In our work on muscarine, certain quaternary ammonium salts with the
substituted 1,4-dioxane nucleus were necessary for studies on biological activity.
For this purpose we followed a new synthetic route for the preparation
of substituted 1 , 4-dioxene derivatives, according to the reaction scheme
I-IV

K. Balenović

N. Bregant

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CR 0 AT I CA CHEM IC A ACT A 28 (1956) 67 KRATKA SAOPCENJA SHORT COMMUNICATIONS CCA-10 547.841 A Route for the Synthesis of Substituted Dioxene Derivatives''" K. Balenovic and N. Bregant Chemical Institute, Faculty of Science, University of Zagreb, Strossmayerov trg 14, Zagreb, Croatia Yugoslavia Received December 31, 1955 In our wol'lk on mu:scarine, certa1n quaternary ammonium salts with the substituted 1,4-dioxane nucleius were necessary for studies on biological acti-vity. Fo1r this pll!Tpose we followed a new synthetic route for the ,P'reparation of substituted 1 , 4-<lio~ene derivatives, according to the reaction scheme I-IV. R . COCHN2 II 0 / ' R II I - , / 0 IV R . COCH20CH2CH20H III As an example for th i!s synthesis a descriJption is now given of the 1prepa-ration of 2-phthalimidomethyl-1,4-dioxene-(2) (IV) . (R = C"H,(COLNCH 2 in I-IV). The diazoiketione II was sus;pended in 1,2-ethanediol and converted, with catalytic quantities of boron trifluoride-diethyl ether complex1 into l-(2'-hydro-xyethoxy)-3-rph thaldmidopirorpaJlJone (III) . A benzene solution of this compound, on 1treating with rphosphoru:s pentoxide, afforded 2-<phtha:limidomethyl-1,4-dioxene-(2) (IV) . The scope of this reaction is being investigated. EXPERIMENT AL All melting pO'ints are uncorrected. 1-(2' -Hydroxyethoxy)-3-phthalimidopropanone (III) A su~pension of l-diaz-0-3-phthalimidoiprnpanone3 (4.6 g., 0.02 mole) in- l ,2-ethanedi-01 (20 ml.) and iborontrifluoride-diethyl ether complex (G.1 ml.) was heated to 50--600. After half an hour the foaming ceased, and the clear yellov1ish solution was poured into a 1tenfold quantity of water and left overn1ght at GO. The crude l-(2'-hydrox yethoxy)-3-phthalimidopropanone was collected and dried, yield 3.3 g. (63°/o), m. ip. 85-1020. The sample for analysis was 0dissolved in benzene and ;passed thr-0ugh a column of a lumina (1 : 10). After removing the solvent by evaporation, the residue was recrystallized three times from dichloromethane-petroleum ether ; * Communication No. 51 fr-0m the Chemical Institute. 68 K. BALENOVIC AND N. BREGANT white needles were obtained, with the m . p . 132-1350 (sintering at 1100). Before ~malysis the substance was fused at 1800/0.05 mm. for a short time. Anai. 3.99 mg. subst.: 0.195 ml. N2 (150C, 745 mm.) C1aH1aN05 (263.24) calc'd.: N 5.320/o found: N 5.680/o 2-Phthalimidomethyl-1,4-dioxene-(2) (IV) A solution of pure 1-(2' -hydroxyethoxy)3-phthalimidopropanone (III, 1 g.) in benzene (40 ml.) was shaken with phosphorus pentoxide (2 g.) at room temperature for 24 hours. The suspension was filtered, evqporated to dryness, and the thus obtained crude 2-phthalimidomethyl-1,4-dioxene-(2) , yield 0.77 g. 830/&), m. p. 145----1530, recrystallized from dichloromethane-petroleum ether and sublimed at 140.o/O.Ol mm.; white prisms, m . p. 164--1650. Anai. 9.68 mg. suibs.t. : 22.63 mg. C02, 4.26 mg. H 20 C1aH11N04 (245.22) calc'd .: C 6.3.67; H 4.520/o found: C 63.81; H 4.920/o The subsrtance gave a s trong positive tes t for unsaturation with bromine in t etrachloromethane. REFERENCES 1. M. rS . Newman and P. F. Be a 1, J. Am. Chem. Soc. 72 (1950) 5161. 2. R. K. Summer be 11 and L . N. Bauer, J . Am. Chem. Soc. 57 (1935) 2364. 3. K. Balenovic, N. Bregant, D. Cerar and M. TkalCi c, J. Org. Chem. 16 (1951) 1308. IZVOD Sinteza supstituiranih derivata dioksena K. Baienovic i N. Bregant Na primjeru 1-diazo- 3-ftalimidoq;iropanona pokazano je, da se iz diazoketona sa 1,2-etandiolom mogu priredi ti, preko 1-(2' -oksietoksi) - ketona III, supstituirani diokseni IV. KEMIJSKI INSTITUT PRIRODOSLOVNO-MA TEMATICKI F AKULTET ZAGREB Primljeno 31. decemb ra 1955. 

A Route for the Synthesis of Substituted Dioxene Derivatives

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