SU1033497A1 - Process for preparing 2-(2-chloroalkoxy)-2-oxo-1,4,2-dioxaphosphepanes - Google Patents

Abstract

METHOD OF OBTAINING 2-

Description

1l The invention relates to the chemistry of seven-membered cyclic phosphonates with a phosphorus atom in a cycle, namely to an improved method of 2- (2-chloroalkoxy) -2-oxo-1. 15 "7 R, R - and R - hydrogen or where R, R is methyl; R and R are hydrogen, alkyl, or phenyl, which can be used as plasticizers for plastics in order to impart flame retardant properties, as monomers for the preparation of polymers, and also as selective extractants for noble and rare metals. A known method for producing 2- (2-chloro-alkoxy) -2-oxo-1, 1,2-dioxaphosphorins by reacting 2-chloro-1,3,2-dioxaphospholanes with 1,3-dioxolans in an inert organic solvent at 0- 150 С in the presence of a catalyst - zinc chloride Cl; The closest to the proposed invention to the technical essence and the achieved result was Ti7 2, a method for producing 1, |, 2-dioxa, phosphepans, in particular 2- (2-chloroethoxy) -2-oxo-1, 4,2-dioxaphosLepane, that is, 2-chloro-1,352-dioxaphospholane is reacted with 1,3-dioxane at 80-100 ° C in the presence of tin tetrachloride catalyst, followed by separation of the target product by distillation. The crude product yield about 15 ° Cgt. The disadvantages of this method are the low yield of the target product, as well as its contamination. The aim of the invention is to increase the yield of the target products and to increase their range. The goal is achieved by the method of obtaining 2- (2-chloral (oxy) -2-oxo-1 ,, 2-dioxaphosphephepans of the general formula (|), juxtaposing zuo unsubstituted or methyl substituted 2-chloro-1,3,2-dioxaphospholane is reacted with 1,3-dioxane when heated to bo-cc in 1, -dioxane in the presence of a catalyst - zinc chloride, followed by neutral hydrolysis of the resulting reaction mixture by neutralizing the liberated acid with alkaline solution and extracting the target product. proceeds according to the scheme:

As can be seen from the diagram, the rearrangement of the intermediately formed pentaorganophosphorane can proceed in two directions, with the opening of the 1,3,2-dioxaphospholane cycle (Scheme A) or c. its preservation (Scheme B). It has been experimentally established that in all the given examples it has places, about the course of regrouping under Scheme B (to a greater or lesser extent). Purification of the target products from the by-products is carried out by hydrolysis at 720. At the same time, by-products (3 chloralkoxy) -alkyl 3-2-oxo-1,3,2-dioxaphospholanes undergo complete hydrolytic decomposition to an acid, which can be titrated with alkali, 1, 2 Dioxaphosphenane under these conditions, they are hydrolytically stable and are separated from the hydrolyzate by extraction with chloroform. The interaction of alkylene phosphorous acids with 1,3 dioxanes is best. carried out at SO-IOO C in the presence of catalytic amounts of anhydrous inClj (1. g. ZnCl. per 1 mole of reagents) and a threefold molar excess, 1, Adioxane. as a solvent. The yields of the target 1 jt.Z-dioxaphosphephepans range from 22 to 8S, S% of theoretical. In order to increase the yield in all cases, the reaction mass is heated for 3-5 hours. The method is simple to perform and is based on the available chemical products. Alkylene chlorophosphites are easily obtained from phosphorus trichloride and glycols with a yield of more than 90, Cyclic 1,3-Dioxanes are also available substances, formed by the condensation of aldehydes and ketones with 1.3 glycoles, by vinylating 1,3-glycols and by synthesizing divinyl and isoprene by Prins reaction. Targeted 2- (2-chloroalkoxy) -2-oco-1 ,, 2-dioxaphosphophane are colorless viscous liquids soluble in alcohols, 1, | -dioxane, chloroform, and other organic solvents with the exception of saturated hydrocarbons. In water they are dissolved by differently. depending on the structure, the radicals P - and R. If, H; H, solubility in water is good. If R and,, H, - (} - dissolution in water is bad. The general procedure for the preparation and recovery of 2- (2-chloroalkoxy) -2-oxo-1, t, 2 dioxaphosphepane. In a glass reactor equipped with water thermostatted jacket, thermometer, dropping funnel, stirrer and reflux condenser, placed 1 mol of 2-chloro-1,3,2-dioxaphos folana, 1 g of anhydrous ZnP, 1 and 3.0 mol of absolute 1, -dioxane. 80-100 ° C while stirring, 1 mol of 1, .3-dioxane is added to the reactor at such a rate that the temperature rise in the reactor does not exceed three degrees from the set. at the end of the addition, the reaction mixture is stirred at the same (80 ° C) temperature for 3–5 hours and cooled, replacing the water in the jacket with flowing cold water. To the cooled reaction mixture, add 100 ml of cold water with a dissolved indicator (bromophenol blue) at such a rate that the temperature does not rise above 20 ° C, and then the reaction mixture, with stirring, is neutralized with an alkali solution until the transition color on the indicator. The resulting hydrolyzate was transferred to a separatory funnel, 300 ml of water was added and extracted with three portions of chloroform (500: 300: 300 ml). The combined extracts were dried with anhydrous NaA (3.504. The solvent was distilled off under reduced pressure, and the residue was distilled in vacuo. Pure 1 ,, 2-dioxaxaphosphinepane was obtained (Tables 1 and 2). Outputs were 2285 from the theoretical. Example 1. Synthesis of 2- (2-chloroethoxy) -2-oxo-1, 2-dioxaphosphine-1 (1), A solution of 38 g (€, 3 M) of 2-HLOR-1,3,2-dioxaphospholane, 0.3 g is placed in the reactor ZnCli and 132 g (0.9 M) of absolute 1, -dioxane. 26.7 g (0.3 M) of 1,3-dioxane are added with stirring. At the end of the addition, the reaction mixture is further thermostatted () for another 5 h, then cool give, replacements thermostating with hot water on flow with a temperature of -7-10 C, and with continuous stirring add tO ml of water with the dissolved indicator (bromophenol blue). Then in the same conditions add the KOH solution to the transition color on the indicator (flow rate KOH 39 ml), and according to the formula M. in. At N end of the 100 hydrolysis, the theoretical amount of phosphepan is 100 where M. in. is the molecular weight of phosphepane; V - alkali consumption, ml; N is alkali normality,% hydrolysis is found, i.e. the approximate content of the isomer with a five-membered cycle (23.21%). Transfer the hydrolyzate to a separatory funnel, add 100 ml of cold water and extract three times with chloroform (200: 100:: 100 ml). The combined chloroform extracts are dried with anhydrous solvents, the solvents are removed, and the residue is fractionated in vacuo. 27 g (41.9) of 2- (2-chloroethoxy) -2-oxo-1 i, 2-dioxa phosphepane (|) are obtained (Tables 1 and 2). T.Kip, C (mm. Mercury.) 106-110 (2-10),. HR ° Jf ° 2 «™, P2., Found,%: C 33.2; H S, 73; R, 19; C1 16.66. . $ 10 Calculated, I: C 33.58; H 5.63; Pk, | 3; C1 16.52. . Note 2. Synthesis of 2-f2-xnopethoxy) -2-pkso-3-methyl-1,4,2-dioxaphosphelane (1 1) .. In a reactor to a solution of 25 g (0.19b 2-chloro-1,3 , 2-dioxaphospholane, 0.2 g of ZnClrj in 52 ml (0.588 m) of absolute 1, α-dioxane with stirring and in the temperature 9bC add 20 g (0.19b of 2-methyl 1.3 dioxane. The reaction mixture is further stirred for another 3 cool and mix the running water with the jacket, add 50 ml of water with dissolved bromophenol blue. With constant stirring and temperature, titre with 10 KOH until the transition color (flow rate 22 ml) 228,621J 22 1,7857 20.14% HYDR g, W –TO Hydrolyzate is transferred to a separatory funnel was added 100 ml of water and extracted three times with chloroform (100, 60, 60 ml). The combined extracts were dried with anhydrous Na Qi, the solvents were removed, and the residue was distilled in vacuo to give 3.6 g (77.2 %) addition of 2- (2-chloroethoxy) -2-oxo-3-methyl -1,4,2-dioxaphosphenepane (11). T. boiling (mm Hg) 110-112 (), 1, 4824, dl 1.3122. 1) .LileA5.70, MKRYY 50, Rev. Found, I: C 36.4-3; H 6.05; P 13.57; C1 15.49. C7H.404PC1 Calculated,%: C, 36.77; H 6.17; p 13.55; C1 15.51. PRI m e-r 3. Synthesis of 2- (2-chloroethoxy) -2-oxo-3,7-dimethyl-1,4,2-dioxaphosphenepane (I.V). In the reactor, to a solution of 39.34 g (o, winters) of 2-chloro-1,3,2-dioxaphospholane 0.3 g of ZnCl and 82 ml of absolute 1.4 dioxane were added 36.1 g (O, winters) 2, 4-dimethyl-1, 3-dioxane. The reaction cMfecb is stirred at this temperature for 3 hours, cooled to 8 ° C. and 20 ml of water are poured with an indicator. When the mixture is titrated with 10% KOH (flow rate 18 ml, the percentage of hydro-lyse is 10.33) to a transitional color and transferred to a separatory funnel with 200 ml of water. Extract three times with chloroform (150: 100: 100. Ml). The combined extracts are dried, 1 Ast 8 Omtel is distilled off, and the residue is distilled in vacuo. 64.5 g (85.5%) are obtained. 7 2- (2-chloroethoxy) -2-oxo-3,7-Dimethyl-1 ,, 2-dioxaphosphenepane, ft bp, C (mm Hg) 112-P (8-10); n | }, k76 (, d | 1,2593. Rt, „, Ld5A ,, MRpBwM5.71.. Found,; C 39.78; H 6.71; R 12.43; C1 J, 6". Calculated,% : C 39.60; H b. P | 2.7 b; .C1 U, 61. Example 4. Synthesis of 2- (2-chloroethoxy) -2-oxo-3 phenyl-1 .i, 2-dioxaphosphenepane (VII). in a reactor at 80 ° C to a solution of 38 g of (0, 3M) 2-chloro-1,3,2-dioxaphospholane, 0.3 g of ZnCl2. R 79 ml of absolute 1,4-dioxane is added to a solution, 3g (0, 3M) -phenyl-T, 3-dioxane in 18 ml of absolute 1,4-dioxane. At the end of the addition, the reaction mixture is thermostatically heated at 80 ° C for 4 more hours, cooled with running water and 50 ml of water are added with a dissolved indicator. The mixture is titrated with 10% - KOH solution to and Transition, color flow 30 mL, 17.85) was transferred to a separatory funnel with 100 ml of water and extracted three times with chloroform, and the residue was distilled in vacuo. 66 g (75.7) of 2- (2-chloro-tothoxy) -2-oxo-3-phenyl-1, 4,2-dioxaphosphenepane are obtained. (Bp, s (mmHg) 165 (41P-3), h% i; 5390, df b3100,: MR. 69.51, ko La Y-RIAa.D. PjBbW 69.02. Found,%: С L9.12; H 5.69; R 10.31; C1 12.55. (Calculated,%: C 49.58; H 5.55; R 10.65; C1 12.19. P P and m e. p 5. Synthesis of 2- (2-chloropropoxy) -2-oxo-6,6-dimethyl-1,4,2 dioxaphosphenepane (VII O. To a solution of 42 g (0.3 M) 4-methyl-2-chloro-1 , 3,2-dioxaphospholane, 0.3 g of ZnClg. In a mixture of 79 ml of absolute 1,4-dioxane, 34.8 g (0.3 m) -5,5-dimethyl-1,3 dioxane are added with stirring. mix: wate at 98 ° C for 4 h and cool with running water. Pour 50 ml of water with the dissolved indicator and titrate with a solution of KOH to a transitional color Hydrolyzate transfer to a separatory funnel with 150 ml of water and extract three times with chloroform (150: 100: 100 ml). The extracts are combined, dried, the solvent is distilled off, and the residue is distilled in vacuum. 3.2 g are drained (kk, k% ) 2- (2-chloropropoxy) -2-oxo-6, 6-dimethyl-1 .tZ-AMOKcaOocphepane (Vlfl). Boil. C (mmHg) 87-90 (310 - "-), 1, t759, d5. ° b23V3,% imA5 78, НРде1,, ч59, Зб. five

Found,%: C, 13; H 7.25; R 11.89; C1 13.80.

CpH g04PC1

by definition, C 2.11; H 7.07; P C1 13,81.10

P m and e R 6. Synthesis of 2- (1-methyl-2-chloroproxy) -2-oxo-3 propyl-1-, 2-dioxaphosphenepane (iX).

In the reactor under stirring to a solution of 31) 5 g (0.2 M), 5-di-t5 methyl 2-chloro-1,3,2-dioxaphospholane, 0.2 g ZriC1 (2 in 53. ml and 26 g (0.2 M) 2-propyl 1 3-di6xane is added to salt 1 of dioxane.Heat the reaction mixture with stirring for 20 3 h and cool to 8 - 0 ° C. At this temperature, 0 ml are added to the reaction mixture water with dissolved bromophenol and titrated with 1.0% KOH (flow rate 75 ml, which corresponds to 25–67% hydrolysis). GiDrolizate is poured into a separating funnel with 70 ml of water and

extracted three times with chloroform (100: 50: 50 ml). The extracts are combined, dried with Ma CS and the solvent is distilled off. Distillation of the residue in vacuo gave 15.7 g (27.6%) of 2- (1-methyl-2-chloropropoxy) -2-oxo-3-propyl-1 ,, 2-dioxaphosphenepane (tX). Q.typ., (MmHg) 136-138 (2-10-2-), 1 ,, d I 1.5151. Smdile 9, MVraych68.b5. .

. Found,%: C. "5.93; H 7, R 10.22; C1 12.2.

1 2gOaS1

Calculated i: C 6, H 7.78; R 10.88; C1 12, it5.

Table 1 gives the synthesis conditions, the starting materials, the yields and the structure of 2- (2-chloroalkoxy} -2-oxo-1, 2-dioxaphosphinepanes, in table 2, their physico-chemical constants ..

So the proposed method

the preparation of 2- {2-chloroalkoxy) -2-oxo-1, 4,2-dioxaphosphepane allows to increase the yield of the target products to 22-85%, as well as to expand the range of 1, 4,2-dioxaphosphan.

13

SWF

. Ij

table 2

Claims (1)

METHOD FOR PRODUCING 2- (2-CHLORALK0XI) -2-0KS0-1,4,2-DIOXAPHOSPEPANOV of the general formula Έ ⁷ C1-en ~ night M at ⁶ n ¹ % Avuhk5 'B ³ V ⁴ where R, R, R, R ° and R are hydrogen or methyl; R and R ⁷ - hydrogen, alkyl or phenyl, by the interaction of 2-chloro-1,3,2-dioxaphospholanes with 1,3 ~ dioxanes when heated to 80-100 ° C in the presence of a catalyst - metal chloride, characterized in that, in order to increase the yield of the target products and expand their assortment, the process is conducted in 1,4-dioxane medium and zinc chloride is used as a catalyst, followed by neutral hydrolysis of the resulting reaction mixture at 7–20 ° С, neutralization of the liberated acid with an alkali solution and extraction of the target product . £ 6ΚβϋΓ ^{, π,} Τϊ§> 1033497 ces to