No abstract

The synthesis of r-fluoroglutamic acid, HOOCCIIFCHyCH(.\'I-I2)COOI-I, was achieved by two independent methods, both of which involved the Michael reaction: (1) methyl a-fluoroacrylate and diethyl acetamido~nalonate gave the transesterilied intermediate, which on hydrolysis produced r-lluoroglutamic acid (3lC% yield); (2) ethyl a-acetamidoacrylate and diethyl fluoromalonate reacted under mild conditions to give, after hydrolysis, the required amino acid in 56% overall yield. Of the two procedures, the second is preferable, since it is based on Inore readily available starting ~naterials and gives a higher yield.

No abstract

I t has been shown that the carbon-oxygen bond of nitrate esters is susceptible to cleavage by certain representative nucleophilic reagents, of which sodium iodide, sodium cyanide, and potassium thiocyanate have received particular attention. Allyl, 3-hydroxypropyl, 4-fluorobutyl, hexyl, and benzyl nitrate were examined in order t o determine the effect if any of functional groups on the ease and efficiency of cleavage.Alkyl and aralkyl sulphonates are well known as synthetic intermediates, undergoing most of the replacement and elimination reactions characteristic of the all;yl halides. However, their preparation, while frequently occurring in very high yield, is time consuming, and the products often have very high boiling points, malting purification inconvenient. Accordingly, attention was directed to esters of other inorganic oxy-acids; these it was hoped would undergo the same reactions, due to oxygen-alltyl fission. From a superficial consideration of structure, nitrates were selected for study:The chemistry of nitrate esters has been reviewed recently (3). Several alkylation reactioils have been reported: benzyl nitrate has been used successfully in benzylating malonic and acetoacetic esters (15); methyl nitrate has been converted to the corresponding isothiouronium nitrate using thiourea (21) ; diphenylmethyl nitrate has been converted to N-diphenylmethylacetamide on treatment with acetamide (6) ; trialliyls~ilpl~onium nitrates have been formed from dialkyl sulphides and alkyl nitrates (18); amiiles have been alkylated using alliyl and arallcyl nitrates (9, 12, 19) ; and the action of sodium ethoxide on nitrates has produced ethyl ethers (4, 5 ) . The reactions of nitrates have received most attention in the field of carbohydrates, and in a t least one instance the nitrate grouping has been replaced by iodide using sodium iodide in acetone (11). No reference has been made to the replacement reactions of the nitrate grouping as a simple alternative t o the use of alkyl halides in preparative organic chemistry. 'Manuscript received March 12, 1956.

No abstract