CS245205B1

CS245205B1 - Process for producing 4,9-di / substituted-phenoxy / -3,5,8,10-tetraoxa-4,9-diphospha spiro [5,5] -undecenes

Info

Publication number: CS245205B1
Application number: CS497082A
Authority: CS
Inventors: Marcela Goeghova; Julius Durmis; Milan Karvas; Jan Masek; Jan Holcik
Original assignee: Marcela Goeghova; Julius Durmis; Milan Karvas; Jan Masek; Jan Holcik
Priority date: 1982-07-01
Filing date: 1982-07-01
Publication date: 1986-09-18

Abstract

Sposob pripravy podlá bodu 1 vyznačený tým, že sa použije zlúčenina obecného vzorca III, kde R je terč·—butyl, R je Λ,Λ-dimetylbenzyl, R3 je vodík a m, n a r sú rovnaké a rovnajú sa číslu jeden a teplota je 50 až 80 °C.The method of preparation according to point 1 characterized by using a compound of general formula III, where R is tert·-butyl, R is Λ,Λ-dimethylbenzyl, R3 is hydrogen and m, n and r are the same and equal to the number one and the temperature is 50 to 80°C.

Description

245 205

The invention relates to a process for the preparation of 4,9-di / substituted-phenoxy, 5,8, 10-tetraoxa-4, β-diphospha-spiroq, δ-undecate. Polymeric materials often require processing and practical application of additives to protect against the effect of oxygen in thermal stress, often even at temperatures above > 00 ° C, as well as against the effect of light radiation under the conditions of 245,255,205 atmospheric aging. Since these factors result in a change in the properties of the polymers, stabilizers are added to the processed polymeric materials, the antioxidants of which are also essential. The phosphorous-containing antioxidants involved in pentaerythritol are the antimicrobial agents. patent 3047_269> 3281381, 3576_91 & and fronts. aut. However, only 4,9-dialkyl-3,5,8,10-tetraoxa-4,9-diphospha-5,5-undecane derivatives (US 3047 269) have found practical use.

Thiete compounds were prepared by direct reaction in one-step pentaerythritol, triphenylphosphite, and an aliphatic component containing a hydroxyl group at 110-120 ° C or two steps by transesterification of the resulting 4,9-di-phenoxy-3,5,8,10-tetraoxa- 4,9-diphosphaspiroalcohol. 5,5 -undecane and the corresponding

The production method of the aforementioned patents does not guarantee the high yields of the desired phosphorous-containing compounds and the product contains high percentages of unreacted starting liquors which, due to the relatively low thermal stability of the phosphorus compounds, can only be difficult to separate by fractional distillation. Preparation of 4,9-dialkyl-3,5,8,10-tetraoxa-4,9-diphosfaspiro-5, 5'-undecenes or. nitrogen-containing compounds. In a two-step reaction through 4,9-dichloro-3,5,8,10-tetraoxa-4,9-diphosphaspiro [5.5] -napecane, it is the subject of the formula. aut. osv. 190 732 and 190 248.

Phosphorus-containing antioxidants used so far have to be combined with other mainly phenolic antioxidants in heat-intensive applications and are already decomposing at low temperatures. 3 245 205

The stabilization of the polymers by the compounds of the formula I, which have advantages over the antioxidants used up to now in the increased thermal stability and the increased resistance to hydrolysis, is the subject of the present invention. No. 211 116.

We found out

that the compounds of formula (I)

Wherein R, R and R are normally or branched alkyls of 1 to 18 carbon atoms, aralkyls of 7 to 9 carbon atoms, cycloalkyls of 6 to 7 carbon atoms, wherein m, n and n are integers from 0 to 3 , pr / t-ow, mr-z-Xa ~ are prepared by reaction of 4,9-dichloro-3,5,8,10-tetraoxa-4,9-diphospha-

spiro-5, 5 -undecane of formula II OCHO CHO x

Cl-P PC | / 11 /

OCH2 CH2OZ

and compounds of formula III

Wherein R, B, R, η, M, r are as defined above, in organic solvents in the presence of orgasmic bones, at a temperature of 10-80 ° C, preferably at 50-80 ° C. 4 245 205

This production mode is also applicable on an industrial scale.

Its advantage is a relatively high yield (90%). The technical product contains only a low percentage of the corresponding unreactedhofenol, which can be easily removed by washing with alcohol.

The compound (II) may be prepared by either the conventional method (US Pat. No. 2834,798, which consists in reacting pentaerythritol and PCl3 in a solvent at temperatures or by virtue of the non-limiting method of preparing compound (III), which, in addition to the small volume, also has a shorter reaction time. However, it is possible to isolate, but not to use, the intermediate as a second step in a common solvent, preferably chlorinated solvents such as dichloromethane, dichloroethane.

The increase in the reaction temperature compared to the laboratory temperature preparation is important both in the case of crystalline products which may be poorly soluble in the solvent used, or in the case of reaction with 2,4-disubstituted phenols by bulk groups or in the case of reaction with 2,4-disubstituted phenols. with 2,6-disubstituted phenols, the yield of the reaction is increased. The solvent for the second stage of the reaction must be selected in which the resulting product is a good soluble and concomitantly precipitated precipitate of the corresponding hydrochloride salt, which is the least soluble in it. Benzene, toluene, and dichloroethane can be used.

Substituted phenols were prepared by a variety of different catalysts depending on the type of substitution. In UAcorgq

In the condensation of compound II with 4-substituted phenols, ia) (TEA) as a base for the binding of liberated HCl is preferred at a temperature range of 20-40 ° C. 245,205 For compounds with a 2-substitution, the reaction temperature increases between 20-70 ° C with increasing substituent volume.

The reaction conditions in the condensation of the 2,4-disubstituted phenols are dependent upon substitution. If the substitution of the poles is 2-, hydrogen, methyl, the reaction temperature is up to 30 ° C, if isopropyl, tert-butyl, phenylethyl, dimethylbenzyl reaction temperature ranges from 50-80 eC.

For the reactions of 2,6-substituted phenols, the same conditions apply as in the case of substitution by bulky groups in the 2-. Example 1 Preparation of 2-substituted Derivatives

To a 250 ml 4-neck flask was added 0.1 mol of 4,9-dichloro-3,5,8,10-tetraoxa-4,9-difluorospiro [5.5] b & ndecane in 100 ml of benzene, added 0.2 mole of 2-substituted phenols, 0.2 mole of TEA is added slowly and the reaction temperature is maintained at a substitution rate of 30-80 ° C. HCl was filtered off, the benzene was evaporated. The resulting product was crystallized with benzene. An overview of the compounds I prepared is given in Table 1. Example 2 Preparation of 4-substituted derivatives

Compounds VI. XI is prepared by reacting 4-substituted phenols and II. at 10-50 ° C in the same manner as described in Example 1. Data prepared by the VI. - XI. are shown in Table 2. Example 3 Preparation of 2,4-disubstituted derivatives

Compounds XII. - XXI. was prepared by reacting 2,4-disubstituted phenols and II. at temperatures of 40-80 ® by the same procedure as in Example 1. The data for prepared substances can be found in Table 3. 6 245 205 Example 4 Preparation of 2,6-disubstituted derivatives

Compounds XXII · - XXIV. was prepared by resection of 2,6-di-substituted phenols and compound II. at temperatures of 60-80 ° C in the same manner as in Example 1. The data for the prepared substances are given in Table S.4.

Table δ. 1

Zl. Phenolic Component RMH Sum. formula π '·% P off. discover. replotatopenia7 [deg.] C. (Reaction) temperature / 0 / I. 1 o 408.341 C19H22 [deg.] 6P2 15.15 14.86 88-91 20-25 II. ^ 0- 464,400 C23H30O6P2 13.30 12.96 100-101 20-25 III. 492.472 C25H34 ° 6P2 12.50 12.06 120-125 40-50 IV. 544,569 C29H38 ° 6P2 11,35 11,20 152-153 40-50 HJ 588,577 C33H34 ° 6P2 10,50 10,14 132-135 60-70

Table S. 2 VI. 408.341 C19H22 ° 6P2 15.15 14.95 152-155 20-25 VII. 464.440 C23H3O ° 6P2 13.30 12.90 182-184 20-25 VIII. + © -0- 492,472 C25H34 ° 6P2 12,60 12,25 135-140 30-40 IX. (h) - @> - 0- 544,569 C29H38 ° 6P2 11,35 12,80 121-123 30-40 X. 588,577 C33H34 ° 6P2 10,50 10,12 '131-132 30-40 XI. 616.604 C35H38O6p2 10.05 9.55 124-126 1 30-40 245 205

Table 5.

Zl. ~ ............ RMH Sum. formula «off. P ziat «, Temperature Topgn Reactor Heat C / XII. + <og-520,549 C27H38 ° 6P2 11.75 11.36 112-113 25-30 XIII. k + <2b ° - i 575.627 C31H46 ° 6P2 10.72 10.30 118-120 25-30 XIV. 604.680 C33H44 ° 6P2 10.25 10.15 172-173 50-60 XV. 548.245 C29H42 ° 6P2 11.29 10, 86 74-75 50-60 II XVI. -Χφ- 520.549 C29H38 ° 6P2 11.75 11.61 181-189! 60-70 ii XVII. 575.627 C31H46 ° 6P2 10.70 10.23 175-176 I 60-70 I i XVIII • <§> + <O> 644.676 C37H42 ° 6P2 9.45 0.05 I 172-175 i 50-60; i XIX. © -ng ^ - 700.860 C41ri5O ° 6P2 8.80 8, 60 j 178-181 i 60-70 1 XX. <o} + <5 ^ - JO} 728.228 C43H54 ° 6P2 8.46 8.26! 160-162 60-80 XXI. - @ - c- 644-676 C37H42 ° 6P2 9.45 i ___ 9.34 248-249 60-80

Table δ. 4 XXII. - λ 436,368 C27H26 ° 6P2 14,10 13,96 166-167 50-60 XXIII Og- J0 548,245 C29H42 ° 6P2 11,29 10,95 160-161 70-80 XXIV. 708.849 C41H58 ° 6P2 8.75 8.52 215-217 70-80 ——

Claims

245 205 OBJECT OF THE INVENTION

A process for the preparation of 4,9-di (substituted-phenoxy) -3,5,8,10-tetroxa-4,9-difosfaspiro [5.5] undecanes of general formula (I).

(1) wherein R1, R1 and RJ are normally or branched alkyls having 1 to 18 carbon atoms, aralkyls of 7 to 9 carbon atoms, cycloalkyls having 6 and 7 carbon atoms ZA-Visam. / m -r ns tr »ϋm, r and n are integers ranging from 0 to 4 in which aa is attributable to the reaction of 4,9-dichloro-3,5 ' -8,10-tetraoxa-4,9-diphosphaspiride. 5, 5-undecary of formula IIOCHO CHO0 Cl - P P-Cl XOCH2 CH 2 OZ / 11 / / 0 Ά of the compound of formula III

Wherein OH, R, R, R, n, m are as defined above, in organic solvents in the presence of an organic base at a temperature of 10-80 ° C, preferably at a temperature of 50-80 ° C.