DE3928291A1 - Novel phosphorous acid aryl ester-amide(s) and amide-halide(s) - the amide(s) being prepd. from the amide-halide(s) and being useful as stabilisers for plastics - Google Patents

Abstract

Phosphorus acid-aryl ester-amides of formula (I) and phosphorous acid-aryl ester-amide-halides of formula (II) are both claimed as are also (i) prepn. of (I) by reacting (II) with a specified Gringard cpd.; (ii) prepn. of (II) by reacting an appropriate dihalide with a specified amine; and (iii) use of (I), alone or together with a phenolic antioxidant, in the stabilisation of plastics. n = 1 or 2; R1 = (i) when n = 1, phenyl (opt. with 1-3 substits.), benzyl, alpha-Me-benzyl or alpha,alpha-di-Me-benzyl, or naphthyl (opt. substd. with 1-5 substits.) where at least one of the substits is 1-8C alkyl-oxy or -thio or 6-10 aryl or aryloxy or halogen of atomic no. 9-35 and the remainder (excluding the naphthyl residue) can be a non-aromatic 1-8C hydrocarbon residues; (ii) when n = 2, phenylene opt. substd. with up to 2 non-aromatic 1-8C hydrocarbon residues, etc., R2 = non-aromatic 1-8C hydrocarbyl, aryl or opt. substd. arylmethyl with the aryl having 6-10C; R3 = H or 1-18C alkyl-oxy or -thio, or as per R2; and R4 and R5 = 1-22C alkyl, 2-21C oxa- or thia-alkyl, 3-18C alkenyl or alkynyl, 3-24C alkoxy-carbonylalkyl, 5-12C cycloalkyl, 6-14C aryl, etc., and X = Cl or Br. USE/ADVANTAGE - (I) can be used directly for polymer stabilisation without the need to isolate it in a pure form.

Description

Phosphoric acid aryl ester amide halides, phosphonous acid aryl ester amides, process for their preparation and their Use to stabilize plastics.

The present invention relates to new phosphoric acid aryl ester amide halides, monophosphonous acid aryl ester amides and diphosphonous acid bis- [aryl ester amides], Process for their preparation and their use for Stabilization of plastics.

It is known that synthetic polymers against unwanted oxidative, thermal and photochemical damage during the manufacture, processing and use by Stabilizers or stabilizer systems are protected have to. Such stabilizers consist, for example a phenolic antioxidant and one or more Costabilizers, some of which also have the effect of can reinforce phenolic component synergistically.

Common stabilizers include. B. Phosphorous acid and phosphonous acid derivatives, where especially the latter due to its very good stability distinguished from hydrolysis.

It is the synthesis of various authors Phosphonous ester amides by stepwise reaction of phosphonous acid dihalides with alcohols or phenols and amines in the presence of acid acceptors [Houben-Weyl, Methods of Organic Chemistry, Phosphorus compounds E1 p. 300 (1982)]. The achieved Yields in these processes were only around 60-75%.

In an analogous manner, according to EP-PS 42 359 Suitable as stabilizers for polymers Phosphonous acid monoester monoamides by reacting  Alkyl or arylphosphonous acid dihalides, e.g. B. -chlorides, with phenols and amines in the presence excess base needed to neutralize the resulting Salszäure serves. Information regarding the purity of the products or the achieved Yields are not made there.

The implementation of the method of EP-PS 42 359 is however because of the difficult manufacture of as intermediate products required dihalophosphines only to a limited extent possible, which is of course disadvantageous if a technical Manufacturing is under consideration. So z. B. from the aromatic derivatives only phenyl dichlorophosphine technically available product, through the only derivatives the benzene phosphonic acid become accessible. this will thereby confirmed that in EP-PS 42 359 except for one all (no less than 17) examples den contain unsubstituted phenyl radical.

In addition to achieving higher yields, it is a fulfillment the high demands that are placed in practice on the Stability, effectiveness, low volatility and that Migration behavior of such stabilizers are provided, desirable, just derivatives of the phenyl radical to have substituted arylphosphonous acids available. Their accessibility by known methods fails however, the fact that this is substituted accordingly Intermediate products are needed that are not yet known or cannot be produced economically.

It is also an object of the invention to provide new stabilizers for plastics with improved properties, in particular with the help of methods that such Do not have disadvantages.

The present invention now relates to aryl ester of phosphonous acid of the formula I (see claim 1), that is to say when n = 1 phosphonous ester amide and when n = 2 diphosphonic acid bis [ester amide], in which
R1 as a monovalent radical is a phenyl radical which has 1 to 3 substituents, benzyl, α-methylbenzyl, α, α-dimethylbenzyl which can each carry 1 to 3 substituents on the core, or naphthyl or a 1 to 5 substituent-bearing naphthyl radical, at least one of the substituents represents an alkoxy radical or alkylthio radical, each with 1-8 C atoms or aryloxy, each with 6 to 10 C atoms or halogen with an atomic number from 9 to 35, and the rest - also exclusively for the naphthyl radical - with a non-aromatic hydrocarbon radical Represent 1 to 8 carbon atoms, and R 1 as a divalent radical is a phenylene radical which is unsubstituted or is substituted by up to 2 non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, or a naphthylene or biphenylene radical which is unsubstituted or 1 can carry up to 4 non-aromatic hydrocarbon radicals each with 1 to 8 C atoms as substituents,
R² is a non-aromatic hydrocarbon radical having 1 to 18 carbon atoms, aryl or an optionally substituted arylmethyl radical, the aryl each containing 6 to 10 carbon atoms, and
R³ represents hydrogen, an alkoxy or alkylthio radical each having 1 to 18 carbon atoms or a group mentioned under R²,
R⁴ and R⁵ independently of one another are each C₁-C₂₂-alkyl, C₂-C₂₁-oxaalkyl or thiaalkyl, C₃-C₁₈-alkenyl or -alkynyl, C₃-C₂₄-alkoxycarbonylalkyl, C₅-C₁₂-cycloalkyl, C₆-C₁₄-aryl, C₇- C₁₅ arylalkyl or an optionally substituted C₅-C₁₇-piperidin-4-yl group. R⁴ and R⁵ together with the nitrogen atom can also form a ring system with 5 to 7 ring atoms, which can additionally contain a hetero atom (O, N, S) bonded via at least one C atom.

A preferred group of compounds are those in which R¹ is a biphenylene radical as a divalent radical, R² and R³ each have a branched butyl radical and R⁴ and R⁵ each a butyl radical or together with the N atom the morpholide Form the rest.

Other preferred compounds are those in which R¹ the trimethylphenyl radical, R² and R³ the methyl or one branched butyl radical and R⁴ and R⁵ together with the Nitrogen either the piperidide or morpholide residue represent or in which R¹ is the tert-butyl-1-phenyl radical, R² is the tert-butyl radical, R³ is the methoxy or tert-butyl radical and R⁴ and R⁵ together with the N atom represent the morpholide residue represent.

Furthermore, such compounds are those in which R1 is unsubstituted or substituted naphthyl are particularly preferred.

In R¹, the substituents can each be the same or different be. The alkyl in the substituents of the aromatic residue R1 is e.g. B. one of the various hexyl or octyl radicals, but preferably has 1 to 4 carbon atoms and is z. B. methyl, Ethyl or one of the various propyl or butyl residues, which are optionally bound to the core via O or S. C nicht-C₈- is a non-aromatic hydrocarbon residue Called cycloalkyl, like the one below under R² listed residues. In particular, for. B. called the Anisyl residues or naphthyl residues, e.g. B. up to 2 Bear substituents with a total of up to 4 alkyl carbon atoms, as well as the various biphenyl residues.

For R¹ as a divalent radical z. B. called the various phenyl radicals that are unsubstituted or 1 carry up to 2 C₁-C₈-, in particular C₁-C₃-alkyl groups, or the various naphthyl and biphenylene residues, the unsubstituted or with 1 to 4 C₁-C₈-, in particular C₁-C₃ alkyl groups are substituted.  

Naturally, the substituents in R¹ can only be in one be combined in such a way that no steric Hindrance occurs. If R¹ contains 3 substituents, should not have more than 5 carbon atoms in the two o-positions be included. In substituted naphthyl residues, the more contain as two substituents, these are appropriate on both rings distributed.

As radicals R² and R³ are, for. B. non-aromatic Carbon residue with 1 to 18 carbon atoms, such as alkyl or cycloalkyl, furthermore aromatic radicals which including aliphatic groups of 6-18 carbon atoms have, wherein no more than 10 carbon atoms part of a aromatic ring system. Preferably contain the Residues R² or R³ 4 to 12 and in particular 6 to 10 C atoms. In particular, be considered non-aromatic Hydrocarbon residues called alkyl such as methyl, ethyl, the various propyl, butyl, pentyl, hexyl, octyl, Decyl, dodecyl, hexadecyl and octadecyl radicals, and Cycloalkyl with 5 to 10 carbon atoms such as cyclopentyl, Cyclohexyl, cycloheptyl and cyclohexylmethyl (i.e. both the hydrogenated benzyl radical as well as the methylcyclohexyl radical); C genannt-C₁₀ aryl and arylmethyl may also be mentioned, the The term aryl in each case includes alkylaryl, at most three of the substituents mentioned under R², and, this included, has a maximum of 14 carbon atoms.

If one of the radicals R² or R³ represents an alkyl radical, are tertiary alkyl groups with 4-10 carbon atoms, such as tert-butyl, 2-methyl-2-butyl, 2-methyl-2-pentyl, 2-ethyl 2-butyl is particularly preferred. Other preferred connections are those in which R² or R³ are phenyl, benzyl, α-methylbenzyl and α, α-dimethylbenzyl.

R⁴ and R⁵ are, for example, the radicals specified for R². If they are alkyl, C₁-C₁₂ alkyl groups are preferred.  

R⁴ and R⁵ are as C₂-C₂₁-oxa- or thiaalkyl for example Methoxymethyl, methylthiamethyl, ethoxymethyl, Methylthiaethyl or Athoxyäthyl. Are preferred Alkoxypropyl and alkylthiapropyl groups such as methoxypropyl, Ethylthiapropyl, butoxypropyl, octylthiapropyl, Dodecyloxypropyl, octadecylthiapropyl or Octadecyloxypropyl.

R⁴ and R⁵ are as C₃-C₁₈ alkenyl, for example allyl, Methallyl, n-hexen-3-yl, n-octen-4-yl, n-undecen-10-yl or n-octadecen-17-yl. Allyl and methallyl are preferred.

R⁴ and R⁵ are as C₃-C₁₈ alkynyl z. B. propargyl, n-butyne 1-yl, n-butyn-2-yl or n-hexin-1-yl. Are preferred Alkynyl groups with 3-6 C atoms, especially propargyl.

Do R⁴ and R⁵ form with the N atom to which they are attached a pyrrolidine, oxazolidine, piperidine, morpholine, Hexamethyleneimine or piperazine ring, so these can Heterocycles with 1 to 5, advantageously at most 2, methyl or ethyl groups. Those are preferred Ring systems unsubstituted.

If R⁴ or R⁵ are piperidin-4-yl groups, it can be act the unsubstituted piperidin-4-yl, or that Piperidine can be substituted with up to 5 alkyl groups. 2,2,6,6-Tetramethylpiperidine-4- is particularly preferred. yl rest.

The invention also relates to a process for the preparation of phosphonous ester amides of the formula I, in which R¹ as a monovalent radical may also be phenyl and phenyl substituted by 1 to 3 non-aromatic hydrocarbon radicals, and also C₁-C₁₈-alkyl and R², R³, R⁴ and R⁵ have the abovementioned meaning, which is characterized in that firstly a halide R¹ (-X) _n , in which R¹ has the abovementioned meaning, n = 1 or 2 and X is a halogen with an atomic weight of at least 35, but is preferably chlorine or bromine, under Grignard conditions, that is to say expediently with thorough mixing, is reacted with finely divided magnesium to give the corresponding Grignard compounds R 1 (MgX) _n and these are further processed in a second stage with phosphorous acid -arylester amide halides of the formula II (see claim 6), wherein R² R³, R⁴ and R⁵ have the abovementioned meaning and X is chlorine or he is bromine, converted to the phosphonous ester amides I. In other words, the inventive method is also applicable to the implementation of such compounds of formula R¹ (MgX) _n , in which R¹ z. B. represents the tolyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl radical.

With regard to economic accessibility are of the compounds II particularly preferred those with X = chlorine.

The first stage of the process according to the invention, which one can perform in any usual way preferably in an aprotic, organic solvent like an ether, e.g. B. Dietyhl, Dipropyl or Diisopropyl ether, ethylene glycol dimethyl or ethyl ether, Diethylene glycol dimethyl or ethyl ether, methyl tert. Butyl ether, dioxane or tetrahydrofuran performed.

Since the Grignard compound hydrolysis and are sensitive to oxidation, it is advisable to Protective gas atmosphere to work. Such an approach is however, in no way imperative for the success of the reaction. Nitrogen and argon are particularly suitable as protective gases.

The reaction temperature in the Grignardation is generally between 20 and 125 ° C, preferably between 30 and 70 ° C. The effect of ultrasound during the Grignarding is sometimes an advantage.  

To produce the end products I is in the second stage the solution or suspension of the Grignard reagent to the Phosphorous acid ester amide halide II, which is advantageous with an inert, aprotic solvent, e.g. B. one aliphatic hydrocarbon fraction, hexane, cyclohexane, Toluene, xylene or one of the above ether diluted is metered in, advantageously at a temperature below 0 ° C. The reaction temperature in this step is generally between -30 ° C and + 50 ° C, but preferably between -20 ° C and + 20 ° C. The implementation takes place in the Usually exothermic; accordingly, it may be appropriate to control the course of the reaction by cooling. The cheapest Results are achieved when you look at the reactants according to the reaction stoichiometry. However, it is also possible to use one reactant in excess; but in general there are no particular advantages connected. Appropriately, stirring is continued until the implementation is complete, and then from the failed Magnesium halide separated. The solvents can from the filtrate in the usual way, advantageously by distillation, especially under reduced pressure.

The synthesis of phosphonous ester amides with the help organometallic compounds, e.g. B. by implementing Phosphoric acid ester amide halides with Grignard No reagents are known yet. Apparently existed due to the known easy interchangeability of amino groups bonded to the phoshore as well as ester groups towards nucleophiles [Houben-Weyl, methods of organic Chemie, vol. 12/1, 44, (1963) and E 1, 302 (1982)] Prejudice that when implementing Phosphorous acid ester amide halides with Grignard reagents to a large extent with the process of reducing yield Side reactions and one caused by it lower yield of the desired product can be expected.  

It is therefore particularly surprising that after the process of the present invention, starting from easily accessible Phosphoric acid ester amide halides, any substituted Phosphonous acid aryl ester amides in such a high yield and Purity can be obtained.

The products I can be preferred by any method however by crystallization, from the raw products be discarded.

The phosphoric acid aryl ester amide halides II, except for that Compound are new in which X is chlorine, R² methyl, R³ Hydrogen and R⁴ and R⁵ are each ethyl [Izv. Akad. Nauk. SSSR, Ser. Khim., (9), 2131-2133 (1968)], can be found in simple way following a procedure that also The object of the invention is to be produced. These However, connection has no technical significance. It is particularly useful as a starting material for stabilizers unsuitable for polymers.

The invention therefore also relates to a method for Preparation of these compounds II, characterized in that is that you have a phosphorus acid aryl ester dihalide of formula III (see claim 12) with an amide Formula HNR⁴R⁵ (IV) in the presence of at least one equimolar Amount of an acid-binding agent is reacted, in which Formulas III and IV R², R³, R⁴ and R⁵ have the meanings the for the manufacturing process of compounds I and X is a halogen with an atomic weight of is at least 35. The process also extends to the preparation of the compound of formula II in which X chlorine, R² methyl, R³ hydrogen and R⁴ and R⁵ each Are ethyl, which was previously produced in a different way.

This process can be done in any usual way carry out. It is preferred to work in an inert aprotic solvent. Are particularly suitable for this  Hydrocarbons such as pentane, hexane, heptane, benzene, toluene, Xylene, chlorobenzene and ethers such as diethyl, dipropyl, Diisopropyl, ethylene glycol dimethyl or ethyl ether.

The compounds of formula II are advantageously in the Way prepared that to the solution of dihalide III an equimolar amount of amine IV and an equimolar amount Amount of a base suitable as an acid-binding agent lively mixing admits. Here you work in generally between -30 and + 30 ° C, preferably between -20 and + 10 ° C. The mixing takes place, for example by stirring and appropriately until the reaction is complete is. Then the precipitated ammonium salt separated. The solvents can be removed from the filtrate in the usual way, advantageously by distillation, where appropriate distilled under reduced pressure.

As bases, which are advantageous with one of the above Solvents are diluted, especially tertiary Amines such as triethylamine and pyridine. An excess of amine HNR⁴R⁵ can also act as an acid binding agent.

The products II obtained with this procedure fall usually in a purity that is easy for the Implementation with the Grignard connections is sufficient. A further cleaning, e.g. B. by vacuum or thin film Distillation is therefore generally not necessary.

The invention finally relates to the use of Compounds of formula I alone or in combination with a phenolic antioxidant to stabilize Plastics, in particular polymerisation plastics. For this application, however, the purity of the resulting raw reaction product sufficient. A Isolation in pure form is then not necessary.

From the examples illustrating the invention, the Production of the starting materials III, z. T. are known  described. As far as these connections are not yet known are analogous to known compounds (e.g. EP-PS 1 58 300) easily from PX₃ (X = Cl, Br) and the phenol in question. As The starting materials used are phenols and amines HNR⁴R⁵ (IV) mostly known compounds; otherwise they can be produced according to analog processes.

I) General regulation for the production of the preliminary products Phosphoric acid aryl ester dichloride III

650 mmol were added with the exclusion of air and moisture (= 89.3 g) phosphorus III chloride, a spatula tip (approx. 100 mg) p-dimethylaminopyridine and 500 mmol des phenol concerned. The solution cooled and it started HCl development. Within 60-90 min was slowly heated to 90-100 ° C. with vigorous stirring and held mixture 2 to complete the reaction Hours at this temperature. Then you pulled the low-boiling components at 50 ° C in a vacuum Water jet pump. The content of phosphoric acid Aryl ester dichloride was determined by 31 P NMR spectroscopy determined and was generally between 70 and 92%.

A) 2,4-di-tert-butyl-phenyl-phosphorous ester dichloride

Distillation of the crude product with a content of 91.7% [31 P NMR: δCDCl₃ = 184.7 ppm] on the above compound delivered 129 g of yellowish oil with a boiling point of 104-105 ° C / 0.05 mbar.

C₁₄H₂₁Cl₂OP (307.20):
Calculated:
54.73% C, 6.89% H, 10.08% P
Found:
54.9% C, 6.7% H, 10.2% P.

B) 2-tert-butyl-phenyl-phosphorous ester dichloride

Distillation of the crude product with a content of 84% [31 P NMR: δCDCl₃ = 185.1 ppm] on the above compound delivered 94 g of colorless oil with a bp 74-76 ° C / 0.01 mbar.

C₁₀H₁₃Cl₂OP (251.09):
Calculated:
47.83% C, 5.21% H, 12.33% P
Found:
47.4% C, 5.1% H, 12.0% P.

C) 2,4-Dimethyl-phenyl-ester-dichloride

Distillation of the raw product with a content of 75% [31 P NMR: δCDCl₃ = 180.9 ppm] on the above compound supplied 72 g of colorless oil with a bp 58-60 ° C / 0.05 mbar.

C₈H₉Cl₂OP (223.03):
Calculated:
43.08% C, 4.06% H, 13.88% P
Found:
42.7% C, 3.9% H, 13.6% P.

D) 2-tert-butyl-4-methoxyphenylphosphoric acid dichloride

Distillation of the crude product provides 110 g colorless oil with a boiling point of 108-110 ° C / 0.05 mbar.

C₁₁H₁₅Cl₂O₂P (281.11):
Calculated:
46.99% C, 5.37% H, 11.01% P
Found:
46.7% C, 5.5% H, 10.7% P.

E) 2,4-di-sec-butyl-phenyl-ester-phosphorous-dichloride

Distillation of the crude product with a content of 71% [31 P NMR: δCDCl₃ = 182.3 ppm] on the above compound supplied 93 g of colorless oil with a bp 108 ° C / 0.05 mbar.

C₁₄H₂₁Cl₂OP (307.20):
Calculated:
54.73% C, 6.89% H, 10.08% P
Found:
54.5% C, 6.7% H, 10.0% P.

F) 2-sec-butyl-phenyl-phosphorous ester dichloride

Distillation of the raw product with a content of 78% [31 P NMR: δCDCl₃ = 182.3 ppm] gave 83 g of colorless Oil from bp 92-93 ° C / 0.1 mbar.

C₁₀H₁₃Cl₂OP (251.09):
Calculated:
47.83% C, 5.21% H, 12.33% P
Found:
47.4% C, 4.9% H, 12.0% P.

II) Examples 1 to 12 - Phosphorous Acid Aryl Ester Amide chloride II General manufacturing regulations

To the solution of stirred at -10 ° C under nitrogen 500 mmol aryl ester dichloride in 400 ml The solution became toluene within 30-40 minutes 500 mmol of the amine HNR⁴R⁵ and 500 mmol (= 50.6 g) Triethylamine in 100 ml of toluene so that the  Internal temperature did not exceed 0 ° C. Then became The reaction is completed in 2 hours Stirred room temperature. After filtration and The solvent was distilled off in vacuo raw ester-amid-chloride mostly as yellow oils. For the further reaction with Grignard reagents is generally no further cleaning is required.

1) Phosphoric acid (2,4, -di-tert-butylphenyl) ester morpholide chloride

Starting from 153.6 g of phosphorous acid 2,4-di-tert-butylphenyl ester dichloride and 43.6 g Morpholine were 165 g of a colorless solid from 70 ° C and a content of 94% [31 P-NMR: δCDCl₃ = 156.9 ppm] of the above compound.

C₁₈H₂₉ClNO₂P (357.86):
Calculated: 60.41% C, 8.17% H, 8.65% P
Found: 60.1% C, 8.4% H, 8.3% P.

2) phosphoric acid (2,4-di-tert-butyl-phenyl) ester di-n- butylamide chloride

Starting from 153.6 g of phosphorous acid 2,4-di-tert-butylphenyl ester dichloride and 64.62 g di-n- Butylamine were about 190 g of a yellow oil with a Content of 94% [31 P-NMR: δCDCl₃ = 162.3 ppm] received above connection.

C₂₂H₃₉ClNOP (399.99):
Calculated: 66.06% C, 9.82% H, 7.74% P
Found: 66.4% C, 9.6% H, 7.7% P.

3) phosphoric acid (2-tert-butylphenyl) ester di-n- butylamide chloride

Starting from 125.54 g of phosphorous acid 2-tert-butylphenyl ester dichloride and 64.62 g di-n- Butylamine were about 165 g of a yellow oil with a Content of 89% [31 P-NMR: δCDCl₃ = 161.8 ppm] received above connection. C₁₈H₃₁ClNOP (343.87)

4) Phosphoric acid (2,4-di-tert-butylphenyl) ester piperidide chloride:

Starting from 153.6 g of phosphorous acid 2,4-di-tert-butylphenyl ester dichloride and 42.57 g  Piperidine was about 170 g of a yellow oil with a Content of 88% [31 P-NMR: δCDCl₃ = 157.7 ppm] received above connection. C₁₉H₃₁ClNOP (355.89

5) phosphoric acid- (2,4-di-tert-butyl-phenyl) -ester-N-n- butyl anilide chloride

Starting from 153.6 g of phosphorous acid 2,4-di-tert-butylphenyl ester dichloride and 74.6 g About 200 g of a yellow oil were added to N-n-butylaniline containing 89% [31 P-NMR: δCDCl₃ = 156.6 ppm] receive. C₂₄H₃₅ClNOP (419.97)

6) Phosphoric acid (2,4-di-tert-butyl-phenyl) ester-N- (hexamethylene-imino) amide chloride

Starting from 153.6 g Phosphoric acid 2,4-di-tert-butyl-phenyl ester dichloride and 49.58 g hexamethyleneimine (also as homopiperidine 176 g of a yellow oil with a Content of 87% [31 P-NMR: δCDCl₃ = 163.9 ppm] received above connection. C₂₀H₃₃ClNOP (369.91)

7) Phosphoric acid (2,4-di-tert-butylphenyl) ester dicyclohexylamide chloride

Starting from 153.6 g Phosphoric acid 2,4-di-tert-butyl-phenyl ester dichloride and 90.65 g dicyclohexylamine, completing the reaction was carried out at 60 ° C, was obtained approx. 205 g of a yellow resin with a content of 84% [31 P NMR: δCDCl₃ = 166.0 ppm] on the above compound. C₂₆H₄₃ClNOP (452.05)

8) Phosphoric acid (2-tert-butyl-4-methoxyphenyl) ester morpholide chloride

Starting from 140.56 g of phosphorous acid (2-tert-butyl-4-methoxyphenyl) ester dichloride and 43.6 g About 152 g of colorless oil were obtained from morpholine Room temperature froze.

C₁₅H₂₃ClNO₃P (331.77):
Calculated: 54.30% C, 6.98% H, 9.33% P
Found: 54.0% C, 6.7% H, 8.9% P.

9) phosphoric acid (2,4-di-sec-butylphenyl) ester morpholide chloride

Starting from 153.6 phosphoric acid 2,4-di-sec-butylphenyl) dichloride and 43.6 g morpholine about 160 g of a yellow oil with a content of 80% [31 P NMR: δCDCl₃ = 159.8 ppm] on the above compound receive. C₁₈H₂₉ClNO₂P (357.86)

10) Phosphoric acid (2,4-dimethylphenyl) ester morpholide chloride

Starting from 111.52 g of 2,4-phosphorous acid Dimethyl phenyl dichloride and 43.6 g morpholine were approx. 120 g of a yellow oil with a content of 90% [31 P NMR: δCDCl₃ = 160.7 ppm] obtained. The distillation gave a colorless oil of bp = 148-150 ° C / 0.05 mbar.

C₁₂H₁₇ClNO₂P (273.70):
Calculated: 52.66% C, 6.26% H, 11.31% P
Found: 51.9% C, 5.9% H, 11.5% P.

11) phosphoric acid (2,4-dimethylphenyl) ester piperidide chloride

Starting from 111.52 g of 2,4-phosphorous acid Dimethyl phenyl ester dichloride and 42.6 g of piperidine were 121 g of a yellow oil with a content of 89% [31 P-NMR: δCDCl₃ = 161.3 ppm] obtained from the above compound. The Distillation gave a colorless oil, bp = 134-135 ° C / 0.05 mbar.

C₁₃H₁₉ClNOP (271.72):
Calculated: 57.46% C, 7.04% H, 11.39% P
Found: 57.1% C, 6.9% H, 11.2% P.

12) Phosphoric acid (2,4-dimethylphenyl) ester di-n- butylamide chloride

Starting from 111.52 g of phosphorous acid 2,4-dimethylphenyl ester dichloride and 64.6 g di-n-butylamine 143 g of a yellow oil with a content of 86% [31 P NMR: δCDCl₃ = 167.7 ppm] on the above compound receive. The distillation gave a colorless oil from Kp = 148 ° C / 0.05 mbar.

C₁₆H₂₇ClNOP (315.82):
Calculated: 60.84% C, 8.61% H, 9.80% P
Found: 60.5% C, 8.4% H, 9.9% P.

III) Examples 13 to 33 - phosphonous acid aryl ester amides I General manufacturing regulations

Under a nitrogen atmosphere and excluding moisture from 250 mmol organobromine compound and 250 mmol (= 6.1 g) Magnesium shavings in 170 ml of tetrahydrofuran the corresponding Grignard connection established. The resulting solution or suspension of the organometallic compound then within 30-40 minutes under brisk Stir at an internal temperature of -20 to -10 ° C to the Solution of 250 mmol of the relevant phosphoric acid amide ester chloride II dosed in 120 ml of tetrahydrofuran. The reaction mixture was then left at room temperature accept and moved to complete the implementation another 2.5 hours. After filtration from the failed Magnesium salt was the solvent first in vacuo the water jet pump and then distilled off in a high vacuum and the colorless or light beige residue is pulverized and dried in a high vacuum.

The content of the desired product in the raw materials was determined by 31 P-NMR spectroscopy. He was lying in the general for the monophosphonous ester amides between 80 and 94% (of total P). In the specified Cases were used to characterize the product Acetonitrile / acetone mixtures crystallized.

13) (2,4,6-trimethyl-1-phenyl) -phosphonous acid- (2 ′, 4′-di- tert-butylphenyl) ester piperidide

Starting from 49.7 g Bromesitylene and 89.0 g of phosphoric acid (2,4-di-ter.- butylphenyl) ester piperidide chloride was about 108 g beige material from the softening point approx. 80 ° C and one 86% content of the above compound obtained [31 P-NMR: δCDCl₃ = 132.7 ppm].

C₂₈H₄₂NOP (439.62):
Calculated: 76.49% C, 9.63% H, 7.04% P
Found: 76.0% C, 9.5% H, 6.7% P.

14) (2,4,6-trimethyl-1-phenyl) -phosphonous acid- (2 ′, 4′-di- tert-butylphenyl) ester morpholide

Starting from 49.7 g Bromesitylene and 89.47 g of phosphoric acid (2,4-di-tert.- butyl-phenyl) -ester-morpholide-chloride were approx. 110 g colorless material with a melting point of 70-80 ° C and a content of 90% of the above compound obtained [31 P-NMR: δCDCl₃ = 132.4 ppm].

C₂₇H₄₀NO₂P (441.60):
Calculated: 73.43% C, 9.13% H, 7.01% P
Found: 73.1% C, 9.5% H, 6.6% P.

15) (2,4,6-trimethyl-1-phenyl) -phosphonous acid- (2 ′, 4′-di- methylphenyl) ester morpholide

Starting from 49.7 g Bromesitylene and 68.43 g of phosphoric acid (2,4-dimethyl phenyl) ester morpholide chloride became about 90 g yellowish Material with a softening point of 90-95 ° C and a content of 91% of the above compound obtained [31 P-NMR: δCDCl₃ = 135.1 ppm].

C₂₁H₂₈NO₂P (357.44):
Calculated: 70.56% C, 7.89% H, 8.66% P
Found: 69.9% C, 8.1% H, 8.2% P.

16) (2,4,6-Trimethyl-1-phenyl) -phosphonous acid- (2 ′, 4′-di- tert-butylphenyl) ester morpholide

Starting from 49.7 g Bromesitylene and 89.46 g of phosphoric acid (2,4-di-sec. butyl-phenyl) -ester-morpholide-chloride were approx. 108 g yellowish oil containing 86% of the above Compound obtained [31 P-NMR: δCDCl₃ = 134.3 and 135 ppm (Diastereomers)]. C₂₇H₄₀NO₂P (441.60).

17) (2,4,5-Trimethyl-1-phenyl) -phosphonous acid- (2 ′, 4′-di- tert-butylphenyl) ester morpholide

Starting from 49.7 g 5-bromo-1,2,4-trimethyl-benzene and 89.46 g of phosphoric acid (2,4-di-tert-butylphenyl) ester morpholide chloride were approx. 100 g colorless resin with a content of 93% Obtaining the above compound [31 P-NMR: δCDCl₃120.9 ppm]. Crystallization from acetonitrile gives colorless crystals from m.p. 130-132 ° C.

C₂₇H₄₀NO₂P (441.6):
Calculated: 73.43% C, 9.13% H, 7.01% P
Found: 73.2% C, 9.4% H, 6.8% P.

18) (4-tert.-butyl-1-phenyl) -phosphonous acid- (2 ′, 4′-di- tert-butylphenyl) ester morpholide

Starting from 53.5 g p-bromo-tert-butyl-benzene and 89.46 g of phosphorous acid- (2,4- About 110 g of di-tert-butyl-phenyl) ester morpholide colorless resin containing 85% of the above Compound [31 P-NMR: δCDCl₃ = 126.3 ppm] obtained. The Crystallization from acetone / acetonitrile (1: 1) provided colorless crystals with a melting point of 106-108 ° C

19) (4-tert-butyl-1-phenyl) -phosphonous acid- (2'-tert-butyl- 4'-methoxyphenyl) ester morpholide

Starting from 53.3 g p-bromo-tert-butyl-benzene and 82.95 g of phosphoric acid (2- tert-butyl-4-methoxyphenyl) ester morpholide chloride approx. 103 g beige material from the softening point approx. 70 ° C and a content of 82% of the above compound obtained [31 P-NMR: δCDCl₃ = 126.7 ppm]. C₂₅H₃₆NO₃P (429.54).

20) 4-biphenylphosphonous acid (2 ′, 4′-di-tert-butyl- phenyl) ester morpholide

Starting from 58.3 g of bromobiphenyl and 89.46 g of phosphoric acid (2,4-di-tert-butyl-phenyl) - ester-morpholide chloride became about 114 g of colorless material obtained with a content of 88% of the above compound [31 P NMR: δCDCl₃ = 125.3 ppm]. Crystallization from acetone provided colorless crystals with a melting point of 124-125 ° C.

C₃₀H₃₈NO₂P (475.61):
Calculated: 75.76% C, 8.05% H, 6.51% P
Found: 75.9% C, 8.35% H, 6.3% P.

21) (4-methoxy-1-phenyl) -phosphonous acid- (2 ′, 4′-di-tert-butyl- phenyl) ester di-n-butylamide

Starting from 46.75 g 4-bromoanisole and 100 g of phosphoric acid (2,4-di-tert-butyl) phenyl) ester di-n-butylamide chloride were about 110 g yellow resin containing 90% of the above compound obtained [31 P-NMR: δCDCl₃ = 127.9 ppm] C₂₉H₄₆NO₂P (471.67)  

22) 1-naphthylphosphonous acid- (2 ′, 4′-di-tert-butylphenyl) - ester-morpholide

Starting from 51.8 g of 1-bromonaphthalene and 89.46 g of phosphoric acid (2,4-di-tert-butylphenyl) ester morpholide chloride, about 112 g of colorless material from Softening point 100-105 ° C and a content of 87% Obtaining the above compound [31 P-NMR: δCDCl₃ = 120.8 ppm].

C₂₈H₃₆NO₂P (449.58):
Calculated: 74.81% C, 8.07% H, 6.88% P
Found: 74.2% C, 8.1% H, 6.4% P.

23) 2-naphthyl-phosphonous acid- (2 ′, 4′-di-tert-butyl- phenyl) ester morpholide

Starting from 51.8 g 2-bromonaphthalene and 89.46 g of phosphoric acid (2,4-di-tert.- butyl-phenyl) -ester-morpholide-chloride were approx. 110 g colorless material from softening point approx. 100 ° C and one 92% content of the above compound obtained [31 P-NMR: δCDCl₃ = 125.0 ppm]. Acetonitrile became colorless Obtained crystals of mp. 120 ° C.

C₂₈H₃₆NO₂P (449.58):
Calculated: 74.80% C, 8.07% H, 6.88% P
Found: 74.5% C, 8.3% H, 6.9% P.

24) 1-naphthylphosphonous acid (2 ′, 4′-di-sec-butylphenyl) - ester-morpholide

Starting from 51.8 g of 1-bromonaphthalene and 89.46 g of phosphoric acid (2,4-di-sec-butylphenyl) ester morpholide chloride were about 116 g of tough resin with a 80% content of the above compound obtained [31 P-NMR: δCDCl₃ = 121.2 and 121.6 ppm (diastereomers)]. C₂₈H₃₆NO₂P (449.58).

25) 1-naphthylphosphonous acid (2 ′, 4′-dimethylphenyl) - ester-morpholide

Starting from 51.8 g of 1-bromonaphthalene and 68.43 g of phosphoric acid (2,4-dimethylphenyl) ester morpholide chloride, about 91 g of colorless material from Softening point 78-80 ° C and with a content of 89% the above compound [31 P-NMR: δCDCl₃ = 121.6 ppm] obtained.

C₂₂H₂₄NO₂P (365.41):
Calculated: 72.31% C, 6.62% H, 8.47% P
Found: 71.9% C, 6.4% H, 8.1% P.

26) (4-methyl-1-naphthyl) -phosphonous acid- (2 ′, 4′-di-tert.- butylphenyl) ester morpholide

Starting from 55.27 g 1-bromo-4-methyl-naphthalene and 89.46 g of phosphorous acid- (2,4- di-tert-butyl-phenyl) -ester-morpholide-chloride were approx. 113 g beige material from softening point approx. 90 ° C and obtained a content of 88% of the above compound [31 P NMR: δCDCl₃ = 121.4 ppm]. Acetonitrile became a obtained colorless powder with a melting point of 110 ° C.

C₂₉H₃₈NO₂P (463.59):
Calculated: 75.13% C, 8.26% H, 6.68% P
Found: 74.7% C, 8.0% H, 6.5% P.

27) (2-methyl-1-naphthyl) -phosphonous acid- (2 ′, 4′-di-tert.- butylphenyl) ester morpholide

Starting from 55.3 g 1-bromo-2-methyl-naphthalene and 89.46 g of phosphoric acid (2,4-di-tert-butylphenyl) ester morpholide chloride about 108 g of almost colorless material from Softening point approx. 70 ° C and a content of 83% Obtaining the above compound [31 P-NMR: δCDCl₃ = 131.8 ppm]. Colorless needles of mp 115-118 ° C. were made from acetonitrile receive.

C₂₉H₃₈NO₂P (463.59):
Calculated: 75.13% C, 8.26% H, 6.68% P
Found: 75.6% C, 8.5% H, 6.3% P.

28) 1-naphthylphosphonous acid- (2 ′, 4′-di-tert-butyl- phenyl) ester homopiperidide

Starting from 51.8 g 1-bromonaphthalene and 92.48 g of phosphoric acid (2,4-di-tert.- butylphenyl) ester homopiperidide chloride (see Example 6) approx. 110 g of colorless, viscous resin with a content of 88% [31 P-NMR: δCDCl₃ = 122.9 ppm] at the above Get connection. From acetonitrile / acetone (1: 1) colorless crystals of melting point 112-113 ° C.

C₃₀H₄₀NOP (461.62):
Calculated: 78.05% C, 8.73% H, 6.70% P
Found: 78.2% C, 8.5% H, 6.5% P.

29) (6-methoxy-2-naphthyl) -phosphonous acid- (2 ′, 4′-di-tert.- butylphenyl) ester morpholide

Starting from 59.3 g 2-bromo-6-methoxy-naphthalene and 89.46 g of phosphoric acid (2,4-di-tert-butylphenyl) ester morpholide chloride were approx. 107 g colorless material from the softening point approx 45 ° C and a 94% content of the above compound obtained [31 P-NMR: δCDCl₃ = 12.79 ppm].

C₂₉H₃₈NO₃P (479.60):
Calculated: 72.62% C, 7.98% H, 6.45% P
Found: 72.2% C, 8.3% H, 6.1% P.

30) 4,4-biphenylene-diphosphonous acid bis- [2,4-dimethyl- phenyl) ester morpholide

Deviating from the general 250 mmol (= 78 g) of 4,4′-dibromobiphenyl were prescribed with 500 mmol (= 12.2 g) magnesium shavings in 500 ml Tetrahydrofuran under the influence of ultrasound (40 kHz) grignardized and with 500 mmol (= 136.9 g) phosphorous acid (2,4-dimethylphenyl) ester chloride in 200 ml Tetrahydrofuran is dissolved, implemented. Man received about 150g of yellowish, tough resin with a content 63% of the above connection [³¹P-NMR: δCDCl₃ = 126.7 ppm] C₃₆H₄₂N₂O₄P₂ (628.68)

31) 4,4'-biphenylene-diphosphonous acid bis - [(2,4-di-tert.- butylphenyl) ester morpholide]

Different from the general instructions, 250 mmol (= 78 g) 4,4'-dibromobiphenyl with 500 mmol (= 12.2 g) magnesium shavings in 500 ml of tetrahydrofuran under the influence of ultrasound (40 kHz) grignardized and then with 178.9 g Phosphoric acid (2,4-di-tert-butyl-phenyl) ester morpholide chloride reacted in 200 ml of tetrahydrofuran. Man received about 200 g of yellowish powder from the softening point 103-105 ° C and a content of 70% of the above compound [31 P NMR: δCDCl₃ = 125.0 ppm]. C₄₈H₆₆N₂O₄P₂ (797.00)  

32) 4,4'-biphenylene-diphosphonous acid bis - [(2,4-di-tert.- butyl-phenyl) -ester-di-n-butyl-amide]

Different from the general instructions, 250 mmol (= 78 g) 4,4'-dibromobiphenyl with 500 mmol (= 12.2 g) magnesium shavings in 500 ml of tetrahydrofuran under the influence of ultrasound (40 kHz) grignardized and then with 500 mmol (= 200 g) Phosphoric acid (2,4-di-tert-butylphenyl) ester di-n- butylamide chloride reacted in 200 ml of tetrahydrofuran. About 210 g of a tough, yellow resin were obtained with a Content of 73% of the above compound [31 P-NMR: δCDCl₃ = 126.9 ppm]. C₅₆H₈₆N₂O₂P₂ (881.27)

33) phenylene-1,4-diphosphonous acid bis- (2 ′, 4′-di-tert.- butylphenyl) ester morpholide

Different from the general instructions, 250 mmol (= 58.97 g) 1,4-dibromobenzene with 600 mmol (= 14.6 g) magnesium shavings in 300 ml of tetrahydrofuran under the influence of ultrasound (40 kHz) grignardized and then with 500 mmol (= 178.9 g) phosphorous acid- (2,4-di-tert-butylphenyl) - ester morpholide chloride reacted in 200 ml tetrahydrofuran. About 170 g of an almost colorless resin were obtained. Out Acetone gave colorless crystals from the softening point 230 ° C [31 P NMR: δCDCl₃ = 124.6 ppm].

C₄₂H₆₂N₂O₄P₂ (720.90):
Calculated: 69.97% C, 8.66% H, 8.59% P
Found: 69.5% C, 8.9% H, 8.3% P.

Claims (13)

1. Phosphoric acid aryl ester amides of the formula I. in which R 1 is a monovalent radical which is a phenyl radical which has 1 to 3 substituents, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, which can each carry 1 to 3 substituents on the core, or naphthyl or a 1 to 5 substituent-bearing naphthyl radical , wherein at least one of the substituents represents an alkoxy radical or alkylthio radical, each with 1-8 C atoms, aryl or aryloxy, each with 6 to 10 C atoms or halogen with an atomic number from 9 to 35, and the rest - with the naphthyl radical also exclusively - one represent non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, and R 1 as a divalent radical is a phenylene radical which is unsubstituted or is substituted by up to 2 non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, or a naphthylene or biphenylene radical, which are unsubstituted or can carry 1 to 4 non-aromatic hydrocarbon radicals each having 1 to 8 C atoms as substituents, R² is a non-flavor is a hydrocarbon radical having 1 to 18 carbon atoms, aryl or an optionally substituted arylmethyl radical, where the aryl each contains 6 to 10 carbon atoms, and
R³ represents hydrogen, an alkoxy or alkylthio radical each having 1 to 18 carbon atoms or a group mentioned under R²,
R⁴ and R⁵ independently of one another are each C₁-C₂₂-alkyl, C₂-C₂₁-oxaalkyl or thiaalkyl, C₃-C₁₈-alkenyl or -alkynyl, C₃-C₂₄-alkoxycarbonylalkyl, C₅-C₁₂-cycloalkyl, C₆-C₁₄-aryl, C₇- C₁₅-arylalkyl or an optionally substituted C₅-C₁₇-piperidin-4-yl group or together with the nitrogen atom form a ring system with 5 to 7 ring atoms, which additionally contains an O-, N- bonded via at least one C atom or can contain S atom. 2. Compounds according to claim 1, characterized in that R¹ is a biphenylene radical as a divalent radical, R² and R³ each have a branched butyl radical and R⁴ and R⁵ each a butyl radical or together with the N atom Form morpholide residue. 3. Compounds according to claim 1, characterized in that R¹ is unsubstituted or substituted naphthyl. 4. Compounds of formula I as shown in claim 1 characterized in that R¹ is the trimethylphenyl radical, R² and R³ are methyl or a branched butyl radical and R⁴ and R⁵ together with the nitrogen either the piperidide or represent morpholide residue. 5. Compounds of the formula I as shown in Example 1 characterized in that R¹ is the tert-butyl-1-phenyl radical, R² is the tert-butyl radical, R³ is the methoxy or tert-butyl radical and R⁴ and R⁵ together with the N atom represent the morpholide residue represent. 6. A process for the preparation of phosphoric acid ester amides of the formula I, as shown in claim 1, in which R¹ as a monovalent radical is a phenyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl radical, each of which has a core 1 to Can carry 3 substituents, or represents naphthyl or a 1 to 5 substituent-bearing naphthyl radical, the substituents being a non-aromatic hydrocarbon radical, alkoxy radical or alkylthio radical, each having 1-8 C atoms, aryl or aryloxy, each having 6 to 10 C atoms, or Represent halogen with an atomic number from 9 to 35 and as a divalent radical a phenyl radical which is unsubstituted or substituted by up to 2 non-aromatic hydrocarbon radicals having 1 to 8 carbon atoms, or a naphthylene radical or biphenylene radical which are unsubstituted or 1 to 4 can carry non-aromatic hydrocarbon radicals each with 1 to 8 C atoms as substituents,
R² is a non-aromatic hydrocarbon radical having 1 to 18 carbon atoms, aryl or an optionally substituted arylmethyl radical, the aryl each containing 6 to 10 carbon atoms, and
R³ represents hydrogen, an alkoxy or alkylthio radical each having 1 to 18 carbon atoms or a group mentioned under R²,
R⁴ and R⁵ independently of one another are each C₁-C₂₂-alkyl, C₂-C₂₁-oxaalkyl or thiaalkyl, C₃-C₁₈-alkenyl or -alkynyl, C₃-C₂₄-alkoxycarbonylalkyl, C₅-C₁₂-cycloalkyl, C₆-C₁₄-aryl, C₇- C₁₅-arylalkyl or an optionally substituted C₅-C₁₇-piperidin-4-yl group or together with the nitrogen atom form a ring system with 5 to 7 ring atoms, which additionally contains an O-, N- bonded via at least one C atom or can contain S atom, characterized in that firstly a halide R¹ (-X) _n , in which R¹ has the abovementioned meaning, n = 1 or 2 and X is a halogen with an atomic weight of at least 35, under Grignard conditions with finely divided magnesium to the corresponding Grignard compounds R¹ (MgX) _n and this further in a second step with aryl ester amide halide of formula II where R², R³, R⁴ and R⁵ have the abovementioned meaning and X is chlorine or bromine, converted to the phosphorous ester amides I. 7. The method according to claim 6, characterized in that the reaction in the first stage between 20 and 125 ° C, is preferably carried out between 30 and 70 ° C. 8. The method according to claim 6 or 7, characterized in that the implementation of the first stage under the influence of Performs ultrasound. 9. The method according to one or more of claims 6 to 8, characterized in that the reaction in the second stage at a temperature between -30 and + 50 ° C, preferably between -20 ° C and + 20 ° C is carried out. 10. Use of compounds of formula I, as in a of claims 1 to 5 defined, alone or in combination with a phenolic antioxidant to stabilize Plastics, especially polymerisation plastics.   1. phosphoric acid aryl ester amide halide of the formula II, wherein R², R³, R⁴ and R⁵ have the meaning given in claim 6 and X is chlorine or bromine, except for the compound in which X is chlorine, R² is methyl, R³ is hydrogen and R⁴ and R⁵ are each ethyl. 12. A process for the preparation of compounds according to claim 11, characterized in that an aryl phosphate dihalide of the formula with an amine of the formula HNR⁴R⁵ (IV) in the presence of at least an equimolar amount of an acid-binding agent, where in the formulas III and IV R², R³, R⁴ and R⁵ have the meaning given in claim 6 and X is a halogen with an atomic weight of at least 35 is. 13. The method according to claim 12, characterized in that the reaction at a temperature of -30 to + 30 ° C, preferably carried out from -20 to + 10 ° C.