SU1268582A1 - Method of producing 5,5-dinitro-1,3-dioxanes - Google Patents

Abstract

The invention relates to substituted dioxanes, in particular 2-alkyl phenyl-5,5-dinitro-1,3-dioxanes (D), which can be used as components of explosives, reactive materials and plasticizers. Increasing the yield and simplifying the process is achieved by other starting conditions and method conditions. The latter is made from the K-salt of 5-nitro-1,3-dioxane (I) and NaNO (II) in the presence of CuCl j (III) in an inert gas atmosphere in an aqueous solution of dimethyl sulfoxide at a molar ratio of 1: 11: 111. 1:

Description

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The invention relates to methods for the preparation of 5,5-dinitro-1,3-dioxanes which may be used as components of explosives, jet fuels and plasticizers. The purpose of the invention is to increase the yield of the target product and simplify the process. Example 1. In the reaction flask, 0.05 mol (6.65 g) of 5-nitro-1,3-dioxane and 0.075 mol (4.2 g) of KOH are dissolved in 50 ml of dimethyl sulfoxide and 50 ml of water and the mixture is flushed over 10 min. Argon ,. The prepared mixture is added dropwise in a stream of argon over 20 minutes to the stirred NaNOp solution. 0.2 mol (13.8 g) and CuCl 0.4 mol (53.8 g) in water (100 ml) and dimethyl sulfoxide (100 ml). After completion of the dropping, the reaction mixture is stirred for another 30 minutes, extracted with pentane three times with 100 ml each time, washed twice with 50 ml water each time, dried over MgSO4, the pentane is evaporated and the crude product is recrystallized from pentane-hexane. 7.92 g of 5,5-dinitro-1,3-diox are obtained (yield 89% on 5-nitro-1,3-pjioKsan), m.p. 53-53.5 ° C. Found,%: C 27.01, H 3.40; N 15.71. C4NbOgKg C 26.96, - H 3.37; Calculated N 153. Example 2, as in Example 1, 0.05 mol (7.4 g of 5-nitro-2-methyl-1,3-dioxane) is used to obtain 8.3 g of 5,5-dinitro-2-methyl-1, 3-dioxane , Yield 86%, mp, .37 Found,%: C 31.10; H 4.18; N 14.49. C HgOgN, C 31.08; H 4.14; Calculated,% N 14.50 Example 3 In a similar manner to Example 1, 0.05 mol (10.45 g of 2-fench 1-5-nitro-1,3-dioxane is used to obtain 10.8 g of 2-phenyl-5,5-dinitro-1, 3 -dioxane: Yield 85%, mp 78. Found:%: C 47.27; H 3.95; N 11.01. ,, Calculated,%: C 47.2; H 3.94; N 11. Example 4. Similarly to example 1, 0.05 mol of 5-nitro - 1.382a-dioxane, 0.25 mol of NaNOj and O, 45 mol of CuClj are taken and 7, 74 g of 5,5-dinitro-1, 3-dioxane are obtained. Exit 87%. Example 5. Similarly In Example 1, 0.05 mol of 5-nitro-1,3-dioxane, 0.15 mol of NaNO and 0.35 mol of CuClj are taken and 7.83 g of 5,5-dinitro-1, 3-dioxane are obtained. 88% yield. Example 6. Analogously to example 1, 0.05 mol of 5-nitro-1,3-dioxane, 0.2 mol of NaNOj and 0.2 mol of CuClj are taken, and 4.54 g of product is obtained. 51% yield Example 7. Analogously to example 1 0.05 mol of 5-Nitro-1, 3-dioxane, 0.2 mol of NaNO and 0.15 mol of CuClj are used, and 3.83 g of product are obtained. Yield 43%. PRI me R 8. Analogously to Example 1, 0.05 mol of 5-nitro is used. -1,3-dioxane, 0.3 mol NaNO.2 and 0.6 mol CuClj and get 3.65 g of the product. Yield 41%. Example 9. Analogously to example 1, 0.05 mol of NaNO and 0.1 mol of CuClj are used and 4.36 g of product are obtained. Yield 49%. The effect of the ratio of reagents on the yield of the target products, taken at 0.05 mol of 5-nitro-1,3-dioxane. presented in the table. The table shows that the optimal ratio (molar) of the reagents 5-nitro-1,3-dioxane: NaNOj: CuCl is 1: 4: 3. The yield of the target product in optimal conditions is 85-89%. In the case of an increase in the concentration of the co-reagents NaNOj rf CuClj, the yield of the target products remains practically unchanged. With a decrease in the concentration of these Co-agents, a sharp decrease in the yield of the target products is observed.

The advantage of the proposed method is that it allows increasing the yield of 5,5-dinitro-1,3-dioxanes to 85-89%, drastically reducing the process and simplifying the process technology.

Claims (1)

Invention Formula The method of obtaining 5,5-dinitro-1,3 g dioxanes of the general formula f Oyo R 12685824 where R is hydrogen, lower alkyl, or phenyl, characterized by the fact that, in order to simplify the process and increase the yield of the target product, 5-NITRO-1,3-dioxane potassium salt of the general formula THAT TO where R has the indicated meanings, it is reacted with sodium nitrite in the presence of copper chloride in an inert gas atmosphere in an aqueous solution of dimethyl sulfoxide at a molar ratio of 5-nitro-1,3 dioxane, sodium nitrite and copper chloride 1: 3-5: 7-9.