Ethyl benzoylacetate → HCID 11064550, compound

HRID 1683147Notes

Reaction equation

[CH3:1][CH2:2][O:3][C:4]([CH2:6][C:7]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=O)=[O:5].[CH:15](=O)/[CH:16]=[CH:17]/[CH3:18].[H-].[Na+].Cl.[NH2:23]O.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.C(O)(=O)C>[C:9]1([C:7]2[N:23]=[CH:15][CH:16]=[C:17]([CH3:18])[C:6]=2[C:4]([O:3][CH2:2][CH3:1])=[O:5])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

Conditions

Temperature: 20 °C

Procedure

In succession at 25° C. and with introduction of nitrogen, 192 g (1 mol) of ethyl benzoyl acetate in 20 min and a solution of 84 g (1.2 mol) of crotonaldehyde in 100 ml of dioxane were added dropwise with stirring in the course of 30 min to a suspension of 2 g of sodium hydride in dioxane. After stirring for 10 hours, the reaction mixture was treated with 800 ml of acetic acid and then with 245 g (3.5 mol) of hydroxylamine hydrochloride. After stirring at 110° C. for 2 hours, the mixture was cooled to 20° C., stirred into 1 kg of ice and rendered alkaline with solid K2CO3. It was then extracted with ethyl acetate, the combined extracts were extracted with 2N HCl solution and the combined aqueous extracts were rendered alkaline with solid K2CO3 and again extracted three times with 300 ml of ethyl acetate each time. After concentrating the combined organic extracts, 62 g of ethyl 2-phenyl-4-methylnicotinate (88.5% of theory) were obtained as a yellowish oil, nD23 =1.5724.

Workup

stirringAfter stirring at 110° C. for 2 hours
extractionIt was then extracted with ethyl acetate
extractionthe combined extracts were extracted with 2N HCl solution
extractionagain extracted three times with 300 ml of ethyl acetate each time
concentrationAfter concentrating the combined organic extracts

Sources & evidence

ORD record: ord-8c2f0dc139384fe18e351e385bd0703f
Source dataset: uspto-grants-1997_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05637554

Reaction notes

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