4-乙烯基苄氯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Carbazole was reacted with 1.5-fold excess of 4-vinylbenzyl chloride in benzene/water using NaOH as a base, and benzyltriethylammonium chloride as phase catalyst to afford 4-(9-carbazolyl)methylstyrene (CMS) at 80° C. for 5 h. The reaction mixture was extracted with chloroform and the organic layer washed with water, evaporated, and washed with hexane several times. The solid was dissolved in and recrystallized from diethyl ether at −20° C. Yield: 80%. The solid monomer was dried over P205 at 10-6 mmHg for 1 week and then dissolved in anhydrous THF and stored at −30° C. in glass ampoules under high vacuum. This reaction scheme is schematically shown in FIG. 2. The monomer is characterized by using 1H-NMR, 13C-NMR and FT-IR. Undesirable side-reaction of the monomer prepared is seen in FIG. 1.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A 1 L (liter) round bottom flask was charged with hexane (400 mL) and 4-vinylbenzyl chloride (104.4 g, 0.68 moles). The reaction flask was placed into an ice/water bath and stirred with a magnetic stir bar. Two equivalents of pyrrolidine (130 g, 1.37 moles) were added over the course of 1 hour. After completed addition the ice/water bath was removed and the reaction was stirred at room temperature overnight. Solids were removed via vacuum filtration and volatiles were removed under vacuum to render the product in quantitative yield. The reaction flask was placed into an ice/water bath was removed the reaction was stirred at room temperature overnight Solids were removed via vacuum filtration and volatiles were removed under vacuum

反应条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a 1 liter round bottomed flask were added 60.0 grams of 9-dicyanomethylenefluorene-4-carboxylic acid, 700 milliliters of N,N-dimethylformamide, 67.1 grams of 4-vinylbenzyl chloride, and 37.0 grams of sodium bicarbonate, and the resulting mixture was stirred at 40° C. for 48 hours. The mixture was poured into 1,500 milliliters of distilled water with vigorous stirring, and the resulting aqueous mixture was extracted with 1,000 milliliters of dichloromethane. The organic layer was separated and was further washed with 1,500 milliliters of distilled water and dried over anhydrous magnesium sulfate. Subsequently, the organic solvent was removed by means of a rotary evaporator and the residue was recrystallized from a mixture of dichloromethane and methanol (2:1 by volume) to give vinylbenzyl 9-dicyanomethylenefluorene-4-carboxylate after filtration and drying in a vacuo for 48 hours. the resulting aqueous mixture was extracted with 1,000 milliliters of dichloromethane The organic layer was separated was further washed with 1,500 milliliters of distilled water dried over anhydrous magnesium sulfate Subsequently, the organic solvent was removed by means of a rotary evaporator the residue was recrystallized from a mixture of dichloromethane and methanol (2:1 by volume)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 20 ml (0.14 mol) of 4-vinylbenzylchloride and 25 ml (0.28 mol) of morpholine were refluxed in 150 ml of methanol for 3 h. The mixture was then concentrated in vacuo, and the resulting residue was partitioned between 1M hydrochloric acid and water [sic]. The acidic phase was washed with ether and then made alkaline with 2M sodium hydroxide solution. This aqueous phase was extracted with ether. This organic phase was dried and concentrated in vacuo, resulting in 24.6 g of the product. The mixture was then concentrated in vacuo the resulting residue was partitioned between 1M hydrochloric acid and water [sic] The acidic phase was washed with ether This aqueous phase was extracted with ether This organic phase was dried concentrated in vacuo

反应条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This Example illustrates the synthesis of polymeric blocked developer PBD1. First, 1-(4-vinylbenzyl)-2-methylbenzimidazole was prepared. A suspension of 2-methylbenzimidazole (25.0 g, 0.19 mol), 4-chloromethylstyrene (31.8 g, 0.21 mol), powdered potassium hydroxide (10.6 g, 0.19 mol), and potassium carbonate (13.1 g, 0.1 mol) in 200 mL of dry tetrahydrofuran was stirred at 25° C. for 5 d. The reaction mixture was filtered, and the solid residue extracted with additional tetrahydrofuran. The combined liquids were concentrated at reduced pressure, and the resulting brown oil was triturated with ligroin and held at −15° C. for a few hours to induce crystallization. The ligroin was decanted from the product, which was then purified by recrystallization from 70% methanol/30% water. A cream colored solid product (43.2 g, 92%) was obtained after drying. 1H NMR (CDCl3) δ 2.61 (s, 3H), 5.28 (d, J=11.0, 1H), 5.33 (s, 2H), 5.75 (d, J=17.6, 1H), 6.7 (m, 1H), 7.05 (d, J=8.1, 2H), 7.25 (m, 2H), 7.37 (d, J=8.2, 2H), 7.78 (d, J=7.3, 1H). Electrospray mass spectrometry (ES-MS) m/e 249+ (M+1). the synthesis The reaction mixture was filtered the solid residue extracted with additional tetrahydrofuran The combined liquids were concentrated at reduced pressure the resulting brown oil was triturated with ligroin held at −15° C. for a few hours crystallization The ligroin was decanted from the product, which was then purified by recrystallization from 70% methanol/30% water was obtained after drying

反应条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 500 μl 4-opening flask equipped with a stirring bar, 49.01 g of sodium cyanide was mixed with 70.07 g of water and 50.96 g of ethanol. Then, the temperature of the flask was elevated to 60° C. and the sodium cyanide was completely dissolved. To said solution; 87.50 g of 4-chloromethylstyrene was slowly added and it was reacted for 3 hours while stirring and maintaining the reaction temperature within 60-70° C. When the reaction terminated, said solution was cooled to 40° C., and 100 g of diethylether was added and the diethylether layer was separated. The separated organic layer was extracted with 300 g of water three times, and the water layer was extracted with 50 g of diethylether and was combined with said organic layer. The separated obtained organic layer was dried with magnesium sulfate for one day, and then the organic solvent was removed using an evaporator to obtain the product 4-cyanomethylstyrene. The yield of the product was 80%, and the product was a deep purple color. In a 500 μl 4-opening flask equipped with a stirring bar was elevated to 60° C. it was reacted for 3 hours When the reaction terminated was cooled to 40° C. 100 g of diethylether was added the diethylether layer was separated The separated organic layer was extracted with 300 g of water three times the water layer was extracted with 50 g of diethylether The separated obtained organic layer was dried with magnesium sulfate for one day the organic solvent was removed an evaporator

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1500 g of methyl isobutyl ketone, 69 g of 4-hydroxybenzoic acid and 58.0 g of triethylamine were charged into a separable flask as used in Reference Example 4, and after the flask was heated to 80° C. while replacing the flask inside atmosphere with a nitrogen gas, 72.4 g of p-chloromethylstyrene was dropwise added thereto over 2 hours. Then, stirring was continued for 6 hours. After the reaction, 3 liters water was added to the reaction mixture, and powdery precipitate was recovered therefrom and washed with n-hexane, whereby 36.2 g of p-hydroxybenzoyloxymethylstyrene of the following chemical formula was obtained (yield: 30%): ##STR8## was dropwise added was continued for 6 hours was added to the reaction mixture, and powdery precipitate was recovered washed with n-hexane, whereby 36.2 g of p-hydroxybenzoyloxymethylstyrene of the following chemical formula was obtained (yield: 30%)

反应条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 4-vinylbenzyl dithiobenzoate (VBThB) was prepared according to reaction scheme 4, as follows. A 500 mL round bottom flask was dried with 3 vacuum/heat/nitrogen cycles. 100 mL of dry THF was added along with 3.3 grams of magnesium turnings. The mixture was placed in an oil bath set to 40° C., and 13.8 grams (0.088 moles) bromobenzene was added. 7.91 mL (0.088 moles) of dry carbon disulfide was added dropwise over the next 15 minutes. When all the carbon disulfide was added, the temperature was increased to 50° C., and 18.62 grams (0.088 moles) of 4-vinylbenzyl chloride was added. The solvent was removed. The crude product was purified via column chromatography over activated alumina (Brockman activity II). The final product was obtained as a red oil. The conversion was estimated at 48% after eluent removal. according to reaction scheme 4 A 500 mL round bottom flask was dried with 3 vacuum/heat/nitrogen cycles 100 mL of dry THF was added along with 3.3 grams of magnesium turnings The mixture was placed in an oil bath set to 40° C. The solvent was removed The crude product was purified via column chromatography over activated alumina (Brockman activity II)

反应条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of (R)-3-[{N-(2-amino-5-(trifluoromethyl)benzoyl)glycyl}amino]pyrrolidine (0.050 mmol), 4-vinylbenzyl chloride (9.9mg, 0.065 mmol), piperidinomethylpolystyrene (60 mg), acetonitrile (1.0 mL) and chloroform (0.30 mL) was stirred at 50° C. for 12 h. The reaction mixture was cooled, loaded onto Varian™ SCX column and washed with CH3OH (15 mL). Product was eluted using 2 N NH3 in CH3OH (5 mL) and concentrated to afford (R)-3-[{N-(2-amino-5-(trifluoromethyl)benzoyl)glycyl}amino]-1-(4-vinylbenzyl)pyrrolidine (Compound No. 1701) (19.6 mg, 88%): The purity was determined by RPLC/MS (92%); ESI/MS m/e 547.2 (M++H, C23H25ClF3N4O2). The reaction mixture was cooled washed with CH3OH (15 mL) Product was eluted concentrated