DE1768011A1 - Alkyl ether-substituted phosphorus compounds, cyclic intermediates and processes for their preparation - Google Patents

Description

ί specimen copy] Dr Walter Beil j

& 2 1968

Frankfurt a. M- -Highest

Our Br. H 540

Stauffer Chemical Company lew York, Μ.Ϊ ·, 17, TStA.

Alkyl ether-substituted hydrochloride compounds ₉ eyoliache intermediates and processes for their preparation

The invention relates to a method of manufacture Clay compounds of the formal

H-O-T-C-P-A

(l ₄ ) _d H (» ₂ Μ ° *

where I ₁ , I ₂ , 1. and I ^ hydroearbylene groups, a, b »e and d are 1 or 0» ind, T is a chalcegene, A is a hydroxyl, a hydrecarbylexy, a hydroearbyl eder is an OH group , for which N is an alkali metal »11 iit. It is produced by reacting an organic phosphorus compound of the formula

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(»2> b ^H
Χ »-

<Vd ^H

where X is a halogen "tee and X '" in halogenated or a hydroxyl group mean not every 2 moles of a basic bond of the formula NTH · The reaction takes place at a temperature τοη 0 to 150 ° C.

New oil-containing ether compounds are used as intermediate products the formula

w naoh the same procedure by transferring the corresponding! • action participants get »where X 'of the formula is a · hydroxyl group and the basic compound NTR is used in an amount · τοη about 1 to« u about 1.2 Hol ·

In preferred embodiments, X is chlorine, T is oxygen and N is

trium.

The basic invention relates to a method of production τοη by alkyl-ether-substituted phosphorus compounds, such as Phosphinates and phosphonates, from the corresponding bie-chloroalkylphosphorus compounds or their actions. In particular, the present invention relates to a method of production τοη alkyl ether-substituted phosphorus compounds in which

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the ether component is a Ghalkogeii of a corresponding bls-chloroalkylphosphorus compound or a chloroalkyl haloalkylphosphoric derivative 1st · Under basic conditions, a cyclic s Ither intermediate is produced, which is then added under Formation of the compound according to the invention as a product cleaved can be.

BIe alkyl ether-eubstituted products prepared by this process Phosphorus compounds are active as bioloside compounds rerwendet, and «was particularly in the field of insecticides, fungicidal and also as sequestering agents «those as intermediates cyclic ether rate obtained according to the invention found as monomer runners for phosphorus-containing polymers, Copolymers with other polymerizable monomers, Chain terminators and reagents use. Tucked double blinds also have biological activity. Bie inventions Polymeric bonds also have sequestering properties.

According to the present invention, it has been found that the Phosphorus compounds substituted by alkyl ethers by reaction of bi8- (chloroalkyl) -phosphinic acid, bls- (chloroalkyl) -phosphine hexides or phosphonates with an alkaline metal salt of a Chalcogen's basic reaction conditions are produced.

About the course of the reaction of the το rl legendary invention can schema | table can be represented as follows!

Reaction scheme I.

-9 · ■ - C - I - O - P-A

? Ü9316 / 18O1

In the above reaction _{scheme I, R 1} , R ₂ , K and K are hydroearbylene groups with 1 to 18 carbon atoms, X is a halogen atom, X ^{1 is} a halogen atom or a hydroxyl group, A is a hydroxyl group, a hydrcoarbeylexy group with 1 to 18 carbon atoms ( -OR), such as an alkylexy group, a hydrocarbyl group with 1 to 18 carbon atoms (-R) or a metallic "OM, in which K is an alkaline metal" and a, b, c and d integers τοη 0 to 1.

As explained Tor below, the R groups, ie, S ₁ , R ₂ , R · and R, are each hydroearbylene groups having 1 to 18 carbon atoms. Examples of these hydroearbylene groups are alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, heptylene, octylene, honylene, decylene, undeylene, dodeoylene, hexadeoylene, octadecylene and the like up to 4 carbon atoms preferred. The hydrecarbylene groups also include the cycloalkylene groups, such as, for example, cyclopropylene, cyclohexylene, cyclopentylene, cyclobutylene and the like. Furthermore, this includes the arylene groups, for example phenylene, biphenylene, haphthylene and the like. The arylene group also includes the alkarylene and aralkylene groups, such as, for example, the tolylene and styrene groups.

The term halogen includes fluorine, chlorine, bromine and iodine

Examples of chalcogenes are oxygen, sulfur, selenium and tellurium ₉ , however, the cklcogen is preferred which has a molecular weight τοη less than 40, which means that T is oxygen or sulfur and preferably oxygen.

The metals designated by M in Reaction Scheme I above are the alkali metals and alkaline earth metals of 1. and 2. Main group of the periodic table of the elements. Examples of alkali metals are lithium, sodium, potassium and the like Examples of the alkaline earth metals are beryllium, magnesium, calcium, strontium, barium and the like. Because of the low Of course, sodium is preferably used as the alkali metal, if such is used in the reaction according to the invention is used. Es muga drirnuf. be advised that the

Group OH can be converted into a group A? for example the group OH is converted to OH by fringing the salt product. It is also possible to use esterification product obtained by carrying out the reaction in an alcoholic medium or using a lower alkylate · Various other derivatives of these compounds may also be used by using different reagents and applying different ones Conditions are established

With regard to the hydrocarbylene groups R, in which Ji is an aliphatic group, the same can contain oxygen or sulfur in the form of ethers, ketones, carboxyl groups or hydrocarbon substituents on the aliphatic chain, but the dunctional chalcogen groups of thorn phosphorus atom should by at least a carbon atom can be separated · R can also contain halogen atoms, which should be inert if they are removed from the phosphorus compound from a position beyond the ß-carbon atom · Of course, alcohols and amines cannot be used, since such substituents are reactive. If R is aromatic, it can be substituted by halogens in any position. Other hydrocarbon groups can be substituted for the same ^{w f; Ise}

It was found that the in the above Reaction Scheme I Implementation shown and explained carried out in several stages is, as illustrated by the following act in scheme II wlrdi

Reaction scheme II

(R ₂ ) _b H (R ₁

KTH

I ^f -

P - A + HTH

X-C

(H,

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(H ₂ ) _b H

Λ «<? 3> c ^H <? Λ ^Η Ο

PA ^ΗΥΗ HCYCP-

where I, X ¹ , H ₁ , B ₂ , Β ~ »R., a, b, c, d, A, M and Y have the meaning given above ·

P The cyclic intermediates identified in Reaction Scheme II can be isolated and used in a separate step to produce the final product of the reaction scheme. These compounds are also useful as monomers in the preparation of polymers and interpolymers and for other uses. However, it is preferred that the cyclic I ischenprodukt fieaktlonoteilnehmer from the manufacture, in which I ¹ is a hydroxyl group, ia remaining necessary for the hydrolysis of the halo group reaction conditions are generally sufficient, in order to favor the production of the ether end product.

In order to simplify the following description, the compounds used to explain the process according to the invention are those in which the integers a, b, e and d are equal to O, M is sodium, I is oxygen and the halo tos are »» chlorine. Ss However, is a _u f $ _eT obvious that this is only for simplicity and clarity and purposes of the present invention, this should not be restricted.

For an explanation you can use the method according to the invention Compounds to be prepared are obtained by placing a bis (chloromethyl) phosphinic acid in a suitable reaction vessel brings that contains a corresponding · basic · compound. In the present Pail, where Y is oxygen, Al-

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Kalimetall- or Brdalkalieetallhydroxyde Terwendet. let If another halogen, e.g. sulfur, then suitable alkali or alkaline earth metal sulfides, selenides or tellurides Can be used. However, it should be pointed out that that although ammonium is generally considered to be equivalent to alkali metal ions, it is not in the present case applies, so that it precipitates as a suitable hydroxide.

The basic compound HYH, such as sodium hydroxide, is used with success in quantities that vary according to the initial connection and the desired product. If, for example, p8- (chloromethyl) -phophinic acid is used, 4 to 4.5 moles of sodium hydroxide to form the sodium methoxymethyl Jj phosphonates required »Will hydroxymethyl- (chloraethyl) -phosphinic acid If the desired product is the cyclic ether, 2 to 2.2 moles of sodium hydroxide are used. If more than 3 moles of sodium hydroxide per mole of hydroxymethyl (chloroiethyl) phosphinic acid If this is used, then the salt of methoxyethylphosphinic acid is obtained. The total amount of people used Base HTH depends on whether the starting compound is an acid is or not. If it is an acid, a regulation of the amount must be carried out in order to neutralize the acid, beTor implementation can continue. Will the bie- | 3hloraethyl) - or bis (chloroalkyl) bond is used, a sufficient Amount of base to be added to the reaction medium set so that one of the chloratoae is removed and the monochloro-monohydroxy species are formed.

After addition of the base to the reaction mixture, the reaction mixture to a temperature of sound is about O heated to 15O ⁰ C, but a temperature is in the range τοη about 20 to 100 C be-Torzugt.

Suitable inert solvents or diluents can be used effectively when carrying out the process according to the invention. It has been found that the use of polar solvents such as ^w ater and alcohols, is highly desirable. For obvious reasons, water is of course the preferred reaction

2 0 9 8 10/1801

tionsaediua. Examples of suitable solvents are alkenes old 1 to 12 carbon atoms, ethyl ether, dioxane, tetrahydrofuran, acetonitrile and the like.

Although this is not necessary, the invention may act Reaction can be carried out for other printing presses » for example in the case of under- and overpressure. From understandable However, inventing is broken down into normal pressure.

For explanation, the cyclic ether is formed as follows laugh treatment tob

Ferael IK) CH ₉

as representative connection old elaea equivalent waterlgea sodium hydroxide at a temperature τοη about 60 to 00 * 0 is obtained

/ ⁰¹ V ^

Foxael XI O

The solution is cooled to a temperature τοη about 10 ⁰ C and about an equivalent terduant (5 * to 10 ige) sagesetst _y inter alia the cyclic ither of the Vorael

Formula III 0

/ ⁰ V

form. The solvent is removed by changing the pressure in a reaction vessel to about 10 to 20 mm Hg pressure at a temperature of 20 to 40 ⁰ C and finally dried at a temperature of about 20 ⁰ C and a pressure of 1 Hg. The product obtained is dissolved in acetone at a temperature τοη about 10 to 15 ° C and the resultant Oemioch

20981B / 1 801

filtered * The sodium chloride formed during the reaction is removed as an insoluble precipitate »The filtrate is again evaporated under reduced bridge τοη about 10 to 20 mm Hg at temperatures ranging from τοη 10 to 15 ⁰ C after the said solvent has been evaporated, is obtained the cyclic product · a Unset ait sung check itself Report asu τ ·, there must be at a temperature τοη be kept ⁰ C to O about -20 · Bas product is a colorless liquid · in the same manner, the preparation τοη Methoxymethylphosphonsäure as an example of τοrllegend Yerfahren described, after treatment of the compound of formula I.

K) OK ₉ 0

Cl-OH /

• that of the corresponding bls-chlorine analog with an excess of τοη aqueous sodium hydroxide at a temperature τοη about 80 to 105 ⁰ C, the solution is acidified by adding τοη 37 ^ iger hydrochloric acid in order to convert the entire! Atrlumhydrexyd au latriumehlorld * The solution is then evaporated to dryness under reduced bridge. The product is extracted from the salt by adding τοη cold hydrochloric acid solution and the insoluble latrium chloride is filtered off. It is also possible to remove the latrium chloride by using alcohols or ketones as solvents Product received as a colorless liquid.

As explained above, the cyclic compound can be polymerized to form a polymer also with compounds such as ethylene oxide, propylene oxide, 1,3-propylene oxide »The other copolymerizable conomers Formation τοη polymers are misohpolymerized. Bie lomc polymcrisation will be according to the action topic below ZXI carried out.

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Action Schoma III

- 10 -

-> HO-CH ₂ -P-CH ₂ - - O-P-CH ₂ _ _ _Q p OH

OH _W j> _nc OH ⁿ

In this scheme, η gives the number of repeating units an This polymerization reaction catalyzes itself, and other catalysts or catalyst systems are not required. However, if a high molar polymer is desired, a Priedel-Crafts catalyst, such as aluminum chloride, Sense chloride, iron (III) chloride, boron trifluoride, Antimen pentafluoride, phosphorus pentafluoride, and the like, τβto be applied »While the gate indicated above is cyclic Ither acidic results in using the cyclic ones Ither that are not acidic, more desirable polymeric polyether products · This is especially the pail if the acidic phosphorus hydroxide content of the output compound dos Heaktionssehemas III is replaced by OR or B, where 1 is a Is hydrocarbyl group. Bio & ahl of the repeating units, which is represented by η is usually in the range of tone 5 to 100.Bs can, however, be formed by using optimal conditions larger numbers τοη see repeating units.

Should the compounds be used as polymeric products or monomeric reagents to improve the flame-inhibiting properties Other polymers are used, it has been found that antimony all known as flame retardants can be used can in order to form salts with the phosphoric acid content and further increase the temperature of these compositions.

In the following examples and throughout the description, the parts and percentages given are unless otherwise indicated, based on weight. These examples serve to explain the fundamental invention

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Example 1 O O

g- (OH) ₂ from (ClCH ₂ ) Ji-

Production τοη CH ^ OCH p g- (OH) ₂ from (ClCH ₂ ) Ji- OH

A solution of 32.6 g (ClCHg) ₂ ^ OH (#, 2 mol) in 70 g water was added dropwise to a refluxing solution of 140 g water and 40 g sodium hydroxide (1.0 Hol). The addition time was about an hour. This solution was refluxed for about 16 hours. Then 59 cca 37% hydrochloric acid was replaced (0.7 mol) and the solution was evaporated to remove all of the solvent. It was then replaced with 200 ml of 37% hydrochloric acid and the mixture was filtered in order to remove the insoluble sodium chloride. Bas filtrate was evaporated to give 23.0 g of the product% (yield of 91.4 # CH ₃ OCH ₂ PO ₅ H _2).

Analysis 23.1 *? 0.35 * Cl
Theoretically 24.6 * P; no Cl

The base product was a thick, colorless syrup. Like titration was found to be a dibasic acid with a molecular weight τοη 127 (theoretically »126).

The nuclear magnetic resonance spectra (NMR) confirmed this Structure.

Example 2 ρ

Production τοη CH-OCHgP (OH) ₂ « _u · chloromethyl- (hydraxymethyl) - * phasphinic acid

A solution τοη 28.8 g

HIGH ₂ - " ^0H

(0.2 mol), 130 g of water and 40 g of sodium hydroxide (1 mol) were heated ^{at about 95 to 100 ° C. for about one hour.} Then 66 ecm of 37% hydrochloric acid (0.8 mol) was added and the

Concentrated solution to remove the solvent. Then, 200 com 37 ^/ 'hydrochloric acid were added and the mixture filtered to remove ts unlönlichen sodium chloride. B.tn Pil was entered

20981G / 1801

evaporated, and 21.1 g of the product or 86 * der were obtained Theory for

The product was purified by forming a Blelsalsea and washing it ■ _H2O. The free acid was regenerated by adding hydrogen sulfide and removing the lead sulfide formed.

The yield of the purified product was 19 »6 g.

Analysis! 23.8 * P; 12.8 * 0 as lther O. fhesriet 24.6 * p; 12.7 * 0 as ether 0.

As determined by titration, "was it d Product around a dibasic acid of a molecular weight ren 127.

Theoretical Moldceular Law 126.

The keraaagnetic resonance pectrua (HIl) played the same Value as for the product of example 1.

Example 3

OH ₂

Production τοη CH ₃ OCH-PO ₃ H ₂ A solution τοη 15 C ClCH ₂

P.

HIGH ^

(0.08 mol) in 23 g of water, the old aqueous * sodium hydroxide had been brought to a pH value τοη 9, was within about 15 minutes at a temperature τοη about 90 to 100 ⁰ C dropwise to a solution of 25 g water and 12 g of hatriuah hydroxide (0.3 mol) were added. The solution was about 30 minutes under reflux - boiled (100 102 ⁰ C). Then became

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■ with 34 ecm 37% hydrochloric acid (0.4 mol) decomposes and the solution evaporated. The residue was with 100 ecm 37 # Lger hydrochloric acid extracted and the insoluble sodium chloride filtered off. The piltrate was evaporated and 11 g of the crude product were obtained or 83 # of theory for GH-OCH -

chC; -

2 - ^CH 3

The product was formed by the formation of an insoluble lead salt » and washing cleaned. The free acid was by adding τοη Hydrogen sulfide regenerates *

Yield: 7.3 g

Analysis »23.0 * Pj 2.8 * Cl Theory 20.2 # P; no Cl

As determined by titration, the product was a Sweibasl acid with a molecular weight τοη 148.

Theoretical molecular weight! 154

The structure of the product was based on an analysis of its nuclear magnetic properties Resonance spectra (HMR).

Example 4 CTClic product and polymer | Sine solution clay 28.8 g

HIGH ₂ OH

in 500 ecm of water was made basic by adding τοη 200 ecm 1 η sodium hydroxide. The reaction mixture was heated to a temperature τοη about 95 to 100 ⁰ C erhiest, and further 200 cc of 1 η sodium hydroxide were added slowly over τοη 5-1 / 2 hours. The solution was evaporated in vacuo.

Yield of 0 P + IaCl »38.9 g

^ CH ₂ OMa

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Analysis »15.3 * Ρ * 17.8 * Cl (total) 17.75 * ionic Cl. The ratio τοη PjCI is equal to 1 ti.

D "e Papierchromategraphie showed _there oduct the ^p ^ not AusgangsTerbindung or CH-OCH ₂ PO ^ Ia _2. The R _f value of the product indicated a phosphinic acid.

The nuclear magnetic resonance spectra (HMR) confirmed this Structure.

CH- 0

Conversion to free JP and polymers.

CH ₂ OH

At about 1 to 2 ⁰ C a solution of 30.6 g

₂ ola + sodium chloride

(from the example above) (0.155 mol, based on the P analysis) decomposed in 150 ecm of water with 39 oca 4 η hydrochloric acid. The solution was stirred at 10 - 20 mm Hg pressure and a temperature Ton 20 to 4O ⁰ C evaporated Anachlieseend 200 cc of cold acetone were added. The mixture was filtered to remove the sodium chloride and the filtrate was ^{evaporated at a temperature τοη about 10 to 15 0} C under vacuum. 18 g of a liquid product are obtained. As determined by titration, the crude product was a monobasic acid with a molecular weight τοη 126.

Theoretical «molecular weight t 126. After drying (over P ₃ O ₅ at 25 ⁰ C) gave a yield τοη

16.7 g.

Theoretically «Yields 16.75 g.

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The Heutralisationeäquiralent after drying was 226, After drying at a temperature ron 10O ⁰ C under 1 to Hg pressure calibration seen was no weight loss.

Neutralization EquiTalent (found) t 306.

after further heating, the product polymerized to a thick one Syrup, which was confirmed by the nuclear magnetic resonance spectrum.

Example 5

CH ₃ OGH ₂ F-OH J.

A solution τοη 58 g

HIGH ₂

ClCH ₂

(0.41 mol) in 50 g of water was reacted at a temperature τοη about 80 to 100 ⁰ C with a dispersion τοη 12.5 g of calcium oxide in 100 g of water. The reaction was completed by adding clay 8.0 sodium hydroxide (0.2 mol) in 50 g of water and heating. ^B »was filtered off with a further 16 g of sodium hydroxide Tersetst and the calcium hydroxide formed. The solution was treated with 84 ml of 37% hydrochloric acid and evaporated. The residue was extracted with 200 μl of 37% hydrochloric acid and the insoluble sodium chloride was filtered off. The piltrate was evaporated and 45 g of the product were obtained.

Theoretical yield 49.6 g
Analysis 1 24.6 * P; 1.1 * Cl
Theory »25.0 * P; no Cl

The product is a liquid with a refractive index τοη NJ = * 1.4553 · As the titration showed, it was egg monobasic acid with a molecular weight τοη 126.

? 0 9 8 1 Π / 1 8 0 1

Theoretically ·· Molecular weightι 124 « Pas nuclear magnetic resonance spectrum confirmed dl structure Example 6

line solution ron 28.8 g ^ \ (0.203 MeI) in

ClCH ₂ O

100 cc of ethanol was erhltst under reflux and treated dropwise 150 com ethanol, the 1st been with 5.05 g sodium (0.22 mole) was reacted ψ, eugesetet. Pas solvent was evaporated and since ^f _s roduct extracted with 100 era Blftthyläther of sodium chloride. After filtering off the sodium chloride, the filtrate was evaporated. "

Roe deer yields 14.5 g (liquid) Pas ^ roduct was purified by distillation. Boiling point at 0.3 mm Hg bridges 80 ° C. Refractive index! Ijj ⁵ «1.4350 Analysis! 20.05 * P J 0.56 * Cl Theory 20.04 * P; no Cl

for CH ₅ OCH ₂ - P - CH ₅
OC ₂ H ₅

Example 7 Manufacture ren S

OH

line solution ren 35 g (ClCHg) ₂ - P

(0.215 MeI), 100 g water, 8.6 g latriumhydroxye (0.215 mol) and 17.2 g of sodium sulfide (0.22 mole) was slowly about within

2 0 9 8 1 Π / 1 8 0 1

one hour to a temperature of about 6O ⁰ C ron heated. The solution was then heated for about 2 hours under Rückflußβ (100 to 102 ⁰ C). Subsequently, "19.5 ce" of 37% salic acid was replaced (0.23 hol) and the solution was evaporated to remove the solvent. 100 cc of 37% hydrochloric acid were added to this residue. The mixture was filtered to remove insoluble sodium chloride. Then lead acetate was added to precipitate out all of the raw dibasic acids as impurities and to remove them by filtration.

The filtrate was evaporated and a colorless one was obtained Solid as product. Yield about 21 g.

Analysis * 24.1 * ^ J 22.2 * S

CR ₉ 0

Theory for S Ρζ "25.0jt F $ 25.8 * S

"^ \ OH

Melting point! 98 - 100 ^tt C,

As determined by titration, 'it was deas Product around a monobasic acid with * i: n® & exact molecular weight.

The nuclear magnetic resonance spectra showed a sharp line. The product has the same structure as

ν f »It the Abweiohuaf that

^x _ψ ixt 4ea Tlerclledrigea Ria "

\ 0 is replaced by 8.

^X Ola

If T is Sohweftl, it is found that the Sohw # f «l« In · leih · ▼ · »1 Wö« t · * 6 to «·! ·« «Tnaft. Si ·· ke * ent * t T «i>» ijtAiuac «a der

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^(H 2> b ^{H (} Va ^H

⁽ Vd ^H <Vc ^H

where alia variables, with the exception of ron x, have been explained above and χ is an integer τοη about 1 to about 6 These compounds are prepared in the same way as sulfur analogues with the exception that an alkali polysulphide such as Matriuapolyeulphid, ie Ia ₂ S _x , instead of τοη Vatrlunsulfid is used. The other reaction conditions remain essentially the same.

These compounds are useful as lubricating oils, as rubber vulcanizing agents And as a sulfur welchacher, these compounds with a higher degree of sulfur can also be easily polymerized.

Example 3 Sine Löeun «τ» η 1g 8. F>. , 20 | water and

g 50% in the 14 "rige * VatriiamhytexyA was ridden" 6 StuUa "under (100 si" 105 * 0) ". Αλλ ilittr Jlmmt

»La» mnttomlmfa * S *** · alt atr Stan & tar

(Ml) ere «* (« la * d-Sp # ktr «a wmvn aeajeaie« n of Ib, similar to the oxygen analogues formed in Examples 1 and 2).

2098 16/180 1 ORIGINAL BATHROOM

Claims (1)

AS Π68011 PiTEHlAISPEUCHEt 1. Technique for making clay compounds of the formula e ^H <* 1> a ^H0 t I Il H-C-Y-C-P-A <V * ^H <W ^XoM wherein R ₁ , R ₂ , R · and Rj are hydrocarbylene groups with 1 to 18 carbon atoms, A is a hydroxyl group, a hydroearbylexy group containing 1 to 18 carbon atoms, a hydrooarbyl group containing 1 to 18 carbon atoms, or a metal salt group of the formula OM, where M is an alkali metal is, Y is a chalcogen with a molecular weight τοη below 40 and a, b, · and d are integers with a value τοη 0 to 1, characterized in that a phosphorus bond of the formula (H ₁ ) _a H wherein R ^, R «, R *, Rj, A, a, b, ο and d have the meaning given above, X is a halogen atom and X * is a halogen atom or a hydroxyl group, at about 0 to about 15O ⁰ C with a Baee of the formula MYH umeetst, in which M is an alkali metal and Y has the meaning given above, with more than 5 moles of the base being used per mole of the phosphorus compound « 2. The method according to claim 1, characterized in that a base of the formula MOH reacts with a phosphorus compound, 2 0 9 8 1 Π / 1 8 0 1 where X and X ^{1 of} the formula are chlorine. 3. The method according to claim 1, characterized in that a base of the formula MOH is reacted with a phosphorus compound, where X is chlorine and X ^{1 of} the formula is a hydroxyl group · 4. The method according to claim 1, characterized germinated * · ⁰ * ¹ * ¹ * * used "that oan a phosphorus compound, wherein A represents the formula is a hydroxyl group. 5. Yerfehren according to claim 1, characterized in that Man a phosphorus compound is used, where A of the formula a fe is a hydrocarbyloxy group having 1 to 18 carbon atoms. 6 «The method according to claim 1, characterized in that one a phosphorus compound is used, where A of the formula is a hydrocarbyl group having 1 to 18 carbon atoms 7 · The method of claim 1, characterized in that "performs the reaction at about 20 to 10O ⁰ C. 8. The method according to claim 1, characterized in that one acidify the product before extraction in order to Obtain phosphoric acid compound zv. W 9 · The method according to claim 1, characterized in that one a phosphorus compound is used, where a, b, ο and d of the formula mean the value 0. 10. The method according to claim 1, characterized in that one al * phosphorus compound a compound of the formal used. 20981 R / 1801 11 · Terfahren according to claim 1, characterized in that a base of the formula MSH is used · 12 · The process of establishing a cyclic ether linkage Formula 4 <«2> b ^H <« 1> a ^{H (1} 4> a * ^ V wherein I ₁ , I ₂ , E and 1. Hydrooarbylengruppsn with 1 to 18 carbon atoms, A is a hydroxyl group, a hydroearbyloxy group with 1 to 18 carbon atoms, a Hydroearbylgruppe with 1 to 18 carbon atoms or a metal group of the formti OM, where M is an alkali metal , Y is a chalcene with a molecular weight of less than 40 and a, b, ο and d gan & o mean numbers between 0 and 1, characterized in that a phosphorus compound of the formula (I ₁ ) _a H where X means a halogen breath, at about 0 to 150 ° C with the iMiMkiB term of the valve tHI «Motst, where X« in alkali metal, Y «I« fTaaüVftfen «« 4 H ei »« aaear material atom, where I »mol 4er lm "epaArrer% indunf about 1 bie 5 HTI of Mmmm einge- ■ • did become · 15. The method makes claim 12, characterized in that you reject a base of the formula MOH is used. 20981 «/ 1801 17680 Π 14. The method according to claim 12, characterized in that «one the reaction is carried out at about 20 to 10 ° C. 15. The method according to claim 12, characterized in that ■ a base of the formula MSH is used. 16. Process for the preparation of compounds of the formula: where I ₁ , R ₂ * ^s x ^ ^{4 R} 4 hydroearbylene groups from 1 to 18 carbon atoms, a hydroxyl group, a hydrocarbyloxy group from 1 to 18 carbon atoms, a hydroearbyl group with 1 to 18 carbon atoms or a metal group of Foreel OH, where M is an alkali metal, χ is an integer τοη 1 to 6 and a, b, β and 4L mean numbers τοη 0 to 1, characterized in that one is a compound of the formula J ^ FA X- 0 where X «la halogen let, ImI #tw» 0 Ms 1 * 0 * 0 alt a basic compound of the fojmtl 3 ^ <S) _e # worl »Il« la Ukalleetall 1st, sS »Ine» ** trlxaBf * Xym * ltU _t «as« tn » V & t · fte Hol dtr Fhospfaor ·« tiMi f to · * «§ 5 H» 3. έ & τ .1Mb «ellgte ^ ftt« «rdon« 17 · Verblaa «ae of Fonteli 209816/1801 BATH ORIGINAL wherein IL, R ₂ »R * and R. Hydrocarbylene groups with 1" to 18 carbon atoms, a, b, c and d integers from 0 to 1, λ a hydroxyl group, a hydrocarbyloxy group with 1 to 18 carbon atoms, a hydrocarbyl group with 1 to 18 carbon atoms or an OH group in which M is an alkali metal and Y is a chalcogen with a molecular weight τοη below 40. 18. A compound according to claim 9 »wherein Y of the formula is oxygen means. 19. A compound according to claim 9 »wherein Y is the ϊοχββΐ sulfur means. 20. Compound of Formula CH ₂ OHa 21. Compound of Formula ^CH 2 OH 22. Linking the formula Ol 25 · Defense ύ · τ 9 · »· 1ι , S ^ * 2s ^ S where χ a · laas · Sahl τ · »(S) / ^p \ ^ 2 bif 2 0 9 8 1 B / 1 8 0 1 ^ CH. OH 24 · Connection of form ·! OH ₅ - O - OH - P; OH- - 25 · Terbl tune of the Porael OH - S - CH ₂ - P 26. Polyoieres the Porael 0 OH OK • OH OH HOCH ₂ -P- CH ₂ --0-P- CH ₂ - - 0 - P - Cl OH CH * ⁿ OHv-H OH ₂ OH OH ₂ -O where η is a yarn number with a value ron about 5 to about 100 means. 27 · Hatriumealjs the polyaieren connection according to claim 26. PtIr Stauffer Chemical Company Hew York, V.T., 17, TStA. Lawyer 209816/1801