DD238798A1 - METHOD FOR PRODUCING FUENBLE HYDROXYALKYLPHENYL SUBSTITUTED PHOSPHORORGANIC COMPOUNDS - Google Patents

Abstract

The invention relates to a oeconomisches process for the preparation of five-bond hydroxyphenylalkyl-substituted organophosphorus compounds from a variety of different hydroxybenzyl compounds, as well as inexpensive trivalent phosphorus compounds, such as. As the phosphorus trichloride, which have great importance as flame retardants and antioxidants and are particularly suitable as stabilizers against thermo-oxidative, as well as light-induced degradation of organic polymers. According to the invention, the object is achieved by preparing compounds of general formula 1 and the compound of formula 3 and formula 5 and preparing the compounds of general formula 2 from the compounds of formula 4 and formula 5, the reaction being carried out in an organic solvent , Preferably methylene chloride is carried out at temperatures of 60C to 50C and the reactive hydrogen halide is removed as a non-soluble compound from the reaction mixture.

Description

Characteristic of the known technical solutions From the literature are essentially 3 ways for the preparation of five-bond hydroxyphenylalkylsubstituierten

organophosphorus compounds known.

Thus, a Hydroxybenzylhalogenid reacts at higher temperatures with a trialkyl phosphite with elimination of a Alkyl halides to phosphonate. This reaction leads to discoloration due to the possible side reactions Product. Cleaning these compounds is often associated with great difficulty. This is especially true Use of higher alkyl halides, e.g. problematic with octadecyl chloride. For hydroxybenzyl halides is due to the

great reactivity of these compounds to promote a selective process at low temperatures.

Thus, US Pat. No. 3,534,127 describes the reaction of hydroxybenzyl halides with corresponding phosphorus-III chlorides

(For example, phosphorus trichloride, Phosphorigsäurediphenylesterchlorid) in the presence of Lewis acids. These

Reaction takes place at low temperatures. This is followed by destruction of the metal complex with water, adequately Fiedel Crafts alkylations. The others Workup is carried out by drying with sodium sulfate and subsequent recrystallization. The disadvantage here is mainly the restriction to the corresponding benzyl halides and the destruction of the Metal complex can lead to undesirable hydrolysis phenomena. This is especially true for Phosphonsäurehalogenide, the

as intermediates of importance.

Another variant is the reaction of hydroxybenzyl compounds, where on the CH ₂ group substitutions

were made with diphosphites at higher temperatures.

For example:

HO

- SC - H-

or

"C H

with diphosphites /

Disadvantages here are also the relatively high reaction temperatures and the associated side reactions, which cause a discoloration of the products and make additional workup necessary.

The aim of the invention is an economical process for the preparation of five-bond hydroxyphenylalkyl-substituted organophosphorus compounds from a variety of different hydroxybenzyl compounds, as well as inexpensive trivalent phosphorus compounds, such as. B. the phosphorus trichloride.

Explanation of the essence of the invention

The invention is to achieve the objective of the object to develop an easily feasible process for preparing fünfbindiger hydroxyphenylalkyl-substituted organophosphorus compounds, in the result of which the by-products are easily removed. According to the invention the object is achieved in that five-bond hydroxyphenylalkyl-substituted organophosphorus compounds of the general formula 1

and general formula 2

ii

hydroxybenzyl-substituted compounds of general formula 3

and general formula 4

and drsibindioen phosphorus compounds of the Allciomelnen Forrr ^ si S

11

~ P - X

12

where η A X Y

= 1 to 18 = oxygen and sulfur = chlorine, bromine, iodine

Is chlorine, bromine, iodine, OH group, SH group, O-alkyl, O-aryl, S-alkyl, S-aryl, O-tosyl, NH ₂ , NH-aryl, N- (aryl), NH- alkyl,

N- (alkyl) ₂

R1.R2. R3. R7. Re. Rg, R10 are independently alkyl, aryl, alkoxy, aryloxy, hydrogen, hydroxy, SO ₂ F, nitro group, chlorine, bromine, iodine, fluorine

R _{6 is} alkyl, aryl, alkoxy, aryloxy, hydrogen, halogen

R ₁₁ , R ₁₂ are each independently alkyl, aryl, alkoxy, aryloxy, S-alkyl, S-aryl, chlorine, bromine, iodine and R ₁₁ and R ₁₂ as cyclic compounds with each other cycloaryl, cycloalkyl and heterocyclic and substituted heterocyclic compounds aromatic and aliphatic nature.

R ₄ , R ₅ independently of one another such as R ₁₁ and R ₁₂ or R ₄ and R ₅ together with the inclusion of the phosphorus atom are a heterocyclic ring such as R ₁₁ and R ₁₂ , and OH groups or SH groups and the compound of the general formula 1 prepared from the compound of formula 3 and formula 5 and the compound of general formula 2 is prepared from the compounds of formula 4 and formula 5, characterized in that the reaction in an organic solvent, preferably methylene chloride at temperatures from -60 ⁰ C to 50 ⁰ C, preferably -40 ⁰ C to 3O ⁰ C carried out and the reactive hydrogen halide is removed as an insoluble compound, preferably as amine hydrohalide from the reaction mixture. It was surprisingly found that by the reaction of 3,5-di-tert. butyl-4-hydroxybenzylalkohol with Phosphorigsäurediphenylesterchlorid not the phosphite, but the phosphonate is formed.

The reaction was carried out by directly reacting the above compounds in a solvent at low temperatures according to Equation 1. Q

^ 0? H

CH ₂ OH

complex

'HCL

* CH ?,

0? L ·

The resulting hydrogen chloride is then bound in the form of a Trialkylammoniumhydrohalogenides, or in the form of another salt-like compound and removed by subsequent filtration. The workup of the organic phase provides here the phosphonate. For this, the solvent is distilled off and the remaining residue is purified by recrystallization. ' "

Because of these unexpected results, it was examined whether structurally other hydroxyphenylalkyl-substituted compounds with trivalent phosphorus compounds give five-bond organophosphorus compounds. According to the invention the object is achieved in that 3.5 di-tert. Butyl-4-hydroxybenzyl bromide as another hydroxyphenylalkyl-substituted compound z. B. be reacted with the Phosphorigsäurediphenylesterchlorid according to Equation 2.

CTh

γ + CL-?

complex

The procedure when using the Hydroxybenzylbromides differs with respect to the Hydroxyb enzylalkoholes in that here the equimolar amount of water must be added, as well as the fact that additionally formed hydrogen halide must be removed. For the synthesis of corresponding sulfur compound hydrogen sulfide is used instead of water. Apart from the variation of the hydroxyphenylalkyl compounds, other trivalent organophosphorus compounds have also been used. According to Equation 3 was formed in the reaction of diphenylchlorophosphine with the 3,5-di-tert-butyl-4-hydroxy-benzyl-diphenyiphosphinoxyd. λ

complex

HO V

When using phosphorus trichloride and hydroxyphenylalkyl compounds also arise five-binding organophosphorus Verbindunaen z. B.

V ^

ho (O VCIt, OHtC I-

complex

In addition to the variation of the compounds which can be used, a further advantage of the process is that the preparation of the hydroxyphenylalkyl-substituted organophosphorus compounds from phosphorus trichloride, corresponding alcohols and the hydroxyphenylalkyl-substituted compounds is possible directly, without isolation of intermediates. Thus, the reaction of phosphorus trichloride with 2,2'-methylenebis- (4-methyl-6-tetrabutylphenol) in the presence of triethylamine and subsequent reaction with 3,5-di-tert-butyl-4-hydroxybenzyl alcohol according to Equation 5 + Equation 6 gives the 4,8-di-tert-butyl-2,10-dimethyl-6 (3,5, -di-tert-butyl-4-hydroxy-phenyl) -methyl-6-oxo-12H-dibenzo (dg) (1.3.2) dioxaphosphocene

The erfindühgsgehnäße method has the advantage that the synthesis of corresponding five-bond organophosphorus Compounds with little effort from basic chemicals and the hydroxybenzyl alcohol is possible. The isolation of intermediate compounds can be omitted here. This reduces the expenditure on equipment for the synthesis

corresponding compounds.

Another advantage of the method is that the solvent used to isolate the five-bonded organophosphorus Distilled off compounds is constantly used again to solve the starting substance. On the other hand, it can be seen from the example given that a further large number of starting materials for the process

can be used. This concerns the trivalent organophosphorus compounds, as well as the

hydroxyphenylalkyl substituted compounds.

The method according to the invention will be explained below with reference to 5 exemplary embodiments:

embodiments

For the reaction of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol with a compound of formula 5, it is necessary to maintain the desired five-bond phosphorus compounds to connect water during the reaction.

As a result, the methylene chloride used is dried with phosphorus pentoxide and the triethylamine with potassium hydroxide.

Embodiment 1 3.5 Di-tsrt.buiyM-hydroxybenzyl-riiphenylphosphinoxyd, 1 mol Diphsnylchlorphosphin and 100 mL of methylene chloride at -30 ⁰ C pre-cooled by a saturated solution of 1 Mo! 3,5 di-tert-butyl-4-hydroxybenzyl alcohol in methylene chloride, wherein -20T are not exceeded. While stirring, be: -25 ° C to -20 ⁰ C 1.1 mol of triethylamine added. A white precipitate of triethylamine hydrochloride forms. For complete reaction is boiled for an hour at reflux. The precipitate is filtered off with suction and the methylene chloride is distilled off from the solution. The remaining residue, after recrystallization from ligroin / benzene, gives the phosphine oxide which melts at 166 ^° C.

Embodiment 2

Diphenyl-3,5-diisocyanate-butyl-4-hydroxybenzylphosphonate In accordance with the above procedure, the diphenyl-3,5-tertiarybutyl-4-hydroxybenzylcohol and the phosphorodiphenyl dicarboxylate are obtained as diphenyl-3,5-tertiarybutyl-4-hydroxybenzylphosphonate , The recrystallized from hexane product has a melting point of 137 "C.

Embodiment 3

Mono-o-hydroxyphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate

The reaction of 2-chloro-benzo-1,3,2-dioxaphospholine with 3,5-di-tert-butyl-4-hydroxybenzyl alcohol according to Example 1 leads to the ring opening of benzo-1,3,2-dioxaphospholine. The recrystallized from ligroin monoester melted at 147 ° C to 150 ⁰ C.

EMBODIMENT 4 Diphenyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate 1 mol of phosphinodiphenylester chloride and 300 ml of methylene chloride are mixed in accordance with Example 1 with 1 mol of 3,5-di-tert.-butyl-4-hydroxybenzyl bromide. Subsequently, at -25 ° C to -2O ⁰ C, the addition of 1 mole of water in 2.1 moles of triethylamine. It is refluxed with stirring for 1 hour and then the amine hydrohalide separated from the solution. The methylene chloride is distilled off and by recrystallization of the remaining residue from hexane to obtain the melting at 137 ⁰ C phosphonate.

Embodiment 5

4,8-di-tert-butyl-2,10-dimethyl-6 (3,5-di-tert-butyl-4-hydroxyphenyl) -methyl-6-oxo-12H-dibenzo (d.g.) (1,3,2) dioxaphosphocene.

O) OH

3 mol of triethylamine are mixed with methylene chloride. At room temperature, 1 mole of 2,2'-isopropylbisbis (4-iVlethyl-6-tert-butylphenoi), and 1 Mo! rhosphorus trichloride added. It is recommended by Niedarschiag of tnethylamine hydrochloride. Mach one hour reaction time, a saturated solution of methylene chloride and 3,5-di-tert-butyl-4hydroxybenzylalkohol slowly added dropwise. It is warmed and boiled for one hour at reflux. The precipitate is filtered off with suction and the methylene chloride is distilled off from the solution. The remaining residue gives the melting at 253.5 to 255 ⁰ C phosphonate after two recrystallizations from toluene.

Dia products gave the following chemical shifts by ³¹ P NMR spectroscopy: final product

ic ssrsucr

yourself for the connections according to Bsispis! 1 br

former shift

SjöDi-tert-butyl ^ -hydroxybenzyldiphenylphosphinoxyd

Diphenyl-3,5-ditert-butyl-4-hydroxybenzylphosphonate

Mono-o-hydroxyphenyl-S ^ -ditert.

butyl 4-hydroxybenzyl phosphonate 4,8-di-tert-butyl-2,10-dimethyl-6 (3,5-di-tert-butyl-4-hydroxyphenyl) methyl-6-oxo-12H-dibenzo (d.g.) (1,3,2) dioxaphosphocene

28.5 ppm

(in methylene chloride)

20.6 ppm

(in methylene chloride)

29.1 ppm

(in methylene chloride)

19.5 ppm

(in methylene chloride)

Plant sheet formulas

formula 1

HO

> Tv-

Formula 3 ν V- ^L \\ ι V no Λ - / A " j V Ϊ3 \

/ D

R ₅

HO

Cv ₁ II

Formula 4

11

Formula 5

P-X

12

23.6.85-26382 '

Claims (4)

-1- 238 Invention claim: 1. A process for the preparation of five-bond hydroxyphenylalkyl-substituted organophosphorus compounds of the general formula 1 and the general formula 2 from hydrobenzyl-substituted compounds of the general formula 3 and the general formula 4 and trivalent phosphorus compounds of the general formula 5, whereη = Ibis 18 A = oxygen and sulfur X = chlorine, bromine, iodine Y = chlorine, bromine, iodine, SH group, O-alkyl, O-aryl, S-alkyl, S-aryl, O-tosyl, NH ₂ , NH-aryl, N (aryl), NH-alkyl, N ( Alkyl) ₂ Chlorine, bromine, iodine, fluorine R ₆ = alkyl, aryl, alkoxy, aryloxy, hydrogen, halogen Rii / P ".2 ~ are independently alkyl, alkoxy, aryl, aryloxy, S-Aikyi, S-aryl, chlorine, bromine, iodine and Rn and _R12 sis cyclic compounds to each other, Zvkloaryl. Cycloalkyl, and heterocyclic, and substituted heterocyclic Compounds of aromatic and aliphatic nature R j, R ₅ = independently of cinchona R ₁₁ and n ₁₂ oc R ₄ and R ₅ together form the phosphatatoma into a heterocyclic ring such as R ₁₁ and R ₁₂ as well as OH groups or SH groups and the compounds of general formula 1 the compound of formula 3 and formula 5 and the compound of general formula 2 from the Compounds of formula 4 and formula 5 is prepared, characterized in that the reaction in an organic Solvent, preferably methylene chloride at Tempe ^r 2turen -6O of ⁰ C to 50 ⁰ C, preferably -40 ° C to 30 ⁰ C uurch-jö'ührt UHU c'isr resi ^ iva Hueico jn / zasäcisioi 'as ur ^ öüiicha compound vci; vizsiaviye of amine- hyroquioanide from dinium-2-pyrrolidine: nG.T! ir, ch is absent. 2. The method according to item 1, characterized in that in the case of Y = S-A! Kyl, Y = S-aryl, Y = O-alkyl, Y = O-aryl, Y = oi-vjfLippO, V ~ «J-ι 03/1 ^ iü Γ.οά. \ ΐίΟΠ uΓ.L ^ i liuoJ ^ Z ϋΙΓιόΓ -jcioiSC ^ iii ^ * 'c · DIITUUr ₁ Cj, V (Ji ZltCjSVv'SISG Oisus ί Γ ίιίαΓοΠ ΑγΠμ'οο is performed. 3. The method according to item 1, characterized gelcannzeichrat that, in the case of Y = chlorine, Y = bromine, Y = iodine, the reaction with the addition of a basic compound, preferably a tertiary amine and the Y corresponding equimolar amount of water or hydrogen sulfide carried out becomes. 4. The method according to item 1, characterized in that in the case of Y = NH ₂ , NH-alkyl, N- (alkyl) ₂ , NH-aryl, N- (aryl) _2, the reaction with the addition of the corresponding equimolar amounts of water or hydrogen sulfide for Y is carried out. For this 1 page formulas Field of application of the invention The invention relates to a process for the preparation of five-bonded hydroxyphenylalkyl-substituted organophosphorus compounds, which have great importance as flame retardants and as antioxidants and are particularly suitable as stabilizers against thermo-oxidative and light-induced degradation of organic polymers.