526-35-2

Usage

Originator

Aloxidone ,ZYF Pharm Chemical

Manufacturing Process

A mixture of 11.4 parts of 5-methyloxazolidine-2,4-dione and 15 parts anhydrous potassium carbonate in 150 parts of dry acetone is stirred for 0.5 hour. 15 parts of allyl bromide are then added and the mixture boiled under reflux with stirring for 4 hours. After cooling and filtering, the solvent and any unchanged allyl bromide are removed by distillation. The residue is extracted with ether end the extract washed with saturated aqueous sodium bicarbonate until the subsequent water-washings are either neutral or just alkaline to litmus paper. The solvent is then distilled and the residue fractionated when 3- allyl-5-methyloxazolidine-2,4-dione is obtained in 65% yield as a colorless oil, BP: 88°-90°C/1.8 mm, nd20 = 1.4710. The dry sodium salt of 5-methyloxazolidine-2,4-dione, obtained from 4.6 parts of sodium, 100 parts of ethanol, 12 parts of urea and 23.6 parts of ethyl lactate, is suspended in 100 parts of dry benzene and 30.25 parts of allyl bromide are added. The mixture is boiled under reflux for 20 hours and the benzene decanted or filtered from any solid. The solution is washed with saturated aqueous sodium bicarbonate until the subsequent water-washings are neutral or just alkaline to litmus paper. The dried benzene solution is then distilled to remove solvent and the residue fractionated, when 3-allyl-5- methylosazolidine-2,4-dione is obtained in 27% yield as a colorless oil, BP: 89°-90°C/1 mm, nd20 = 1.4712. The dry sodium salt of 5-methyloxazolidine-2,4-dione obtained as above is mixed with 100 parts of dry dioxane and 31.25 parts of allyl bromide are added. After boiling under reflex for 24 hours, decanting the solution and distilling off the dioxane under reduced pressure, the residue is dissolved in ether and the ethereal extract mashed with aqueous sodium bicarbonate as above. Fractionation of the residue after removing the olvent furnishes 3-allyl- 5-methyloxazolidine-2,4-dione in 48.5% yield as a colorless oil; BP: 94°- 95°C/11.75 mm; nd20 = 1.4710.

InChI:InChI=1/C7H9NO3/c1-3-4-8-6(9)5(2)11-7(8)10/h3,5H,1,4H2,2H3

Upstream product

• 27770-23-6 5-methyl-2,4-oxazolidinedione 
• 106-95-6 allyl bromide 
• 124-38-9 carbon dioxide 
• 220316-77-8 N-allyl-2-bromopropionamide 
• 17351-61-0 tetraethylammonium bicarbonate 
• 556-56-9 allyl iodid 
• 105-58-8 Diethyl carbonate 

Relevant academic research and scientific papers

A safe and mild synthesis of organic carbonates from alkyl halides and tetrabutylammonium alkyl carbonates

A safe and mild procedure for the synthesis of mixed organic carbonates is described. Reaction of commercially available tetrabutylammonium methoxide and ethoxide with carbon dioxide yields the corresponding methyl and ethyl tetrabutylammonium carbonates (TBAMC and TBAEC). The reactions of these new compounds with several different alkyl halides give methyl and ethyl carbonates in high yields. The use of classic toxic and harmful chemicals such as phosgene and carbon monoxide is avoided.

Tetraethylammonium hydrogen carbonate in organic synthesis: Synthesis of oxazolidine-2,4-diones

Oxazolidine-2,4-diones were synthesised by tetraethylammonium hydrogen (TEAHC) promoted carboxylation of secondary carboxamides bearing a leaving group at the α-position. Several oxazolidine-2,4-diones, including clinically used malidone, have been prepared in moderate to excellent yields as a results of a formal proton extraction-carboxylation- intramolecular S(N)2 one-pot sequence.

Electrochemical Studies on Haloamides. Part XII. Electrosynthesis of Oxazolidine-2,4-diones

Electrogenerated bases promote the carboxylation of NH-protic carboxamides bearing a leaving group at the position 2 to give oxazolidine-2,4-diones.The process is believed to involve acid-base reaction with the substrate, carboxylation of its conjugate base to corresponding carbamate and ring-closure following intramolecular SN2 reaction.A variety of oxazolidine-2,4-diones, including clinically used trimethadione and malidone, have been prepared in high to excellent yield, which established the scope and generality of this new ring-forming process.

DIASTEREOSELECTIVE SYNTHESIS OF TRANS-4,5-DISUBSTITUTED OXAZOLIDIN-2-ONES AND VICINAL AMINO ALCOHOLS THROUGH ALKYLATION OF N-ACYLIMINIUM ION INTERMEDIATES

Treatment of 5-substituted 4-ethoxyoxazolidin-2-ones (10a-f, 13a,b) with allyltrimethylsilane in the presence of titanium tetrachloride gave the corresponding trans-4,5-disubstituted oxazolidin-2-ones (14a-f, 16a,b), respectively, with high diastereoselectivity.Methallylation of 13a,b with methallyltrimethylsilane yielded 16c,d, respectively.Ring cleavage of 14a-f afforded the corresponding threo vicinal amino alcohols 17a-f, respectively.