J. Chem. Eng. Data 1981, 26, 219
219
Energetic Azido Monomers Milton B. Frankel' and Edgar R. Wilson Rocketdyne, A Division of Rockwell International, Canoga Park, California 9 1304 dropwlse in 50 mln. The reactbn mlxhrre was refluxed for 114 h, cooled, washed with water, and then passed through a neutral alumina cdumn to remove color and statting materials. The solution was concentrated to give 3.2 g (65%) of a colorless oil, n2,' 1.5100. In our work directed to the synthegis of energetk "ers, 3-Azklo-2,2-dkrltropropyl Awl Ether. A mixture of 4.0 g we have reported on the preparation of fluorodlntromethyl e p (0.01 12 mol) 6f 3 - t o s y L 2 , 2 d i n b ~ ~aryl y l ether, 1.2 g (0.0185 oxides ( 1). This work has now been extended to two new mol) of sodium azlde, and 20 mL of dimethylformamlde was classes of energetic monomers, 3-azido-2,2dlnitropropyl glyheated with sthlng at 50 OC for 90 h. The mixture was cooled, cklyl ether (V) and 3,3-bis(azidomethyl)oxetane (VI). poured Into 100 mL of water, and extracted with 50 mL of methylene chlorlde. The organic extract was washed with 6 KOH CH3C(N02)3 KOH [CHz=C(N02)2] HOCH~CH=CH~ X 100 mL of water to remove the dimethyiformamlde, passed CHZO TrOCl through a neutral alumina column, and concentrated to glve 0.6 KC( N02)2CH20CH2CH=CH2 H~CH~C(NO~)~CH~OCH~CH=CHZ g (23%) of colorless oil, n 2 b 1.4768. I I1 3 - ~ - 2 , 2 - ~G&klyl f l Ether. A mlxture of 1.5 TSOCH pC( N O ~ ) Z C H ~ O C HH Z=C C HZ !?!% l ether, 5 g (0.035 g (0.0065 mol) of ~ 2 , 2 d l n l t r o p r o p yallyl 111 mol) of disodkrm hydrogen phosphate, and 15 mL of methylene CF3C03H N$HzC( N O ~ ) ~ C H ~ O C H Z C H = C H ~ N ~ C H ~ ( N O ~ ) ~ C H ~ O C H Z C H C H Zchloride was heated to reflux, and a solution of 1.43 g (0.01 1 \I0 mol) of freshly prepared peroxytrlfluoroacetlc acid (2) In 5 mL IV of methylene chlorlde was added In 15 min. The reaction V mixture was refluxed for an additha12 h and cooled, and 25 CH z-C(CHzN& CH2-C(CHzCI 12 mL of water was added to dissolve all solids. The methylene chloride layer was separated, and the aqueous layer was exO-CH2 0-CH2 tracted with 2 X 10 mL of methylene chlorlde. The combined VI methylene chbrlde extracts were washed with 20 mL of 10% sodium bicarbonate solution, dried over anhydrous sodium Experimental Section sulfate, and concentrated to give 1.3 g (81%) of yelbw oil, nnD 1.4796. General Procedure (CaufrOn). Most of the products de3,3-8Is( azk%nwfhyl)oxetane. A mixture of 59.5 g (0.38 scribed in this paper are expbshres of moderate to considerable mol) of distMed 3,3-bls(chbromethyl)oxetane(Columbia Chem sensitivity to inhiation by impact, shodc,fraction, or heat. They Ical Co.), 54.3 g (0.84 mol) of sodium azlde, and 200 mL of should therefore be handled with care. All distillations should dimethylformamlde was heated at 90-100 OC for 2 h. The be well shielded. Elemental analyses have been reviewed and reactlon mixture was cooled to ambient temperature, poured are in accord with theory. into 1 L of water, and extracted with 200 mL of methylene 3 - H y ~ ~ ~ - 2 , 2 - d l n f f m pAllyl r ~ yEther. l To a mixture of chloride. The methylene chloride extract was washed twice 59.1 g (0.11 mol) of the potassium 2,2dlnitroethyl allyl ether with 500-mL portions of water, dried over anhydrous sodium and 200 mL of water was added 18.0 g (0.15 mol) of 37% sulfate, and concentrated. The resultant pale yellow oil was formaldehyde. Then 9.0 g (0.15 mol) of acetic acid was added distilled to give 48.3 g (76%) of colorless liquid: bp, 79-81 dropwise. The reaction mixture was stirred for an additional 15 "CI0.4 mm Hg; n26D1.5054. min at ambient temperature and extracted with 3 X 33 mL of methylene chloride. The combined extracts were washed with Literature Cited 2 X 100 mL of water and concentrated to give 22.0 g (97.1%) of light yellow liquid, n25D1.4630. (1) Wltucki, E. F.; Rowiey, G. L.; Warner, M.; Frankel, M. B. J . Cbm.. 1976, 37, 1952. 3-Tosyl-2,2-dlnnmpmpyl Allyl Efhsr. A mixture of 4.0 g (2) E m m a , W. D.; Pagano, A. S.; Freemen, J. P. J . Am. Chem. (0.019 mol) of 3-hydroxy-2,2dlnitropropyl allyl ether, 4.0 g 1919, 75, 4623. (0.021 mol) of tduenesulfonyl chlorkle, and 20 mL of chloroform was heated to reflux with stirring, and a solution of 2.0 g (0.021 Received for review July 7, 1980. Accepted November 3, 1960. We are mol) of pyridine-N-oxide in 10 mL of chloroform was added indebted to the Offlce of Naval Research for financial support of thls work.
The preparation and the properties of two new classes of energetk monomers, 3-azldo-2,2dlnitropropyl glycldyl ether and 3,3-bls( azldomethyl)oxetane, are reported.
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0021-9568/81/1726-0219$01.25/0
0 1981 American Chemical Society
