2,2-bis(hydroxymethyl)butyl acrylate synthesis

Yield:-

Reaction Conditions:

Stage #1:1,1,1-tri(hydroxymethyl)propane with toluene-4-sulfonic acid at 50; for 12 h;Dean-Stark;
Stage #2:acrylic acid methyl ester with tetramethoxytitanium at 105 - 110; for 2.5 h;Inert atmosphere;

Steps:

2 Synthesis of trimethylolpropane monoacrylate
Calcium tube,145.7 g of trimethylolpropane, 300 ml of acetone, 3 g of p-toluenesulfonic acid monohydrate and 300 ml of petroleum ether were added to an eggplant type flask equipped with a cooling tube and a Dean-Stark trap, and the temperature was raised to 50 ° C. And heated under reflux in an oil bath set. After 12 hours, after it was confirmed that no more water was generated, the reaction mixture was cooled to room temperature. Next, 3 g of sodium acetate was added and the mixture was further stirred for 30 minutes, then the petroleum ether and acetone were distilled off with an evaporator. The obtained crude product was distilled under reduced pressure to obtain ketalized trimethylolpropane (intermediate 2). In a 3 L four-necked flask, 104.8 g of the intermediate 2 obtained in the step (1), 258.0 g of methyl acrylate and 3.7 g of tetramethoxytitanium were charged. Then, the reaction liquid was stirred and transesterification reaction was carried out at 105 to 110 ° C. for 2.5 hours while introducing nitrogen gas into the liquid. After completion of the reaction, acrylate ester of ketalized trimethylolpropane (Intermediate 3) was obtained by fractional distillation. In a 3 L four-necked flask, 90.2 g of water,28.4 ml of a cation exchange resin RCP 160 M (manufactured by Mitsubishi Chemical Corporation) and 115.3 g of the intermediate 3 obtained in the step (2) were charged.Then, the reaction solution was stirred and a ketal deketone reaction was carried out at 24 ° C. for 27 hours while nitrogen gas was introduced into the solution.After completion of the reaction, the cation exchange resin was separated from the reaction solution by filtration,The filtered reaction mixture was washed six times with 100 ml of hexane to remove unreacted starting materials,200 ml of ethyl acetate was added to the aqueous layer to extract the product.Then, this ethyl acetate extract was concentrated under reduced pressure (800 Pa)Ethyl acetate and water were distilled off at 40 ° C. or lower,Trimethylolpropane monoacrylate was obtained.

References:

POLA CHEMICAL INDUSTRIES INCORPORATED;TAKEYAMA, YUICHIRO;KAJI, MEGUMI;TSUYUKI, MOE;NIO, ATSUSHI JP6144466, 2017, B2 Location in patent:Paragraph 0027-0029