Frankland-Duppa

Reaction XLI3I. (d) Condensation of Diethyl Oxalate with Alkyl Halides in the presence of Zinc (Frankland- -Duppa). (A., 185, 184.)—This is a type of condensation very similar to those just described. The zinc alkyl is not isolated, and simple halogen compounds are used. The product is a derivative of glycollic acid. 

Frankland-Duppa reaction. Formation of a-hydroxycarboxylic esters by reaction of dialkyl oxalates with alkyl halides in the presence of zinc, or amalgamated zinc, and acid. 

Forster Diazoketone Synthesis Forster Reaction Four-Component Condensation Franchimont Reaction Frankland Synthesis Frankland-Duppa Reaction Freund Reaction... 

This preparation was discovered independently by Geuther (1863) and by Frankland and Duppa (1865). The reaction was subsequently investigated in detail and so w idely extended by Claisen that it has become solely a specific example of the more general process known as the Claisen Condensation. Claisen showed that an ester under the influence of sodium ethoxide would not only condense with itself (as in the preparation of ethyl acetoacetate), but also with (i) another ester, (ii) a ketone, if of formula RCHgCOR, (iii) a nitrile, if of formula RCH CN, in each case with the elimination of alcohol. Examples of these modifications are ... 

As discussed previously, A. Geuther described the former, Edward Frankland and B. F. Duppa the latter. 

About the same time Frankland and Duppa, using the same reaction, discovered that the hydrogen atoms of the methylene group are replaceable by sodium and various organic radicles. 

Geuther represented the substance as CHg.C OH) CH.COOC2H6, that is /3-hydroxycrotonic ester, but Frankland and Duppa preferred the keto formula CH8.CO.CH2.COOC2H6, and represented it as aceto-acetic ester,7... 

Halogens, e.f/. iodine. Alcoholic solution. Methyl mercury iodide methyl iodide, Buekton, AnnaU-n, 1858, io8, 103 Frankland and Duppa, Trans. Claim. Noc., 1863, x6, 415 Annalen 1864, 130, 104 Hilpert andDitmar, Ber, 1913, 46, 3738. 

Cadrainm. Heat at 100- 130 C. Cadmium diethyl (not free from mercury). Frankland and Duppa, Tran Chem. Soc., 1864, 17, Annalen, 1S64, 130, 117. 

Its inactivity gives preference to the second formula the first, however, contains an asymmetric carbon atom, for which reason I hope to be able to produce the acid named by following the method of Frankland and Duppa from oxalic acid and iodo acetic acid esters by the aid of zinc. 

By the end of 1865 Frankland began publicly to advocate Crum Brown s notation for use in certain contexts. He probably first encountered it in reading a reprinting of Crum Brown s 1864 paper, which appeared in the Journal of the Chemical Society in the summer of 1865. On 28 May 1866 he wrote to Crum Brown, "1 am much interested in graphic formulae and consider that yours have several important advantages over Kekule s." He told Crum Brown that he had used them in his course presented in winter term 1865-66 "with very great advantage." By return post Crum Brown informed Frankland where his publisher could procure the necessary type fonts, and Frankland proceeded to use the formulas systematically in his new textbook. Frankland and his student Baldwin Duppa had synthesized lactic acid and... 

Frankland and Duppa, "Synthetical Researches" (1867). This paper, read 17 January 1867, provided several complex graphic formulas of newly synthesized compounds, e.g., on p. Ill, "ethylic isopropaceto-acetate" (today denominated ethyl a-isopropyl-(3-ketobutyrate). 

A complex graphic formula by Frankland and Duppa, after Crum Brown. Source Frankland and Duppa, Journal of the Chemical Society 20 (1867) 111. 

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