DE2256783A1 - PROCESS FOR THE PREPARATION OF NEW DIPHENYLMETHANE, DIPHENYLOXIDE AND DIPHENYLSULFIDE PHOSPHONIC ACIDS, THEIR SALTS WITH INORGANIC CATIONS, THEIR ESTERS AND THIOESTERS - Google Patents

Description

Patent attorneys

DipL-ing. Ρ! Wirth

Dr. V. Schmied-Kcwarzik

Dipl.! Ng. G. Dan-Anborg

Dr. P. vV-tiild · !. Dr. D. Gudel

6 Frankfurt / .Vi., Gr. Eiciienhsimer Str. 39.

SÄHDOZ Α.Θ. - · ·

BASIS L CSchwete> , Case

Process for the production of new diphenylrcethane, diphenyl oxide and diphenyl sulfide phosphonous acids. their salts with inorganic cations, the esters and thioesters .

The purpose of the invention are new diphenylmethane, IDiphenylOXid-UlId diphenylsulfid-phosphonous acid compounds which contain one or two phosphorus atoms. The new compounds are free acids, their salts with inorganic cations, their esters and thioesters. The invention also relates to the preparation of these phosphonous acid compounds and their use for stabilizing organic materials.
The invention thus relates to a method for production

309822/1209

BATH ORIGINAL

Case

of new diphenylmothane, diphenyl oxide and diphenyl sulfide phos phonetic acids, their esters and thioesters of the formula

(D

n-1

wherein one or both benzene rings are optionally substituted by alkyl groups, η is the number 1 or 2, X is methylene, oxygen or sulfur, Y., Y ₃ , Y, and Y ^ independently of one another is oxygen or sulfur, FL. Rp, R-, and R ₂ , independently of one another, denote hydrogen or a hydrocarbon radical consisting of aromatic and / or saturated aliphatic units, and the salts of the phosphonous acids of the formula (I) with inorganic cations, characterized in that 1 mol of a Compound of formula

(Shark), =

M shark),

(II)

n-1

of the formulas HY JR-, and HY _{2 (}

where Hal is halogen, with 1 mol each of a compound of the formulas HY ₁ R ₁ and HY ₂ ¹ ^ ^{and mifc} ^ ^e ^ ¹¹ " ¹ ) ^M ° I of a compound

condensed, and then, as regards the preparation of the salts, the phosphonous acids thus obtained of formula (I) with inorganic hydroxides or salts.

The compounds used as starting materials in the present process of formula (II) are known to Toil, wLe beispiolnv / oi.r. in the Journal of the Chemical Society (London), 1932, page 2'vO

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BATH ORIGINAL

3 -. ' ^Gases 150-3342

described compound of the formula

They are made of diphenylmethane, diphenyl oxide (diphenyl ether) or diphenyl sulfide, optionally substituted by alkyl groups, by reaction with a. Phosphorus trihalide, preferably obtained with phosphorus trichloride. This reaction can be carried out in the gas phase at very high temperatures. In order to avoid side reactions, however, it is generally more advantageous to work under milder conditions with the use of catalysts. Friedel-Crafts catalysts, in particular anhydrous aluminum chloride, are suitable. It is preferred to work with phosphorus trichloride in excess at its boiling point. In the work up of the first Reaktionsgernisches the aluminum chloride complex can decompose with the resulting chlorophosphine, for example _t with phosphorous oxychloride or pyridine. These production methods are known in principle. These and other analogy processes for the preparation of compounds of the type of formula (II) are summarized by K. Sasse in the manual by Houben-Weyl, methods of organic chemistry, ^. Editions (1963) »Volume XIl / 1, organic phosphorus compounds, part 1, pages 302-318.

In the case of the general formulas HY ₁ ^ ₁ > H-YgR _2,. H / Y, R, and H Y4R4 defined starting materials are water, hydrogen sulfide, alcohols, phenols, mercaptans and thiophenols. The implementation of the starting materials of the formula (IT) with those of the formulas HY ^ i HY ₅ R ₃ , HY ^ R, 'and H Y ^ takes place in general

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-iP- Case 150-3542

smooth, it is often necessary to avoid side reactions, to dampen the stormy implementation by external cooling .. If you reacts with water, it is advantageous to present this in excess, to cool and stir the halophosphine of the formula (II) add so slowly that the temperature does not rise too much due to the exothermic reaction. In the hydrolysis carried out in this way one obtains colorless, powdery compounds, which remains of contain the following structure:

ir "

These derivatives of benzene phosphonous acid have acidic properties and are converted into their corresponding salts on treatment with inorganic bases or with salts containing inorganic cations. Examples of such inorganic reagents are: calcium hydroxide, zinc oxide, sodium carbonate, potassium hydrogen carbonate, aluminum acetate, barium chloride, nickel acetate and zinc chloride. The hydrolysis of halophosphines of the formula (II) and the conversion of the hydrolysis products which contain residues of the above formulas (IVa) or (IVb) into their salts can also be carried out in one operation. For this purpose, as just described, the water used for the hydrolysis is introduced in excess, together with the desired inorganic reagent, and then the halophosphine of the formula (II) is slowly added with stirring. If one does not use water, but other of the * formulas HY ₁ R ₃ , HY ₂ R ₂ , HY, R, and H Y ^ Ji ^

, 3 0 9 8 7 2/1208

ir. Gases s

converting speaking compounds, moisture is carefully excluded. Phenols generally react smoothly on heating, for example to 100-150 ⁰ Ci, the split off hydrogen halide escaping.

But you can also use acid-binding agents, such as. Pyridine or trialkylamines add and so bind the split off hydrogen halide.

This method is preferably used when dealing with alcohols implements. The implementations described are ana-

Logical procedures that are well known. A comprehensive overview of this has been published in the above-described book by K. Sasse (see page 318 ff.) Both benzene rings in the compounds of the formulas (I) and (II) can be substituted by alkyl radicals; however, they are unsubstituted in the preferred compounds. . The radicals R .., R, R and R ₂ can mean the normal alkyl radical with up to 20 carbon atoms such as methyl, ethyl, propyl, butyl, dodecyl, etc. or a secondary alkyl 'radical such as isopropyl, 2- Butyl, J-methyl-2-butyl, 2-pentyl, 2,2-dimethyl-3 "butyl, 2-hexyl, 5-hexyl, 2-methyl-3-pentyl, 3-methyl-2-pentyl, 4- Methyl-2-pentyl, 2,2-dimethyl-> pentyl, 2,4 ^ dimethyl-3-pentyl, 2-heptyl, 3-heptyl, 4-H.eptyl, 2-methyl-> hexyl, 4-methyl- 3-hexyl, 5-methyl-3-hexyl, 3-ethyl-4-hexyl, 2,2 ^ dimethyl-3-hexyl, 2,4-dimethyl-3-hexyl, 2,5-dimethyl-j5-hexyl, 3,4-Dlmethyl-2-hexyl, 2-methyl-3-heptyl, 3-methyl-2-heptyl, ^ -Methyl- ^ - heptyl, ^ -Methyl-J-heptyl, 5-methyl-> heptyl, 6 -Methyl-2-heptyl, 2-Oetyl, 3-Octyl, 4-Octyl, 2,2,4-Trlmethyl -> - pentyl, ^ -Aethyl ^ -heptjl, 2,2-

'309822/1209

Dimethyl 1-3-heptyl, 2,6-dimethyl-4-heptyl, 2-methyl-3-octyl, 3-methyl-4-octyl, 6-ethyl-3-octyl, 2-decyl, 5-decyl, 2, 2-dimethyl-> octyl, 2-methyl-4-nonyl, 3-methyl-4-nonyl, 6-ethyl-3-decyl, 7-ethyl-2-methyl-4-nonyl, 2-dodecyl, 2,6 , 8-trimethyl-4-nonyl, 2-trideeyl, 2-tetradecyl, 2-pentadecyl, 2-hexadecyl, 2-nonadecyl, cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-methyl-cyclohexyl, cyclooctyl, 2 , 5-, 2,6-, 3,4- or 3,5-dimethyl-cyclohexyl, 1-cyclohexyl-propyl, 2-propyl-cyclohexyl, 31.5-trimethyl-cyclohexyl, 2-butyl-cyclohexyl, 4-tert. Butyl-cyclohexyl, 3-methyl-6-isopropyl-cyclohexyl and cyclododecyl. The remnants of R., R _? , R ^ and R ₂ ^ can also have a primary carbon atom on Y ₁ , Y _? , Y Υ * bound, but otherwise branched. Examples of such alkyl radicals are: 2-methyl-1-propyl, 2,2-dimethyl-1-propyl, 2-methyl-1-butyl, 2-ethyl-1-butyl, 2,2-dimethyl-1-butyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2,4-dimethyl-1-pentyl, 2-ethyl-1-hexyl, 2,2-dimethyl-1- hexyl, 2,2,4-trimethyl-1-pentyl, 4-methyl-2-propyl-1-pentyl, 3 »7-dimethyl-1-octyl, 2,2-dimethyl-1-decyl, cyclohexyl-methyl, 2- Cyclohexylethyl, cycloheptylmethyl, 3-cyclohexylpropyl, cyclooctylmethyl, cycloundecylmethyl and cyclododecylmethyl. R-, R _? , R and R ₂ can also stand for aromatic radicals which are unsubstituted or substituted by alkyl radicals; the latter can be primary, secondary, straight-chain and branched alkyl radicals, as numerous examples have already been listed above. In addition, the aromatic radicals can also be substituted by tertiary alkyl radicals, for example by tert. Butyl, 2-methyl-2-butyl, 2,5-dimethyl-2-butyl, 2-methyl-2-pentyl, 3-methyl-3-pentyl, 3-ethyl-3-pentyl, 2,4-dimethyl 2-pentyl, 2-methyl-iMiexyi,> methyl-3-hoxyl, ^^ - üim ^ thyl - ^ - hexvl 3 5-dine

309822/1209 '

t'hyi-3-hexyl, 2-methyl-S-heptyl, 3-methyl-3-hepty.1, 4-methyl-4- ■

■ ·

heptyl, ^, ^, ^ - trimethyl-J-pntyl, '2,4 * 4-tr! methyl-2-pentyl, 3-ethyl-3-heptyl, 2-methyl-2-octyl, 4-methyl-4 -octyl, 3,6-BiTnethyl-3-octyl, 3,7-dimethyl-3-octyl, 2 H, _J 4.6 6-pentamethyl ~ 2-heptyl, 1-methyl-cyclopentyl, 1-methyl-cyclohexyl , 1-methyl-cyclolieptyl, 1-propyl-cyclopentyl, 1-butyl-cyclopentyl, 1-butyl-cyclohexyl and 1-pentyl-cyclopentyl. Finally, the radicals R, > H, R _v and Rji can also mean arylalkyl radicals. Particularly suitable aromatic radicals are phenyl and the phenyl radical. Examples of hydrocarbon radicals which consist of aromatic and saturated aliphatic units are: 2-> 3- and 4-methylphenyl, 2,3-, 2,4-, 2,5-, 3,4- and 3,5-dimethyl -phenyl, 2-, 3- and 4-ethyl 1-phenyl, 2,3,5- and 2,4,5-trimethyl-phenyl, 3-ethyl-5-methyl-phenyl, 4-sec-butyl-phenyl , 2- and -4-tert-butyl-phenyl, 5-isopropyl-2-methyl-phenyl, 2-isopropyl-5-diethyl-phenyl, -3-isopropyl-5-methyl-phenyl, 4-tert-pentyl phenyl, 2-tert-butyl-4-ynethylphenyl, 4-tert-butyl-2-methyl-phenyl, δ-tert-butyl ^ -niethyl-phenyl, 2,4-di-tert-butyl-phenyl, 4- ( l ', 1', 3 ', 3'-tetramethyl-butyl) -'- ■■ phenyl, 2-methyl-4 -. (l', 1 ', 3', 3'-tetramethyl-butyl) -phenyl, 4-nonylphenyl (mixture of isomers), 2,4-di-tert-octyl-phenyl, aryl, aralkyl, benzyl, 1- and 2-phenyl-ethyl, 1-phenyl-1-propyl, 1-phenyl-2-propyl, 2-phenyl-1-propyl, 3-phenyl-1-propyl, 1- (o-tolyl) -ethyl, 1-Cm-ToIyI) -ethyl, 1- (p-tolyl) -ethyl, 1-phenyl-1 -butyl, 2- (2 ', 4', 6'-trimethyl-phenyl) -ethyl, 1-phenyl-1-pentyl, 1- (4'-tert-butyl-phenyl) -ät hyl, 4-methyl-1 ~ phenyl-2-pentyl and benzhydryl.

3 0 9 8 2 2/1209

If R ₁ , R ₀ , R, or R ^ are alkyl radicals, these are primary or secondary and have 1-20, preferably 1-12 and especially 4-12 carbon atoms

If R, R, R or R _{2 are} an aryl radical, this has 7-20 carbon atoms, this aryl radical being optionally substituted by 1, 2 or 5 alkyl radicals having 1-12, preferably 1-6, carbon atoms.

If R *, Rp, R_ or R _{2 are} aralkyl, this has 8-20 carbon atoms, the alkyl part having 1-12, preferably 1-6 carbon atoms and the aryl radical optionally having 1,2 or 5 alkyl radicals 1-12, preferably 1-6 carbon atoms is substituted.

Means R ,, R _p , R-. or R ₂ , cycloalkyl, this radical has 3-2o, preferably 3-12 and especially 5-8 carbon atoms, where the ring can optionally be substituted by 1, 2 or J5 alkyl radicals with 1-6 carbon atoms.

If R ,, Rp, R., or R _{2 are} a cycloalkylalkyl radical, this radical has 4-2o, preferably 4-12 and especially 6-8 carbon atoms, the alkyl radical bonded to the cycloalkyl radical preferably having 1-6 C- Has atoms. The cycloalkyl radical can be substituted by one or two further alkyl radicals with 1-6 carbon atoms.

The two benzene rings of the formula (i) can each have 2 primary and / or carry secondary alkyl radicals with 1-6 carbon atoms.

3 Π M η 7 / / 1 2 U ¹ J

¹ y

Case 15O-3342,

A particular embodiment is given by the fact that R ,, R _p , IU or R ^ is hydrogen, a primary or secondary alkyl radical with 1-12, preferably 4-12 carbon atoms, phenyl or diphenyl, which can optionally be replaced by 1 or 2 alkyl radicals 1-4 carbon atoms are substituted, X is preferably oxygen, η is preferably 2, Y ,, Yp, Y and Y ^ and R ,, R _? , R_ and R ^ jevieils are identical, and the substituents on the benzene rings of the formula (I) are in the para position. .

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lo- Case 15o-33 ^ 2

The invention also relates to the new compounds of the formula (I) and their use as stabilizers. For this purpose, the new compounds are incorporated into substances sensitive to light, oxygen and heat or applied as a protective layer to the substances to be protected. Thanks to their stabilizing effect, the new compounds used in this way protect the sensitive substances from destruction. The possible applications in the plastics sector are particularly numerous. It can be used, for example, with the following plastics: Cellulose acetate, cellulose acetobutyrate, polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, silicone rubber, cellulose propellant, MeIamί Fortn-formaldehyde-urine - Resins, Allylglessnrze, Polymethy Irnethacryiat, polyester and Poly-.acrylonitril, as well as corresponding; Copolymers.

It also germinates! Iatur:; tof fo stab i 1 I r; Ie rt v / ground, such as Rubber, cellulose, wool and silk. The substances to be protected can be in the form of plates, rods, coatings, foils, films, Ribbons, fibers, granulates]), powders and in other processing forms, or as solutions, emulsions or dispersions. The incorporation or coating of those to be protected Materials is carried out according to methods known per se. A particularly important application method is intimate mixing of a plastic, for example of polypropylene in granulate form with the new compounds, for example in a kneader, and in itself subsequent extrusion. In this way a very homogeneous mixture is obtained, which is important for good protection. leg Extruding results in, for example, films, hoses or fabrics

6AD ORIGINAL

_ 11 - Case 15 Q-33 ¹ ^ 2

the. The latter can be woven into textiles. In this way of working becomes the stabilizer before processing into a textile material mixed with the polypropylene. But you can too Treat textile thread and textile fabric with the new stabilizers, for example in an aqueous liquor which is a contains finely dispersed compound of formula (I). Textiles made of polyethylene terephthalate and Cellulose acetate. ".

Plastics do not necessarily have to be fully polymerized or condensed before they are mixed with the new compounds. It is also possible to mix monomers or prepolymers or precondensates with the new stabilizers and only afterwards convert the plastic into its final form by condensing or polymerizing. · ..'..-

The new stabilizers just can't be used around clear films, plastics and the like to stabilize; they can also be in opaque, semi-opaque, or translucent Materials are used whose surface is sensitive to degradation by ultra-violet light, air and heat Examples of such materials are: foamed plastics, opaque Films and coatings, opaque papers, clear ones and opaque colored plastics, fluorescent pigments, ■ polishes for automobiles and furniture, creams and lotions and the like, regardless of whether they are opaque, clear or are translucent. ■.

The procedure described above permits the synthesis of very different variants of ^ e-rb-j iv.lun: * en öor Forme] (l), -rocUiss

3 0 9 8 2 2 / ι 2 0 ^ \

BATH

_ 12 _ Case 150-3342

the constitution can be designed in such a way that the stabilizing effect in certain plastics is particularly high. For example, about the relationship between the constitution of compounds of the formula (I) and their action, it should be mentioned that the stabilizing action in polyalkylenes, in particular in polypropylene, is particularly good when the molecule becomes an 'essential'. Part consists of saturated aliphatic groups. The protective effect of the new compounds against light, especially against ultra-violet light, is particularly high if the phosphonous acids of the formula (I), in which R-, R ₂ , R_ and R ^ are hydrogen, are used in the form of the nickel salts, especially in polyalkylenes. The manganese and copper salts are particularly suitable for stabilizing polyamides against UV light. Salts of other transition metals, such as vanadium and cobalt, are also suitable as UV light stabilizers in various substrates. The present invention also relates to the materials which contain compounds of the formula (i) for stabilization. As shown above with a few examples, the incorporation of the new compounds into the materials to be protected can be carried out in any processing stage according to methods known per se, the amount of incorporated protective agents varying within wide limits, for example between 0.01 and 5% preferably between 0.05 to 1 %, based on the materials to be protected. The stabilized organic materials can only contain compounds of the formula (i) or, in addition, other auxiliaries for improving the properties. Such aids are, for example: UV absorbers and stabilizers against destruction by

309822/1209

. $ 1 case 150-3342

Heat and oxygen. From the latter come mainly those in question what other classes of substances than the compounds of the formula (I), such as organic compounds of sulfur, of the 'tin and the five-value! for phosphorus, sterically hindered phenols, 2-hydroxy-benzophenones and hydroxybenzotriazoles. With such mixtures of stabilizers the stabilizing effect is often particularly high because there is a synergistic effect. Benzolphosphonlgsäureester and their stabilizing effect are already known from literature. Compared to these compounds, for example compared to those in the Belgian patent 724 802 described, the new compounds of the formula (..I) have "significant advantages". They are less volatile and less prone to migrate and are better in many materials to be protected soluble.

In the following examples, F is the melting point, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

309 822 / 1-209

- 14. Case

Example of the preparation of an intermediate of the formula (I I).

A solution of 51.3 parts of diphenyl ether, 165 parts of phosphorus trichloride and ΙΟβ is heated with the exclusion of moisture Parts of Al-Cl, refluxing for 3 hours, then gives 122.6 Add phosphorus oxychloride and stir for a further 1/4 hour. After cooling to 0 °, the granular form is filtered off AlCl, -POCl., - complex, washes well with chlorobenzene and the filtrate is evaporated in vacuo. The residue obtained is 4, V-diphenyl ether (bis-dichlorophosphine) of the formula

(V)

in the form of a light red, pungent smelling oil.

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Examples of the production of end products of the formula (I )

Example 1 . "

At 0-5 °, with exclusion of moisture, 29.9 parts of dodecyl mercaptan and 15 parts of triethylamine in 100 parts of toluene are added to a solution of 20 parts of biphenylether dichlorophosphine of the formula (III) in 50 parts of toluene, left to react at 40 ° overnight, filtered the precipitated salt is evaporated, the filtrate is evaporated in vacuo and the residue is crystallized from absolute ether. F: 25-26 °. ■ - - =: - ■ .. ■■■

Basic tariff analysis found C. K-. -. 9 H 5 , 6 ^C 36 ^H 59 ^OPS ber. 71. 6th "9 .9 5 .2 - - ■ 71. .8th; Example 2 ■. " \ -

At 0 ° -5 °, with the exclusion of moisture, a solution of 33 parts of diphenyl ether dichlorophosphine of the formula (III ) in 50 parts of toluene, left to react at 40 ° overnight, the precipitated salt is filtered off, the filtrate is evaporated in vacuo and the residue is crystallized from ether / methanol. F: 88-89 ⁰ .

Elemental Analysis, P

■ nu o, P ^gef · ^5Λ '■' ■ '\.

ber., 5.1 '

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- w - Casi

Example 3

At 0-5 °, 211 parts are added with the exclusion of moisture 2,4-di-tert-butylphenol and 104 parts of triethylamine in 300 Parts of toluene, a solution of 95.5 parts of 4,4'-diphenyl ether (bisdichlorophosphine) of the formula (V) in 50 parts of toluene, left to react overnight at 40 °, the precipitated salt is filtered off and evaporated the filtrate in vacuo, the residue triturated with methanol and crystallizes from benzene. F: '77 -80 °.

Elemental analysis ^C 68 ^H 92 ° 5 ^P 2

C. 2 8th H 5 P. found 77. 6th 8th .4 5 .6 ber. 77- .8th .9

Example 4

At 0-5 °, 116.2 parts are added with the exclusion of moisture 2-Tert.butyl-4-phenylphenol and 52 parts of triethylamine in 300 parts of toluene, a solution of 48 parts of 4,4 '- diphenyl ether (bis-dichlorophosphine) in 50 parts of toluene, left to react overnight at 40 °, the precipitated salt is filtered off and evaporated in vacuo the filtrate and the residue triturated to a white powder. F: 70-74 °.

Example 5

At 0-5 °, with exclusion of moisture, ^{a solution of 45 parts of 4,4'-diphenyl ether is added to 136.3 parts of 2.4 l} -di-tert-butyl-4-phenylphenol and 49 parts of triethylamine in 300 parts of toluene. (bis-dichlorphocphin) in 50 parts of toluene, left to react overnight at 40 °, filtered off the precipitated salt, evaporated in the Va-

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. · J 17 - Case 150- ^ 2. ·

the filtrate hardly enters and the residue is ground to a white powder. F: 82-85 ⁰ *

Example 6 '.

At 0-5 ° is added, with exclusion of moisture to 9 * 9 parts of butanol xxnä I ¹ I parts of triethylamine in 150 parts of toluene, a solution of 5 parts of 4,4'-12j Mphenyläther- (bis-diehlorphosphiri) in 50 - parts Toluene is allowed to react overnight at 40 °, the precipitated salt is filtered off, the filtrate is evaporated in vacuo and a light yellow oil is obtained

Example 7 (usage)

Unstabilized polypropylene is at 180 ° C and at 22o C with 0.2 % 2,2'-methylene »bis- (4-methyl-6-tert-butylpheiiol) and 0.1 % of the compound from Example 2 on one Roller mill mixed, processed into platelets and then tested for stability. '

The structural formulas of the compounds described in the above Examples 1 to S are in Table 1 below zusammengestelIf.

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Case 150-3342

Table 1

Example no.

Meaning of Q

■ Q

n-1

(tert.

(tert. do.

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Claims (1)

P.a tenta nsprttche Process for the production of new diphenylmethane, diphenyl, oxide and diphenyl sulfide phosphonous acids, their esters and thioesters of the formula (D in which one or both benzene rings are optionally substituted by alkyl groups, η is the number 1 or 2, X is methylene, oxygen or sulfur, Y, Y ^, Y., and Y ^ independently of one another is oxygen or sulfur, R- ", R _p , R-, and Rj. Independently of one another hydrogen or a hydrocarbon radical consisting of aromatic and / or saturated aliphatic units, and the salts of the phosphonous acids of the formula (I) with inorganic cations, characterized in that 1 mol of a compound of Formula '■> - ■>-' · (Hal), = 11-1 (ID where Hai is halogen, condensed with 1 mole each of a compound of the formulas HY ₁ R _n and HY ₀ R ₀ and with each (n-1) mole of a compound of the formulas HY-ZFU and HYkRh, and then, if it is the production of the Salts relates to the phosphonous acids of the formula (I) thus obtained with inorganic hydroxides 309 822 /, 12 09 ^: ORIGINAL INSPECTED . 2ο _ Case or converts salts. II. The compounds of the formula (I). III. Use of compounds of the formula (I) for stabilization of organic materials. IV. Organic materials that act as stabilizers compounds of formula (i) included. V. Organic materials which, as stabilizers, compounds of the formula (I) and other stabilizers and costabi- i lizers against the effects of oxygen, heat and Light included. The patent application 309 822/1209