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    • 专利摘要:

    公开号:SU923371A3
    申请号:SU792859605
    申请日:1979-12-19
    公开日:1982-04-23
    发明作者:Пуассон Пьер；Штюрц Жорж
    申请人:Ато Шими (Инофирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR PRODUCING BIS- (4-OXYPHENYL) ALKYL PHOSPHANIC ACIDS ETHERS
    (.1,923371
    权利要求:
    Claims (2)
    [1]
    392 The purpose of the invention is to develop an affordable method for the preparation of ester salts of bis- (oxyphenyl) alkyl-phosphonic acids of general formula (1). that phenol is reacted with ketodialkylphosphonate of the general formula (RO) ap- (cHa) nc-CHn, cl o, 0 where R is alkyl, n O or 1, in the presence of boron trifluoride at a temperature of 10-40 C for 1- 2 h, followed by treatment of the resulting bis- dialkyl ester C-oxiphenyl) alkylphosphonic acid 2-3 n. an alcoholic solution of sodium hydroxide or potassium at a molar ratio of 1: 3 at boiling and neutralizing the resulting reaction mixture with concentrated hydrochloric acid, followed by removing the solvent under reduced pressure, filtering off sodium chloride or potassium and drying the resulting product in vacuum 0.5 -2 mm Hg Example 1. Preparation of 2,2-bis-y-oxyphenyl) propyldimethylphosphonate. 370 g of phenol (3.97 mol) are saturated with boron trifluoride at a temperature of from 20 to 25 ° C, then 108 g of 2-oxo-propyl dimethylphosphonate (0.65 mol) are added dropwise within 30 minutes, maintaining the temperature below 20 ° C The reaction is then carried out at ambient temperature. The temperature of the reaction medium rises to 30-35 ° C and is maintained in this temperature range for one hour without preheating. After one hour, set the temperature of the reaction medium equal, maintaining this temperature for 30 minutes. Then it is cooled and diluted with 320 m of acetic acid and the acetic solution is poured into 7 l of water. The resulting oily substance hardens for about 20 hours. The resulting solid is washed with water, dried out and dried to obtain 18 g of a crude slightly colored product, which is again dissolved in dioxane under reflux, then crystallized by the addition of water, and dried out after cooling with ice. Get the target product in the form of a white powder, which melts at. The output in mole x 75 (181 g). Elemental analysis of Ci7H7iP05. It is calculated D: SBO 1; Nb, 25; P9, 22. Found: C 70, 77; H6.21; P8,. Infrared spectrum. 3300 1225 cmo f-0-C 1050, 1020 cm-1 Proton NMR spectrum (dissolve etherized DMSO) DMSO dimethyl sulfoxide. act CH3 23 1 cL 9.16 ppm (S) 2 On c 7.15-6.55 ppm (t) 8HH, 28 ppm (d) bHe, 1P-He 11H, b2 ppm (d) 2Hd, IP-Hd 20H. 5 1.76 ppm (s) ZNS NMR Spectrum (solvent deiteritized DMCOj cL 15b, 6 (, 8-141.6 c 129.3, 1, 9, 86 cL 30 pp C P PR and measure 2, Obtaining 2, Sodium 2-bis- (4-hydroxyphenyl) propyl methyl phosphonate, In a cylinder equipped with a stirrer, a condenser with reflux condenser, a thermometer and a nitrogen inlet tube, dissolved in an alcoholic sodium solution prepared by dissolving 0.3 mol of sodium in 27 ml of water and in 100 ml of methanol, 33.6 g (0.1 mol) 2,2-bis- (A-hydroxyphenyl) propyl dimethylphosphonate. After passing a stream of nitrogen into the mixture, incubate for 2 hours under reflux, cooling The mixture is cooled to ambient temperature, neutralized with concentrated HC1 to 5. pH 7 under cooling, then concentrated under reduced pressure, the dry residue is dissolved in a small amount of methanol and the precipitated sodium chloride is filtered off, then the filter is concentrated under reduced pressure and then dried at 150- 160 ° C under a vacuum of 1 mm Hg. 32.3 g of the expected product is obtained in the form of a hygroscopic white powder, which decomposes at 220-225 ° C 95. Elemental analysis gives the following results for sodium and phosphorus. Calculated,%: P 9.01; Na 6.68. Found,%: P 8.9; Na 6.93 Determination was carried out by X-ray fluorescence of phosphorus. Proton NMR as a solvent, 3-6.7 .ppMLm), 20 ppm (5) 3He ;: p-He 10.5H, 62 ppm (a) 2H 3P-Hd 21.6H2. , 83 ppm IS) ISS Integration clearly confirms the presence of a single methoxy group AXIS j Proton NRT in deuterated 10–9 ppm phenolic protons Na, 02 ppm (a) He, J: 0, 7 ppm, 5; 145.2 ppm, 9 ppm, 7 ppm, 22. Fri, trpm. C, 4ppmCo. Example 3- 2,2-bis (4-hydroxyphenyl) propylmethyl potassium phosphonate. 8.4 g (0.025) mol of 2, 2-bis- (4-hydroxyphenyl) propyldimethylphosphonate is dissolved in 118 ml of a solution of potassium 2.6 N in methanol. Heated under reflux (28 hours. 1) Then, in order to separate the product, do the same as in Example 2. 7.5 g of the expected product are obtained. The resulting product decomposes at 235 ° C. Elemental analysis of Cif | H; j 05K. Calculated,%: P 8.61; K 10.83. Found,%: P 8.10; K 9. NMR of a proton in .3-6.75 ppm (t) 8 Hb, 20 ppm (d) 3 Not IP-He-10.5 Hj .., 60 ppm (d) 2 HdlP-H 18H2 (, 82 ppm C) 3 He LMR of the proton in t36. Phenolic protons Do not detect between 10.5 and 9.5 PPM., 10 ppm (d ) 3 HelP-He 10.5H NMR carbon 13 in DoO., 7 ppm C, 3-1 +, 6 ppm C, 9 ppm C3 ppm Cij, 2, 73-53.3 ppm Cg ppm Cj (45.22 ppm C-, (, 38, ppm .Cf) A. Preparation Example 2.2-bis - (- oxyphene l) propyl diethyl phosphonate. 97 g of 2-hydroxypropyl diethyl phosphonate (0.5 mol) and 282 g of phenol (3 mol) are mixed. By cooling, the temperature is brought to 10-15 ° C and boron trifluoride is bubbled up to saturation, maintaining the medium temperature below 25 ° C. The reaction medium, which is orange in color, is heated to 40 ° C for one hour, during which it becomes more and more viscous and takes on a violet-red color. Cool and dissolve the reaction mixture in about 250 ml of acetic acid, then pour the acetic solution into 6 l of water. A yellow mass is obtained (Lossy substance which is separated. The product hardens within 48 hours. 7 The solidified product is milled several times, washed with water with stirring, dried and dried. A slightly colored powder is obtained, which is recrystallized from ethyl acetate / cyclohexane in a ratio of 1: 2. I get 126 g of the desired product in the form of a white powder that melts at 152 ° G. The yield (in mole x) is 69%. The infrared and NMR spectra of the product, as well as elemental analysis, confirm the following chemical structure 0- SI2 Y3 O-CHg-CHj 89 Elemental en Lysis of C gHijjPOs. Calculated,%: C 62.63; H 6.86 P8.51. Found,%; C b2, B1; H 6.88; R 8.9. Infrared analysis: l) OH, 3300 cm -1 l) ONAR 3100 cm l) l255 cml) P-0-C YubO cM-i 1025 cm 960 830 cm-V NMR H spectrum (solvent dirumed DMSO), cL 8.6 ppm. . 0 7.2 6.6 ppm 0 3.9 ppm 2na, IP-Hd 1, 72 PPM cf 1.9 ppm cL 1.15 ppm Spectrum 13c (deuterated DM with 156.7 ppmCi s / - 141.6-140 , 8 ppm C4 0 129.3 ppmS 115.9 sL 61.9 ppm Cd with 43.9 ppmGS - cL 30.2 ppm C (, cL 34.7 ppm-C cr 17.86-17,41 ppm Cd Approx. 5. Preparation of sodium 2,2- (4-hydroxyphenyl) propylethylphosphonate. Dissolve 36.4 g (0.1 mol) of 2,2-bis- (4-hydroxyphenyl) propyl diethylphosphonate in 116 cm sodium alcohol solution prepared also as in Example 2. Heated under reflux for 24 hours, cooled to ambient temperature, neutralized with concentrated hydrochloric acid to pH 7 with cooling and, at this stage, an insoluble substance is detected, which is identified with the bisphenol diethylsulfonate. After the alkaline hydrolysis, the resulting product is treated with a hot mixture of ethyl acetate / cyclohexane to get it completely.To obtain 10.8 g (30 mol%) of the target The resulting products are powder that decomposes at 220-225 ° C. Elemental analysis. Calculated,%: R.8,65; Na 6.42. Found,%: P 8.4; Na 5.7V. Proton NMR (solvent DgO) 0-cNg cNhce) U) 4-hydroxyphenyl) propylethylphosphonate ca. 36.4 g (0.1 mol) of 2,2-bis- (4-hydroxyphenyl) propyl diethylphosphonate in 116 cm of an alcoholic potassium solution, prepared as in example 3. Heats under reflux for 24 hours, then cooled to ambient temperature and neutralized with concentrated hydrochloric acid at pH 7. A sticky precipitate is detected at this stage, which is removed by filtration. The filtrate is concentrated to dryness, taken up in a small amount of methanol. 5 The precipitated sodium chloride is removed by filtration, then the methanol filter is concentrated under reduced pressure, then dried under a vacuum of 2 mm Hg. The resulting product is subjected to gry treatment in a mixture of ethyl acetate. cyclohexane in the same manner as in the example. 20.0 g (53 mol) of the desired product are obtained. The product decomposes at 225-230. Elemental analysis of Ci- (H9 (05K. Calculated,%: P 8.28; K 10.42. Found,%: P 8.0; K 9.71. Example 7. Preparation 3, ( 4-hydroxyphenyl) butyldimethylphenate: Proceed as follows: 5b, 7 g (yield, 86) of the desired product with the following characteristics are obtained: Melting point 170 ° C. Elemental analysis of C gHQopOj. Calculated,%: C 61, 71; H 6.57; P 8.85. Found,%: C 61, Zb; H 6.50; P 8, Infrared spectrum. OH 3290 O 1225 cm Proton NMR spectrum (solvent deuterated DMSO) (jTs) -H 1 No.) lai (vf ICHg) 2 a) On Hb 6 Hf, Hd + 2He, 5PPM (s) 3 He Example B. Preparation of L, 1-bis- (oxyphenyl) e ilmetilfosfo sodium tension. 32, is dissolved. g (0.1 mol) 1,1-bis- (4-hydroxyphenyl) ethyldimethylphosphonate and in an aqueous-alcoholic sodium solution prepared according to the conditions listed in example 2. Reflux for 2k hours, then the product is separated as in Example 2. A white powder is obtained, which decomposes at 2 W. C. 1 Output - 29.7 g (90%; elemental analysis (Na. Calculated,%: P 9.39; Na 6.96. Found,% : R 8.5; Na 7.17. Proton NMR (solvent) ,, 7 ppm (g ≈ 7 8 Hv, 32 ppM (ci) 3Hd; :), 75 H. 1.80 ppM (d; 3Нс; sr-H 15.27 HZ% 0, 19 ppm, 27 ppm, 12-133.67 ppm, 27 ppm, 02 ppm (51 ppm C53P-C5- "(doublet) H (28.39-28.19 ppm PPM R 9. Preparation, 1- potassium bis - (- hydroxyphenyl) ethylmethyl phosphate. Dissolve 32.2 g (0.1 mol) of bis (hydroxy-phenyl) -1, tetra dimethylsulfonate in 118 ml of potassium, 6 in methanol. After setting up a stream of nitrogen into the mixture, kept in countercurrent for 2k hours. Then do the same as in the prier
    [2]
    2. The resulting product is a hygroscopic powder that disintegrates at 220-225 ° C. Yield 28.37 g (82). Elemental analysis of C (. Calculated,%: P 8.95; K 11.27. Found,%: P 8; K; 10.70. NMR of proton () g 3 "CH3 j7 5, OK. W), 5- 6.76 ppm (m) 8 Hb, 7 ppm (d) 3 But, Hj, 95 ppm (d) 3 Hc, 3R-Hc 15 i Proton NMR in deuterated DMSO. Phenolic protons are detected and 9.85 ppm ppm (t) 8 Hb, ii ppm (d) 8 Hd, IP-Hd 9.75 H, 0 ppm (d) 3 Is; 1P-Hc 13.5 Hj, 72 NIR C E, 06 ppm C / 1, ppm C 132.99-132.60 ppm Cz, 21 ppm C1, 9 "-55.22 C53P-C5 133.8 N, 36, 45-28.26 Sat The invention formula for preparing ester salts of bis {1-oxyphenyl) a kylphosphonic acids of the general formula {I) n “O or 1; M sodium or potassium; R is alkyl, 9233 5 10 15 20 25 1 12 consisting in that phenyl is reacted with general Formula (RO) ketodialkylphosphonate, lP-tCHib-C-CH3, in which Kip have the indicated values in the presence of boron trifluoride at a temperature for 1-2 hours followed by treatment of the resulting (bis ((o-hydroxyphenyl) alkylphosphonic acid) dialkyl ester) with an alcoholic solution of sodium or potassium hydroxide at a molar ratio of 1: 3, at boiling and neutralization of the resulting reaction mixture with concentrated hydrochloric acid acid with subsequent removal m the solvent under reduced pressure, filtering off the sodium or potassium chloride, and drying the resultant product under vacuum of 0.5-2 mm Hg information sources, the received note in the examination 1. And U.S. Patent 3,702,879, kl.2bO953 1972.
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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