2-butenoic acid

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

实验步骤: Using the method of Example 2, 516 g (6 mol) of crotonic acid were first admixed, at from 75 to 90° C. in the presence of 73.4 g of a 7% strength hydrogen peroxide solution, with 636 g (6 mol) of sodium hypophosphite monohydrate dissolved in 860 g of water. The resultant reaction mixture was then reacted with ethylene in the presence of 73.4 g of a 7% strength hydrogen peroxide solution. Appropriate work-up gave 623 g (58% of theory) of 3-(ethylhydroxyphosphinyl)butyric acid as colorless solid; chlorine content: <0.1 ppm. The resultant reaction mixture

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

实验步骤: Dimethylamine (30 g) was added to a pressure-resistant container (reactor), and the reactor was hermetically sealed. The temperature of the reactor was adjusted to 20° C., and crotonic acid (14.3 g) was fed into the reactor by means of a high-pressure pump. During addition of crotonic acid, heat of neutralization is generated. Therefore, while the reactor was cooled in an ice bath, crotonic acid was added dropwise to the reactor at a rate of 5 to 7 mL/minute, so as to adjust the temperature in the reactor to 25 to 35° C. After completion of dropwise addition, reaction was allowed to proceed for one hour, and then analysis was carried out. The reaction time (as measured from initiation of dropwise addition) was one hour and three minutes. the reactor was hermetically sealed was adjusted to 20° C. heat of neutralization Therefore, while the reactor was cooled in an ice bath to 25 to 35° C After completion of dropwise addition, reaction The reaction time (as measured from initiation of dropwise addition) was one hour and three minutes

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

实验步骤: 17.8 g of N,N'-dicyclohexylcarbodiimide were added while stirring within 5 minutes to a solution of 7.0 g of 4-hydroxybenzaldehyde, 7.4 g of (E)-but-2-enoic acid and 0.1 g of 4-(dimethylamino)pyridine in 50 ml of dichloromethane. The reaction mixture was stirred overnight, then filtered. The filtrate was washed with saturated sodium bicarbonate solution and with water and concentrated. Chomatographic purification of the residue on silica gel with hexane/ethyl acetate (vol. 3:7) and two-fold recrystallization of the fractions which were pure according to thin-layer chromatography gave 12.2 g of 4-[(E)-but-2-enoyloxy]benzaldehyde. filtered The filtrate was washed with saturated sodium bicarbonate solution and with water concentrated Chomatographic purification of the residue on silica gel with hexane/ethyl acetate (vol. 3:7) and two-fold recrystallization of the fractions which

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

实验步骤: A solution of 86 g of crotonic acid (1 mole) and ethanol-amine (1 mole) in pyridine (200 ml) is refluxed for 2-3 hours and subsequently cooled. The resulting produce is filtered and recrystallized to yield the title compound having m.p. 178°-180° C. (compound 1.1, Table 1). Following analogous procedure, the compounds 1.2-1.7, 1.10, 1.11, and 1.13-1.15 set forth in Table 1 are obtained. subsequently cooled The resulting produce is filtered recrystallized

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

实验步骤: To a solution of 4.86 g (5.52 mL, 21.0 mmol) of 1-(2-dimethylamino-ethoxy)-1-trimethyl-siloxy-2-methyl-1-propene, 0.1 mL of tetrabutylammonium biacetate hexahydrate (0.04M in THF) in 30 mL of THF was added a mixture of 6.6 g (7.1 mL, 42 mmol) of 2-dimethylaminoethyl methacrylate (purified by distillation and passage over a column of basic alumina under argon), and 31.6 g (31.6 mL, 168 mmol) of 2-phenylethyl methacrylate (purified by passage over a column of basic alumina under argon) from an addition funnel. The temperature of the reaction mixture rose to 62° C. during the course of the addition, and an ice bath was used to moderate the temperature rise. When, following the conclusion of the addition, the temperature was 26° C., the dropwise addition of 43.2 g (49 mL, 273 mmol) of trimethylsilyl methacrylate was begun. During the course of the addition the temperature of the reaction mixture rose to 45° C. while a total of 1.25 mL of tetrabutylammonium biacetate hexahydrate (0.04M in THF) was added in 9 additions. Analysis of an aliquot of the solution by 1H NMR showed that there was no residual monomer present. After addition of 55 mL of THF, 56 mL of methanol, and 0.086 g (2.7 mmol) of tetrabutylammonium fluoride trihydrate the solution was refluxed for 9 hr. Then 50 mL of THF was added, and refluxing was continued for an additional 9 hr. The solution was evaporated under reduced pressure with a rotary evaporator. The solid residue was dried in a vacuum oven at 80° C. for 8 hr to give 57 g of poly ω-2-β-dimethylaminoethyl isobutyrate(2-dimethylaminoethyl methacrylate [9 mol %]-co-2-phenylethyl methacrylate [35 mol %]-b-methacrylic acid [56 mol %]) 1H NMR analysis of the polymer showed that virtually no trimethylsilyl groups remained. purified by passage over a column of basic alumina under argon) from an addition funnel The temperature of the reaction mixture rose to 62° C. during the course of the addition, and an ice bath the conclusion of the addition was 26° C. During the course of the addition the temperature of the reaction mixture was added in 9 additions was refluxed for 9 hr refluxing The solution was evaporated under reduced pressure with a rotary evaporator The solid residue was dried in a vacuum oven at 80° C. for 8 hr

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

实验步骤: To a solution of 5.55 g (6.31 mL, 24 mmol) of 1-(2-dimethylaminoethoxy)-1-trimethylsiloxy-2-methyl-1-propene and 0.1 mL of tetrabutylammonium biacetate (0.04M in propylene carbonate) in 30 mL of THF was added a mixture of 7.6 g (8.1 mL, 48 mmol) of 2-dimethylaminoethyl methacrylate (purified by passage over a column of basic alumina under argon), and 23.9 g (26.7 mL, 168 mmol) of n-butyl methacrylate (purified by passage over a column of basic alumina under argon) from an addition funnel. The temperature of the reaction mixture rose from 27° C. to 61° C. during the course of the addition, and an ice bath was used to moderate the temperature rise. When, following the conclusion of the addition and removal of the cooling bath, the temperature was 32° C., the dropwise addition of 49.4 g (56.1 mL, 312 mmol) of trimethylsilyl methacrylate was begun. During the course of the addition the temperature of the reaction mixture rose to 56° C. while a total of 1.2 mL of tetrabutylammonium biacetate (0.04M in propylene carbonate) was added in 4 additions, and 20 mL of THF was added to reduce viscosity. Analysis of an aliquot of the solution by 1H NMR showed that there was no residual monomer present. After addition of 70 mL of tetrabutylammonium fluoride trihydrate (0.03M in methanol), the solution was refluxed for 12 hr. The solution was concentrated under reduced pressure with a rotary evaporator to give 80 g of a 40.58% solids solution of poly ω-2-β-dimethylaminoethyl isobutyrate(2-dimethylaminoethyl methacrylate [9 mol %]-co-n-butyl methacrylate [32 mol %]-b-methacrylic acid [59 mol %]). purified by passage over a column of basic alumina under argon) from an addition funnel The temperature of the reaction mixture rose from 27° C. to 61° C. during the course of the addition, and an ice bath the conclusion of the addition and removal of the cooling bath was 32° C. During the course of the addition the temperature of the reaction mixture was added the solution was refluxed for 12 hr The solution was concentrated under reduced pressure with a rotary evaporator

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

实验步骤: A mixture of 2,4-diamino-5-(3-hydroxy-4,5-dimethoxybenzyl)pyrimidine (2.76 g, 0.01 mole) and crotonic acid (0.87 g 0.01 mole) in polyphosphoric acid (27 g) was stirred and heated on a steam bath for 4 hr. The reaction mixture was cooled to 50° and poured onto ice (100 g) with stirring. The resulting solution was basified to pH 8.0 with concentrated ammonium hydroxide, giving a suspension which was then extracted with methylene chloride (3×100 mL). The combined extracts were washed with 0.1N sodium hydroxide (2×100 mL), water (100 mL) and then dried over anhydrous magnesium sulfate. Evaporation of solvent in vacuo gave the title compound (1.0 g, 29%). This was recrystallized from 95% ethanol to give 2,4-diaino-5-(3,4-dihydro-7,8-dimethoxy-2-methyl-4-oxo-2H-1-benzopyran-5-ylmethyl)pyrimidine as the hemihydrate, mp 128°-132°. Anal. Calcd for C17H20N4O4.1/2H2O: C, 57.78; H, 5.99; N, 15.85. Found: C, 57.79; H, 6.02; N, 15.86. heated on a steam bath for 4 hr The reaction mixture was cooled to 50° poured onto ice (100 g) with stirring giving a suspension which was then extracted with methylene chloride (3×100 mL) The combined extracts were washed with 0.1N sodium hydroxide (2×100 mL), water (100 mL) dried over anhydrous magnesium sulfate Evaporation of solvent in vacuo

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

实验步骤: In 200 ml. carbon tetrachloride are dissolved 0.5 mole (43.07 g.) crotonic acid and the equimolar amount of 2,2,2-trichloroethanol, 1 ml. concentrated sulphuric acid is added thereto and the reaction mixture is heated under reflux on a water separator until the theoretical amount of water (9 ml.) has separated off. Subsequently, the organic phase is shaken out twice with, in each case, 100 ml. aqueous 2N sodium hydrogen carbonate solution and twice with, in each case, 50 ml. of water, the organic phase is then dried with anhydrous magnesium sulphate and the solvent is distilled off in a vacuum. There is finally obtained the desired product (i) in the form of a bright yellow oil in a yield of 95% of theory. C6H7O2Cl3. (217.4791). the reaction mixture is heated has separated off of water, the organic phase is then dried with anhydrous magnesium sulphate the solvent is distilled off in a vacuum

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

实验步骤: In 200 ml. carbon tetrachloride are dissolved 0.5 mole (43.07 g.) crotonic acid and the equimolar amount of 2,2,2-trichloroethanol, 1 ml. concentrated sulphuric acid is added thereto and the reaction mixture is heated under reflux on a water separator until the theoretical amount of water (9 ml.) has separated off. Subsequently, the organic phase is shaken out twice with, in each case, 100 ml. aqueous 2N sodium hydrogen carbonate solution and twice with, in each case, 50 ml. of water, the organic phase is then dried with anhydrous magnesium sulphate and the solvent is distilled off in a vacuum. There is finally obtained the desired product (i) in the form of a bright yellow oil in a yield of 95% of theory. C6H7O2Cl3. (217.4791). the reaction mixture is heated has separated off of water, the organic phase is then dried with anhydrous magnesium sulphate the solvent is distilled off in a vacuum

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

实验步骤: A series of vinyl acetate-crotonic acid interpolymers is prepared by the method of example 1 with variation in the following parameters; acid monomer content, polyvinyl alcohol content, the amount of ammonia added with crotonic acid during the suspension polymerization, and the amount of ammonia added for the final pH adjustment at the stage of latex formation. The results are presented in table 1. In examples 9, 10, 11 and 14, all the crotonic acid is added initially; however ammonia is added incrementally during the suspension polymerization step. In example 14, ammonia is also added to the initial polymerization mixture. Because of low conversion of vinyl acetate, the crotonic acid content of the interpolymer is generally about 15 percent higher than theoretical based on the crotonic acid charged to the reaction kettle. polymerization mixture charged to the reaction kettle

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

实验步骤: A series of vinyl acetate-crotonic acid interpolymers is prepared by the method of example 1 with variation in the following parameters; acid monomer content, polyvinyl alcohol content, the amount of ammonia added with crotonic acid during the suspension polymerization, and the amount of ammonia added for the final pH adjustment at the stage of latex formation. The results are presented in table 1. In examples 9, 10, 11 and 14, all the crotonic acid is added initially; however ammonia is added incrementally during the suspension polymerization step. In example 14, ammonia is also added to the initial polymerization mixture. Because of low conversion of vinyl acetate, the crotonic acid content of the interpolymer is generally about 15 percent higher than theoretical based on the crotonic acid charged to the reaction kettle. polymerization mixture charged to the reaction kettle

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of diisopropylamine (2.42 g, 24.0 mmol) and 8.88 ml (24.0 mmol) butyllithium (2.7M in Heptan) in THF (20 ml) at −70° C. is added a soln. of crotonic acid (1.03 g, 12.0 mmol) in THF (10.0 ml). After stirring at −70° C. and 0° C., a soln. of cyclopropanecarboxylic acid N,O-dimethylhydroxylamide (1.29 g, 10.0 mmol) in THF (10.0 ml) is added. The solution is heated to 48° C. After cooling to −50° C., a solution of glacial acetic acid (5 ml) in THF (10 ml), and 20% aq. NaCl (25 ml) are slowly added. The pH is adjusted to 1.5 with 2M HCl and the mixture is extracted with CH2Cl2 (3×25 ml). Organic phases are washed with 20% aqeous NaCl (2×25 ml) and evaporated to dryness under reduced pressure. The resulting yellow oil is dissolved in toluene (100 ml). 4-Fluoro-2′-aminobenzophenone methansulfonic acid salt (3.23 g, 10.4 mmol) is added and the solution is refluxed in a water separator apparatus for 24 h. Upon cooling, a brown precipitate is formed, which is separated from the mother liquor and purified by chromatography on silica gel (CH2Cl2—MeOH) to afford (E)-3-[2-cyclopropyl-4-(4-fluoro-phenyl)-quinolin-3-yl]-acrylic acid. MS (ES): [M−H]− 332. is added a soln The solution is heated to 48° C After cooling to −50° C. the mixture is extracted with CH2Cl2 (3×25 ml) Organic phases are washed with 20% aqeous NaCl (2×25 ml) evaporated to dryness under reduced pressure The resulting yellow oil is dissolved in toluene (100 ml) Upon cooling a brown precipitate is formed which is separated from the mother liquor purified by chromatography on silica gel (CH2Cl2—MeOH)