SU1177301A1 - Method of producing 2(e)-r-5(e)-iodmethyl-5(a)-chlormethyl-1,3-dioxanes - Google Patents

Abstract

1, a method for the preparation of 2 (c) (e) -IODMETHyl-5 (a) -chloromethyl-1,3 dioxanes of the general formula CHgCl where PI is isobutyl or phenyl, characterized in that 2-R-5.5-5c (chloromethyl ) -1,3-dioxane of the general formula C 1 CH 2 K R C 1 CH,) 0 where R has the indicated meanings, is reacted with sodium iodide at 60-62 C, 2. The method according to claim 1 and with the fact that the process is carried out at a molar ratio of 2-, 5.5-5is (chloromethyl) -1,3-dioxane and sodium iodide equal to 1:

Description

I The invention relates to a process for the preparation of new compounds, namely, 2 (e) -R-5 (e) -iodomethyl-5 (a) chlorine of 1, 3-dioxanes of the general formula CHjCl, where R is isobutyl or phenyl, which can be used in the synthesis of biologically active compounds. The purpose of the invention is to obtain new derivatives of 1,3-diocane, which can be used to synthesize valuable biologically active compounds. Example 1 A three-neck flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 24.1 g (O, 1M) 2-isobut 15, 5-St (C (chloromethyl) -1,3-dioxane, 15.0 g sodium iodide, and 110 ml of acetone. The reaction mixture is stirred at 62 ° C for 250 hours. But when the reaction is complete, the acetone is evaporated, the mixture is filtered. The filtrate is treated with 10% baking solution, dried with anhydrous magnesium sulfate and the residue is distilled in vacuum. 18.3 g ( 35.1%) 2 (e) -isobutyl 5 (e) iodomethyl-5 (a) chloromethyl-1,3 dioxane Example 2. Similarly to Example 1, 36.1 g (0.11 M) io were charged to a reaction flask sodium sulfide and 115 ml of acetone. The reaction is carried out at 230 hours, 2t is obtained, 4 g (62.2%) 2. (e) -fench1-5 (e) iodomethyl-5 (a) -chloromethyl-1 , 3-dioxes Example 3. 0.1 M 2-phenyl-5.5 & Os (chloromethyl) -1,3-dioxane and 0.125 M sodium iodide are heated — in 120 ml of acetone at 62 ° C. for 175 h. “Receive 26.5 g (75.2%) 2 (e) 01 2 phenyl-5 (e) -iodomethyl-5 (a) -chloromethyl 1, 3-dioxane Example 4. 0.1 M 2-isobutyl 5, 5-Slic (Chloromethyl) -1,3-dioxane, 0.132 M iodide, etc., in 130 ml of acetone, heated at 62 ° C. for 170 hours. 25 g (74%) 2 (e) of isobutyl-5 (e) -iodomethyl-5 are obtained (a) chloromethyl- 1, 3-dioxane. Example 5. 0.1 M 2-phenyl 5, (chloromethyl) -1,3-dioxane, 0.125 M sodium iodide in 120 ml of acetone is stirred at 198 hours. 25.2 g (71.5%) 2 (e) are obtained fenil-5 (e) -iodomethyl-5 (a) -chloromethyl-, 1,3-dioxane. The data of elemental analysis and the physicochemical constants of the compounds of formula (I) are presented in table. 1, the conditions for carrying out the process in Table 2, the conditions for conducting and the result of the interaction of 2R-5,5-bos (chloromethyl) -1.3 dioxane with sodium iodide in an acetone solution are given in Table III. The process is carried out at a molar ratio of dioxane: sodium iodide, 15-1.35) (Table 2). The selected process conditions provide a stereoselective exchange of halogen chlorine for iodine in the starting heterocyclic dichloro derivative. In this case, nucleophilic substitution of chlorine for iodine is carried out in the equatorial chloromethyl group. At temperatures below the yield of the target product decreases, increasing the process temperature requires replacing the solvent. A decrease in the content of sodium iodide in the reaction mixture increases the duration of the process, an increase in the content of sodium iodide does not lead to an increase in the yield of the target product and a decrease in the process time. 2-Isobutyl 5-iodomethyl 5-chloromethyl 5, 28 1,3-dioxane 35.88 2-Phenyl -5 iodomethyl-5 chloromethyl 4, 00 CHO, CtJ 1,3-dioxane 40.65

Table2 36.11 5.46 1.5286 1.5211 125-126 / 2 40.88 4.00 -1.5890 170-175 / 1

0.9: 1.15

0.9: 1.30

0.85: 1.00

1.0: 1.35 From-TsNd1: 1 1: 1.160 1: 1.25 62 From-С Н,. 1: 1.32 62 170

70 75.1

175 175 60 75.2 200 175

Table 3 2 (e) -Isobutyl-5 (e) -iodomethyl5-chloromethyl-1, 3-dioxane 2 (e) -Phenyl-5 (e) -iodomethyl 5 (a) -chloromethyl-1,3-dioxane 2 (e ) -Phenyl-5 (e) -Iodmetnl5 (a) chloromethyl 1,3-dioxane 2 (e) Isobutyl-5 (e) -iodomethyl5 (k) chloromethyl-1,3-dioxane

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Continuation of table 3

2 (e) -Phenyl-5 (e) -iodomethyl-5 (a) tosyloxymethyl-1, 3-dioxane

72.7

Claims (2)

1. METHOD FOR PRODUCING 2 (c) -R · 5 (e) -METHYL-5 (a) -CHLOROMETHYL-1,3-DIOXIDE of the general formula CH ₂ C1 _R where R is isobutyl or phenyl, characterized in that 2-R-5.5-8is (chloromethyl) -1,3-dioxane ^{1 of the} general formula С1СН ₂₎ Л- \ С1СнД _ (< ^к where R has the indicated meanings, is reacted with sodium iodide at 60-62 ° С, 2. The method according to claim 1, characterized in that the process is carried out at a molar ratio of 2-R5.5-5ds (chloromethyl) -1,3-dioxane and sodium iodide equal to 1: (1,151.35). I