tetrahydrofuran; hexane at -50 - 20℃;
Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: o-(phenylethynyl)benzaldehyde In tetrahydrofuran; hexane at 20℃;
  • 42
  • [ 3762-25-2 ]
  • [ 106824-45-7 ]
  • (E)-1-(hex-1-yn-1-yl)-2-(4-methylstyryl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-(hex-1-yn-1-yl)benzaldehyde In tetrahydrofuran; hexane at -50 - 20℃;
Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-(hex-1-yn-1-yl)benzaldehyde In tetrahydrofuran; hexane at 20℃;
  • 43
  • [ 3762-25-2 ]
  • [ 108-95-2 ]
  • ethyl phenyl 4-methylbenzylphosphonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% Stage #1: diethyl 4-methylbenzylphosphonate With pyridine; trifluoromethylsulfonic anhydride In dichloromethane at 20℃; for 0.166667h; Sealed tube; Stage #2: phenol In dichloromethane at 20℃; for 0.5h; Sealed tube;
  • 44
  • [ 3762-25-2 ]
  • [ 78832-95-8 ]
  • 4-(4-methylphenyl)vinylphenyl benzylsulfide [ No CAS ]
YieldReaction ConditionsOperation in experiment
64.4% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hydride In N,N-dimethyl-formamide Stage #2: 4-(benzylmercapto)benzaldehyde In N,N-dimethyl-formamide at 20℃; for 12h; 3.2 2. Synthesis of 4-(4-methylphenyl)vinylphenylbenzyl sulfide Take the reaction product of p-methylbenzyl chloride and an excess of triethyl phosphite (2.91 g, 12 mmol) in a three-necked flask.After adding NaH (1.23 g, 50 mmol) and 100 mL of DMF, it was found that a gas was generated, and then 4-benzyl mercaptobenzaldehyde (2.25 g, 10 mmol) was added, and the reaction was stirred at room temperature for 12 h, and the reaction was completed by thin-plate chromatography. The system was poured into 10 volumes of distilled water, and the precipitate was collected by filtration, and the solid was collected by recrystallization from ethanol, and stored in a vacuum oven at 40 ° C, yield 64.4%.
  • 45
  • 2-formyl-5-styrylthiophene [ No CAS ]
  • [ 3762-25-2 ]
  • C21H18S [ No CAS ]
YieldReaction ConditionsOperation in experiment
58% With sodium hydride In tetrahydrofuran 2 General procedure: DNT-2112 derivatives 20-22 were created using the synthetic route shown in Scheme 2. First, 2-bromothiophene was coupled with a trans-2-(4-Phenyl)vinylboronic acid using a Suzuki-Miyaura coupling to create compound 15 in 76% yield. [34] The 5-position of the thiophene ring was then formylated using n-Butyllithium and DMF, giving compound 16 in 36% yield. [35,36] The 5-position is preferentially formylated due to its relatively low pKa (33) compared to the 3 or 4 positions (39) resulting from its location next to the sulfur in the thiophene ring.[37] A Horner-Wadsworth-Emmons reaction using a 4-substituted phosphonic acid diethyl ester was used to add a second styryl group to the other side of the thiophene ring (Table 3) to create 2,5-distyrylthiophenes 17-19. The methoxy-substituted phosphonic acid diethyl ester gave a 14% yield that was significantly lower than the methyl and trifluoromethyl-substituted phosphonic esters, which gave yields of 58% and 76%, respectively. The DNTs 20-22 were created via the same oxidative photocyclization used in the synthesis of DNTs 9-14 (Table 4).
  • 46
  • [ 3762-25-2 ]
  • C13H10OS [ No CAS ]
  • C21H18S [ No CAS ]
YieldReaction ConditionsOperation in experiment
16% With sodium hydride In tetrahydrofuran 3 General procedure: DNT-1221 derivatives 32-36 were synthesized using the route shown in Scheme 3. Formylation with n-butyllithium and DMF was used to convert 3,4-dibromothiophene to 3-bromothiophene-4-carbaldehyde 23 in 77% yield.[38,39] Suzuki-Miyaura coupling was then used to add the first styryl group to one side of the thiophene ring to give 3-formyl-4-styrylthiophenes 24-26 in 10-77% yield (Table 5), from which asymmetric distyrylthiophenes could easily be synthesized. The trifluoromethyl-substituted styrylboronic acid gave the highest yields. A Horner-Wadsworth-Emmons reaction was used to add the second substituted styryl group to the other side of the thiophene ring (Table 6), creating 3,4-distyrylthiophenes 27-31 in yields from 16-95%. The CF3-substituted benzylphosphonic esters used in the creation of 29 and 30 gave higher yields compared to those with other substituents. The Suzuki-Miyaura coupling was performed before the Horner-Wadsworth-Emmons reaction in this route because the 1,4-diphenyl-1,3-butadiene byproducts formed from the Suzuki-Miyaura reaction were easier to separate from the more polar 3-formyl-4-styrylthiophenes than from 3,4-distyrylthiophenes. An oxidative photocyclization was then used in the same manner as the previous routes to fuse the rings together to give DNT-1221 derivatives 32-36 in yields of 6-20% (Table 7).
  • 47
  • [ 3762-25-2 ]
  • ethyl hydrogen (4-methylbenzyl)phosphonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% Stage #1: diethyl 4-methylbenzylphosphonate With pyridine; trifluoromethylsulfonic anhydride In dichloromethane for 0.166667h; Stage #2: With water In dichloromethane for 1h; Stage #3: With sodium hydroxide In diethyl ether for 0.5h;
With sodium hydroxide In ethanol at 85℃; for 12h;
  • 48
  • [ 3762-25-2 ]
  • [ 914220-97-6 ]
  • (E)-1-(cyclopropylethynyl)-2-(4-methylstyryl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-(2-cyclopropylethynyl)benzaldehyde In tetrahydrofuran; hexane at 20℃;
  • 49
  • [ 21403-38-3 ]
  • [ 3762-25-2 ]
  • (E)-1-methyl-4-(2-(2-(phenylethynyl)cyclohex-1-en-1-yl)vinyl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% Stage #1: diethyl 4-methylbenzylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-(phenylacetylenyl)cyclohex-1-enecarbaldehyde In tetrahydrofuran; hexane at -50 - 20℃;
  • 50
  • [ 63409-06-3 ]
  • [ 3762-25-2 ]
  • (E)-7-methyl-1-(4-methylstyryl)naphthalene [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 6.5h; Inert atmosphere;
  • 51
  • [ 3762-25-2 ]
  • diethyl 1-(4-methylphenyl)-1-diazomethylphosphonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% Stage #1: diethyl 4-methylbenzylphosphonate With 4-toluenesulfonyl azide; potassium-t-butoxide In benzene at -55℃; for 1h; Inert atmosphere; Stage #2: With chloro-trimethyl-silane In tetrahydrofuran; benzene at 20℃; Inert atmosphere;
  • 52
  • [ 59378-82-4 ]
  • [ 3762-25-2 ]
  • tert-butyl (E)-2-(4-methyl)styrylpyrrolidine-1-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: diethyl 4-methylbenzylphosphonate With lithium hexamethyldisilazane In tetrahydrofuran at 0℃; for 1.25h; Stage #2: 2-formylpyrrolidine-1-carboxylic acid tert-butyl ester In tetrahydrofuran at 0 - 20℃; for 13h;
Same Skeleton Products
Historical Records