DE2200137A1 - Process for the preparation of esters of phosphoric acids - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

8 MUNICH 8O. MAUERKiRCHERSTR.

Dr. Berg Dipl.-Ing. Stopf, 8 Munich 80, Mauerkircherstraße 45

Your reference your letter Our reference date '* υ3Π. 1972

Lawyer file 21 926 Be / Sch

Monsanto Company St. Louis / Missouri / USA

"Process for the preparation of esters of phosphoric acids"

This invention relates to a process for the preparation of halogen-containing organophosphoric acid esters, and in particular an amine-catalyzed reaction of halides of phosphorus and thiol or hydroxyl containing organic materials.

002-21-2663 -2-

209831/1081

{^ 3310} Ttltflramm ·: BERGSTAP

70 43 ($ 8 70 43) 48 33 10 (9 * 33 10} Ttltflramm ·: BERGSTAPFPATENT MOndiin TELEX 05 24 560 BERG d Bank ι Bayeriiche Vtrainibanlc Munich 453100 PoiUchedti Munich 053

Numerous processes for the preparation of triorganophosphoric acid esters have been known for a long time. Naqh one of these Process uses a phosphoryl halide with a monohydric, organic compound without the use of one Catalyst implemented. Such a method is because of the long reaction times and the resulting low rates Yields not technically feasible. Further disadvantages of the method of this type are that it is necessary is to use excessive amounts of the monohydric, organic compound.

Another known method is to give certain Amines to the aforesaid reaction mixture to effect higher yields. So is in the U.S. ”patent

1 785 951 the use of certain aromatic amines, for example of aniline and pyridine, as catalysts for the production of triaryl phosphates from phosphoryl chloride and a phenol at high temperatures. Similarly, U.S. Patent

2,678 9 ^ 0 aromatic primary amines, for example aniline, and certain tertiary alkylamines, for example triraethylamine, are used as catalysts for the preparation of triaryl phosphates from phosphorus trichloride and a phenol. However, the specified processes relate exclusively to the production of triaryl phosphates and not to the selective production of halogen-containing mono- and diesters of phosphoric acids.

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220013?

According to further processes, the reaction is catalyzed with the formation of greater yields, for which purpose a metal is used Reaction mixture, such as copper powder, iron filings, calcium, Aluminum or magnesium, or a halide such as aluminum chloride, Magnesium chloride or boron trifluoride, or a Sulfate such as copper sulfate, or an oxide such as magnesium oxide or adding copper oxide.

The use of these catalysts brings various internal disadvantages accompanying them, to which low conversion of the starting materials and long reaction times to complete the reaction belong. As in U.S. Patents 2,610,978 and 2 652 018, an insoluble complex is formed during the reaction when aluminum chloride is used as a catalyst is used.

When alcohols with a phosphoryl halide either without a catalyst or with any of the above-mentioned catalysts, apart from magnesium chloride, undesired by-products are formed. These by-products lead to difficult distillation problems, low yields of the desired product and low reaction efficiency. The one disclosed in U.S. Patent 2,410,118 The processes described are typical distillation problems that occur described. In this process, the distillation is due to the high salt concentration of the

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different phosphoric acids in the distillation plant
difficult.

U.S. Patent 2,868,827 uses it
of titanium tetrachloride as a catalyst for the formation of
Organophosphate esters described. The disadvantages associated with the use of titanium tetrachloride are based on the fact that excessive and long times are required in order to obtain desirable yields and that they are relative

large amounts of metal halide catalysts are required
are. Furthermore, when the reaction is carried out in the presence of a titanium halide catalyst, recovery of the desired reaction product becomes a problem. It was found that upon completion of the reaction
it is necessary to wash the reaction mixture with a citrate or tartrate solution which forms a complex with the titanium catalyst. The complex is then removed by washing with water, after which the product obtained is dried.

Another disadvantage associated with the use of many of the above-mentioned catalysts is
in that complicated material handling procedures are necessary for the catalyst.

In addition, the production of organophosphoric esters is narrowed by means of the catalyzed reactions described above

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the manufacturer so that only. a specific type of " Organophosphoric acid esters of high purity can be prepared by means of the reaction. It would not be accordingly possible, compounds of high purity, such as oresylphenylchlorophosphoric acid ester, bromophenylphenylchlorophosphoric acid ester and the like. With the advance described method it would only be possible to use relatively impure triorganophosphoric esters or esters that are the same Contain aryl groups, for example triphenyl phosphate, To produce trieresyl phosphate and the like. There were therefore, in the preparation of the organophosphoric acid esters by the processes described above, the specific ones Organophosphoric acid ester contaminated by side reactions, the by-products only by long-lasting and difficult washing and distillation processes could be removed.

This invention relates to a new and improved process for the preparation of mono- and diorganophosphoric acid esters, in which the disadvantages of the method according to the prior art are eliminated and with the selective esterification is possible with high yields without significant contamination by by-products.

The object of this invention is achieved by means of a novel process in which one critical Combination of catalyst and reaction temperature for

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Production of * halogen-containing organophosphoric acid esters combined, whereby by means of the process a high yield of product with essentially no side reactions and impurities obtained and the stepwise formation of the ester is allowed in such a way that mixed Esters produced in a simple and economical manner will. As an example of the novel process of this invention, a compound such as chlorophenyl cresyl chlorophosphoric acid ester easily and cheaply manufactured while following those available in the prior art This method of manufacture is difficult and expensive. Mixtures of mono- and diorganophosphoric acid esters can also be used produced in the same reaction vessel and

by means of a distillation process without undesired disproportionation be separated.

Unexpected and surprising in the process of this invention is the fact that so far only different amines as catalysts for the reaction of, for example, phosphoryl chloride and phenol to produce triaryl phosphates are described, it has now been found that not all such amines give the same type of reaction Production of mono- and diorganophosphoric acid esters can catalyze under the process conditions of this invention. This is how aniline has been, among others Amine compounds, described as a suitable catalyst. In contrast, it was found that aniline in the

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The process of the present invention does not act as a catalyst, although dimethylaniline is suitable. It will it is believed that this difference is due to the difference in the basicity of the amines, which with respect to on the temperatures used in the present process is critical.

Wake up the method of the invention at specific Temperatures halides of phosphorus of the formula

- ^Z n

wherein X is oxygen or sulfur, YR or R ¹ X, wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, LeteroeyeIyI or aryl, R ^{1 is} alkyl or aryl, m = O when η = 3 and m = 1 when η = 2, Z is chlorine or bromine and η = 2 or 3, with a compound of the formula

(II) R ¹¹ XH,

where R "is aryl and X is oxygen or sulfur, reacted in the presence of an amine catalyst.

The course of the reaction of the process according to the invention runs through the following stages, the reaction of phenol with phosphoryl chloride being shown as an example will:

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fo \ - OL

+ POCl ₃ - ■> HCl + (0> - 0 - POCl ₂

OH + (0 / -0 - FOüia - ^ nux -t- _V \ 0) -oj ^ -POCl

The mono- and dihalophosphoric acid esters are valuable intermediates for the production of plasticizers, oil additives and functional fluids and are suitably prepared in accordance with the method of this invention and essentially produced in high yield without significant contamination by side reactions.

The amine catalysts used in the process according to the invention can generally be any area characterized by the presence of a nitrogen atom is that is suitable, in a liquid complex with the phosphorus portion of the formula I under the conditions of present proceedings. Essentially all amines that are suitable for forming such a complex are are intended as catalysts in this process. .

The concentration of catalyst that is most effective in the process is a function of many variables Sizes, but generally ranges from about 0.001 to 2.0 mol # based on the phosphorus halide. Preferably 0.01 to 0.1 mol # is used as

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practical amount viewed. Of course, larger and smaller amounts can be effectively used by (fine expert by Experience or attempt to be determined. It is therefore the The following compilation of amine compounds should only be viewed in such a way that the broad range of amines which are used as Catalysts are suitable to be pointed out because it would actually be impossible to use any intended amine to be specified individually.

Typical amines that can be used as catalysts in the process of this invention include the following compounds, which are given for illustration only and do not fall within the scope of the invention in any way should restrict, as has already been stated. Any amine is suitable provided that it is capable of complexing with the phosphorus portion of the formula without limitation to the number of carbon atoms in the amine molecule itself and without limitation with regard to the substituent groups that either have the carbon or nitrogen atoms of the amine are present

can. For example, an amine of the formula R - N "" 1

Compounds include wherein no more than two

the radicals R, R ^, and Ro are hydrogen and in which R, R ^, and Ro independently of one another alkyl, alkenyl, alkynyl, Cycloalkyl, cycloalkenyl, cycloalkenyl, aryl, heterocyclyl radicals or combinations and variations of these radicals, substituted or unsubstituted, are. Further-

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- ίο -

the radicals R, R ^ and R ^ can be linked to form a cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclic or aryl radical, both substituted and unsubstituted, and one of the radicals Ry and R ^ ocLer can both Rxi and Rp radicals form a ring closure with R to form an aryl, cycloalkyl, cycloalkenyl, cycloalkynyl or heterocyclic radical which may or may not be substituted. Furthermore, there is actually no limitation on the number of carbon atoms or other atoms in the amine molecule. The only restrictions on the type or structure of the amine used are therefore reasons of convenience and cost. The following compilation of connections takes place with this in mind.

Aliphatic and alicyclic amines, methyl amine ,, n-butylamine, tetramethylammonium chloride, Neopentylaminhydrochlorid, di-n-hexylamine, tridecylamine, diheptylamine, dimethyl-n-butylamine, Ditetracontylamin, trioctadecylamine, Dihexadecyleicosylamin, triethylamine, trimethylamine, cyclopropylamine, cyclohexylamine, dicyclohexylamine, i-cyclohexyl -2-aminopropane, tricyclopropylamine, methyl diethylamine, nonyldiundecylamine, isopropylarain, n-amylamine, di-n-butylamine, octadecylcyclobutylamine.

Aromatic amines

Toluidine, benzylamine, N-methylaniline, o-phenylethylamine,

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HN-dibutylaniline, N-methyl-alpha-phenethylamine, N-ethylm-toluidine, benzylmethylethylamine, 2-naphthylamine, alpha-aminoethylnaphthalene, 2-aminobiphenyl, ethyldiphenylamine, 1-arrainophenanthrene, triphenylamine, methyldibenzylamine, triphenylamine, methyldibenzylamine, triphenylamine, methyldibenzylamine, triphenylamine, thiopanthenylamine, thiophenophenylamine, triphenylamine, thiopanthenylamine, thiophenylamine, thiophenophenylamine, triphenylamine, methyldibenzylamine, N-ethylm-toluidine, triphenylamine, methyldibenzylamine Butylcyclohexylamine, dibenzylamine, NN-dimetb-ylaniline.
Heterocyclic amines

Furfurylamine, ethyleneimine, pyridine, 2-auiinopyridine, 1,5-di - ^ - piperidylpropane, piperidine, picoline, 2-aminom et hypiperidine, 1-furyl-2-aminopropane, 3-aminothianaphthenquinoline, 1-aminodibenzofuran, 2-aminoacridine, 3-atninodibenzothiophene, Pyridylamine, pyridoohinolinylainine, piperidinylamine, Picolinylamine, benzofuranylamine, butyl peridinylamine, Isoamylthienylamine, dipyridylamine, gresylfurfurylamine, Imidazole, 1-methylitnidazole.

Polyamines

Ethylenediamine, l'etramethylenediamine, hexamethylenediamine, i-diethylamino-2-aminopropane, diethylenetriamine, triethylenetetramine, Tetraethylene pentamine, pentamethylene hexamine, 1.2 — diaminocyclobutane, 1.4 — diaminocyclohexane, phenylenediamine, Triaminobenzene, 3 »3'-diaminobiphenyl.

Olefinic amines

Allylamine, diallylamine, triallylamine, p-aminostyrene, N-allylaniline, cis ~ p-aminostilbene, ethyl-3-pentenylamine, Octadecyl-6-decenylamine, decylcyclohexenylamine, di-n-

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propenylamine, 2-propenylcyclobutylamine, 2-butenyl-3-cyclopentenylamine, IQ-Qctadecenylphenylamine, 2-butenyltoluidylamine, Cyclohexylcyclohexenylamine, dicyclohexenylamine, 2-glyclobutenylfurylatin.

Acetylenic amines

3-dimethylamine-i-butyne, 5-dibutylamino - $ - heptyne, ßutyl - $ -

hexynylamine-6-an] inodecyn, decynylcyclohexenylamine.

Haloamines

Beta-bromoethylamine, i-amino-2-bromopropane, 1-dimethylamino-3-ctilorbutane, Chloraniline, fluoraniline, chlorobenzylamine, Aminobenzyl bromide, dibromobenzides.

Hydroxyamines

3-amino-i-hexanol, diethylaminomethanol, 3-amino-2-butanol, 5-diethylamino-1-pentanol, 2-aminocyclohexanol, 2-amino-2-cyclopentyl-1-propanol, Arainophenol, 2-anilinoethanol, 3-anilino-i-propanol, 4-amino-1-naphthol.

Amino ketones

Aminoacetophenone, 2-phenylamino-3? -Butanone, aminobenzo-

phenone.

It should be noted that the amine catalysts identified herein are used in the process of this invention are useful and desirable. The salts of the amines mentioned above with mineral acids, such as hydrochloric acid and sulfuric acid, and organic acids, such as benzoic acid and acetic acids, in the definition of the

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■ - 13 amines included »

Other amines contemplated as catalysts in the process of this invention are known and continue on pages 683 to 7 "Ί4 of Synthetic Organic Chemistry described by Wagner and Zook (Wiley and Sons, 1953).

The types of phosphorus halides used and prepared in accordance with this invention can be either starting materials or intermediates or end products of the
Be procedural. For example, phosphoryl halide can be a starting material used to make a ^{dihalophosphoric acid monoester such as an R 1} dihalophosphoric acid ester. The R'-dihalophosphoric acid ester can be an intermediate product in the production, for example a monohalophosphoric acid diester such as a di-R'-halophosphoric acid ester. At the same time, however, the R'-dihalophosphoric acid ester and di-R'-halophosphoric acid ester can be regarded as mono- and diester end products of the process according to the invention. The phosphorus halides used are known to the person skilled in the art. Many are commercially available and are easily made by the process of this invention. The compounds fall within the scope of general formula I and include compounds such as
for example:

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PhosptiorylhaloRenide:

Il

PZ thiophosphoryl halides;

P-Z

S.

Il

5 R'-DihaloRenphosphoric acid ester:

R. ¹ O 0
II
- P - Z ₂ O-R ^ Dihalosenttiiophosp hearing acid ester: R. ¹ O S.
Il
_ ρ _ ^Z 2 S-R-Dihalo-kenthiophosphoric acid ester: R.
SR dihalodithiophosphoric acid ester: ¹ p 0
Il ^Z 2

It

R ¹ S - P Di-R'-halophosphoric acid ester /

(R ¹ O) ₂ -P- 0, Q-Di-R'-halo-kenthiophosphoric acid ester:

(R ¹ O) ₂ -P-

Q.S-Di-R'-halo thiophosphoric acid ester:

0 ό «ο"

/ PZ R ¹ S

-15- 209831 / 1OtI

S.d.-Bi-R'-halodithiophosphoric acid ester:

(R ¹ S) ₂ - P - Z ₁

O.S-Di-R'-halodithiophosphoric acid ester:

BR ¹ O "

R ¹ S.

S. S-Di-R '-halogentrittiioplaosplioräureest er:

* - Il

(R ¹ S) ₂ - PZ ₁

R-Ptiosptionsauredihalogenide t

Il

RPZ ₂

R-Pkosphonthioäureditialogenide:

Il

RPZ ₂

Di-R-phosphinic acid halides;

Il

R ₂ -PZ,

Di-R-phosphinthioic acid halides;

Il - -C - Us

R ¹ R '-halophosphonic acid ester:

It

R ¹ O - P - Ζ _Λ

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R'R-HaloKenthiophosphoDäureester:

Il

R ¹ O -P ι

S-R'R-halothiophosphonic acid ester:

Il

R ¹ S -PZ ,,

ι I

R S-R'R- halodithiophosphonic acid ester:

Il

R ¹ S - P - Ζ _Λ R

In the formulas given above, R, R ¹ and Z have the meanings defined for general formula I.

As described in formula I, R is alkyl, for example methyl, ethyl, propyl, butyl, amyl, flexyl, heptyl, octyl, decyl, undecyl, dodecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl and eicosyl, in terms of structure straight or branched chain; Cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, ethylcyclopropyl, cyclohexyl, methylcyclopentyl, toethylcyclohexyl, decahydronaphthyl, bicyclohexyl (cyclohexylcyclohexyl), tetrahydrophenanthryl, tricyclohexylmethyl; Alkenyl, for example athenyl, propenyl, jßutenyl, isobutenyl, pentenyl, methylbutenyl, trimethylethenyl, hexenyl, heptenyl,

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20 ·· 31/10 · 1

Octenyl-, nonenyl, decenyl, dodecenyl, trideeenyl, hexadecenyl, octadecenyl, eicosenyl; Cycloalkenyl, for example cyclopropenyl, cyclopentenyl, cyclohexenyl, cyclohexylcyclohexenyl; Alkynyl, for example athynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, tridecynyl, octadecynyl, eicosynyl; Cycloalkynyl, for example i-cycloden-4-yl; heterocyclic R radicals with oxygen or sulfur in the heterocyclic ring, for example thiophenyl, furanyl, tetrahydrofuranyl, pyranyl, sulfolanyl; Aryl, for example phenyl, ilaphthyl, biphenyl, phenanthryl, anthracyl, terphenyl or quaterphenyl; and E ¹ alkyl or aryl as described with reference to R.

As described above, R and R ¹ can be unsubstituted or substituted. It should be noted that the afflink catalysts of this invention catalyze the preparation of halogenated organophosphoric acid esters according to this invention regardless of the type or extent of substitution of the radicals defined ^{in the context of β and R 1 above.} Therefore, the radicals represented by R and R ¹ may be substituted in any proportion, except for a carboxyl or hydroxyl group, which would interfere with the reaction.

The following residues are illustrative of substituents that R ₁ and R may groups denoted the amine catalysts ₂ occur at the by R and R * of the phosphorus halides and _R,:; -18-

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Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl and aryl as described above. Furthermore halogen, for example chlorine, bromine, fluorine, iodine} alkoxy, for example

ι -

Methoxy, propoxy, butoxy, hexoxy, decoxy; Cycloalkoxy, for Example cyclohexoxy, cyclobutoxy; Alkenoxy, for example propenoxy; Cycloalkenoxy, for example cyclopentenoxy; Aryloxy, for example phenoxy, naphthoxy; Cyano; Nitro; Isonitro; Aldehydes, ketones, alkoxycarbonyl, for example Methoxycarbonyl; Aryloxycarbonyl, for example phenoxycarbonyl; Alkylcarbonyloxy, for example acetyl; Alkoxycarbonyloxy, for example acetoxy; Arylcarbonyloxy, zaun example benzoyl; Alkylthio, for example ethylthio; Arylthio, for example phenylthio, llaphthylthio; Trihaloalkyl, for example trifluoromethyl; Alkylsulfinyl, for Example butylsulfinyl; Arylsulfinyl, for example phenylsulfinyl; Alkylsulfonyl, for example propylsulfonyl; Arylsulfonyl, for example phenylsulfonyl.

About specific phosphorus halides that are in the frame fall of this invention and which can be regarded as starting materials and / or desired products,

hear phosphoryl chloride, phosphoryl bromide, phosphoryl dibromide chloride, Thiophosphoryl chloride and broraide, phenyl dichloro, p-chlorophenyldibroni-, p-nitrophenyldichlor-, p-Nitrophenyldichlorthio-, cresyldichlor-, o-methoxyphenyldichlor-, Nonylphenyldichlorophosphoric acid ester,

20Ö831 / 10I1 " ¹⁹ "

-.19 - ■

Cumylphenyldichlor-, o-biphenyldichlor-, naphthyldichlor-, Isopropylphenyldichloro-, tert-butylphenyldichloro-, isodecyldichloro-, S-Phenyldichlorthio, S-P-Nitrophenyldichlorthio-, S-phenyldichlorodithio-, diphenylchlor-, Dicresylchlor-, O.O-Diphenylehlorthio-, S.S-Diphenylbromditliio-, S.S-diphenylchlorotrithiophosphoric acid ester, Phenylphosphonic acid dichloride, p-chlorophenylphosphonic acid dibromide, Methylphosphonic acid dichloride, chloromethylphosphonic acid dichloride, Butyl dichloro, hexyl dichloro, octyl dichloro, Decyldichlorophosphoric acid ester, phenylthiophosphonic acid dichloride, Cresylthiophosphonic acid dibromide, methylthio- phosphonic acid dichloride, chloromethylthiophosphonic acid di- chloride, phenylphenylchlorophosphonic acid ester, p-nitrophenylphenylchlorophosphonic acid ester, Cresylphenylchlorophosphonic acid ester, O-phenylphenylchlorothi © phosphoric acid ester, S-phenylphenylchlorodithiophosphonic acid ester, S-r-phenylphenylbromothiophosphonic acid ester.

The alcohols and thioalcohols as part of the general formula II include such compounds wherein R "aryl Bind, as discussed with respect to R and R ¹ for the phosphorus halides. R" are phenyl, alkylphenyl, halophenyl, arylphenyl, Cycloalkylphenyl _t naphthyl , Biphenyl, P.henanthryl, Anthracyl, Terphenyl, Quarterphenyl, substituted or unsubstituted radicals.

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Specific alcohols of the formula R ¹¹ XH that illustrate the types of compounds used include phenol, o- _r m-, p-cresol, o-methylphenol, jO-, m-, p-isopropylphenol, p-tert-butylphenol, p -tert-amylphenol, nonylphenol, 2.4-xylenol, 2.6-xylenol, 2.5-xylenol, 2.3-xylenol, o-, m-, p-chlorophenol-, p-bromophenol, p-iodophenol, 2.4-dichlorophenol, 2.4.5- Trichlorophenol, pentachlorophenol, o-phenylphenol, p-cumylphenol ^ o-cyclohexylphenol, alpha _T naphthol, beta-naphthol, o-methoxyphenol, p-athoxyphenol, o-phenoxyphenol, p-nitrophenol, p-trifluoromethylphenol, 2- allylphenol, 2-allylphenol Benzylphenol, vanillin, 4-chloro - $. 5-dimethylphenol, 4-chloro-1-naphthol, 2-chloro-4-nitrophenol, 4-cyanophenol, 2,4-di-tert-butylphenol, 2,4-dimethoxyphenol, methyl salic aat, 2-fluorophenol, p-hydroxyacetophenone, 4-hydroxybenzaldehyde, thiophenol, p-chlorothiophenol, ptert-butylthiophenol, thiocresol, thioxylenol, phenylthiophenol, thionaphthol, allylthiophenol.

The compounds of the formulas I and II as described above are well known and methods of making them are in standard and reference works refer to.

A preferred class of compounds of the formula I are compounds of the formula

^Y m - ^P - ^Z n

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where Y = R or R ¹ O, where R ¹ = aryl or substituted aryl and R, Z, m and η have the meaning defined in formula I. Typical compounds of this preferred class are phosphoryl chloride, phosphoryl bromide, Phenyldichlorphosphorsäureester, p-Chlorphenyldibromphosphorsäureester, Butyldichlorphosphorsäureester, Hexyldichlorphosphorsäureester, Octyldichlorphosphorsäureester, Decyldichlorphosphorsäureester, p-Nitrophenyldichlorphosphorsäureester, Gresyldichlorphosphorsäureester, · o-Methoxyphenyldichlor-, Nonylphenyldichlor-, Cumylphenyldichlor-, o-Biph'enyldichlor-, Naphthyldichloro-, isopropylphenyldichloro-, tert-butylphenyldichloro-, diphenylchlor-, dicresylchlorophosphoric acid esters, phenyldichlorophosphonic acid, p-chlorophenyldichlorophosphonic acid, methyldibroraphosphonic acid, chylomethyldichlorophosphonic acid, chylomethyldichlorophosphonic acid, chylomethyldichlorophosphonic acid, chylomethyldichlorophosphonic acid, chylomethylphenyl-chlorophosphonate, phenyl-chlorophenyl-phenyl-chloro-phenyl-chlorophenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-phenyl-chlorophenyl, chylomethyldichlorophosphonate, chloromethyl-phenyl-chlorophenyl-phenyl-chlorophenyl-phenyl-phenyl-chlorophenyl-phenyl-chlorophenyl-chlorophenyl, diphenylchlor-, dicresylchlorophosphorate.

A preferred class of compounds of the formula ± 1 are compounds of the formula R ¹ OH. Typical compounds of this preferred class are phenol, o-, m-, p-cresol, o-ethylphenol, o-, m-, p-isopropylphenol, p-tert-butylphenol, p-tert-amylphenol, nonylphenol, xylenol, o- , m-, p-chlorophenol, p-brqmphenol, p-iodophenol _s dichlorophenol, trichlorophenol, pentachlorophenol, p-cumylphenol, o-cyclohexylphenol, naphthol, methoxyphenol, ethoxyphenol, phenoxy

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phenol, nitrophenol, trifluoromethylphenol, allylphenol, Benzylphenol, vanillin, 4-chloro-J.5-dimethylphenol, 4-chloro-1-naphthol, 2-chloro-4-nitrophenol, gyanophenol, di-tert-butylphenol, dimethoxyphenol, methyl salicylate, Fluorophenol. Particularly preferred from this group are phenol, gresol, umylphenol, nonylphenol, chlorophenol, tert-butylphenol, xylenol, phenylphenol, isopropylphenol and their mixtures.

A specific class of alcohols which can be used in accordance with this invention are alcohols of the formula

(III) HO - R " ¹ - OH, where R" ^{1 is} isopropylidenediphenylene, for example

or phenylene, for example

is. Typical

Alcohols of this special class are isopropylidenediphenol, hydroquinone, catechol and resorcinol. .

In accordance with the process of this invention, the reaction between the phosphorus halides and alcohols for preparation proceeds of organophosphorus esters in two stages. When using the amine described above in conjunction the desired temperatures are obtained with specific temperatures

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Results of This Invention "Thus, in the presence of the zinc catalyst of this invention, the first chlorine is changed from, for example, phosphoryl chloride at a temperature of from about 85 to about 135 °", preferably 105 ° C. The second chlorine, ie the Disubstituierung, is substituted at a temperature of about 130 to about 165 ⁰ C, preferably 15O ⁰ G. Of course, the specific temperatures for mono- and disubstitution vary with the particular reactants used in each case, but the comparable differences in the temperature ranges for the stages of substitution remain approximately the same.

Accordingly, it enables the combination of the specific temperatures for the mono- and disubstitution of the desired Phosphorus halides, together with the catalysts of this invention, will give those skilled in the art mono- and diorganophosphoric esters to be produced in selected proportions. Diorganophosphoric esters can be produced in two stages , whereby a different alcohol is added at each stage. Mixtures of esters in a reaction vessel. For example, if you have a naphthyl group in the first Stage and a chlorophenyl group in the second stage, you can use the same phosphorus halide, however, simply introduce different suitable alcohols at the temperature levels indicated above so that

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one Naphthylchlorphenylchlorphosphorsäureester and ^ Naphthylaichlorphosphorsäureester receives. The different compounds can be separated, according to methods known to the person skilled in the art be won. Furthermore, selected proportions of different compounds can be used in the same reaction vessel getting produced. So, if you wish, a mixture of phenyldichlorophosphoric acid ester and naphthylphenylchlorophosphoric acid ester in ratios of 2: 1, with such selective proportions of the desired products according to the present invention by eating the intended proportion of any suitable alcohol in admitted to the separate stages.

! the following examples serve to explain more specifically Embodiments of this invention without the scope of the invention to restrict. It should be noted that according to the method of this invention Promotes reaction between virtually any phosphorus halide and any alcohol as defined above will.. ;

example 1

94 g of phenol are added to a mixture of 225 g of phosphoryl chloride and 2.6 g of aniline hydrochloride over the course of 2 hours at a temperature of 105 ° C. The temperature is held at 107 to 110 ^° C. for 2 hours, then it is cooled and the low-boiling substances are stripped off. The analysis

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of the residue shows that this is substantially phenol ₀

Example 2

To a mixture of 225 g and 1.6 g Phospiiorylchlorid ΪΓ.Ν-dimethylaniline to 94 g of phenol are for 2 hours at a temperature of 100-106 ⁰ C to. The temperature is kept at 105 to 110 ^° C. for 1 ^ 2 hours, then allowed to cool to room temperature and stripped off. The distillation yields $ 73.5 phenyl dichloro and $ 4.8 diphenyl chlorophosphoric acid esters.

■ Example 5

One 94 g of phenol are added to a mixture of 225 g of phosphoryl chloride and 1.6 g of 1-methylimidazole for 2 hours at a temperature of 105 to 107 ° C to, The temperature is maintained for 1 hour at 105 to 110 ⁰ C, then is cooled and stripped off. The distillation gives 198 g of phenyldichloro and 7.4 g of diphenylchlorophosphoric acid ester

Example 4

94 g of phenol are added to a mixture of 225 g of phosphoryl chloride and 2 g of diethylamine hydrochloride at a temperature of 105 ° C. over the course of 2 hours. The temperature is then raised to 110 ⁰ C and maintained for 2 hours, after stripping off and allowed to cool to room temperature. Distillation of the reaction mixture (212 g) gives 89.9 ° 1 ° phenyldichloro and 4.5 ° 1 ° diphenylchlorophosphoric acid ester

209831/1031

Example 5

To a mixture of 225 g of phosphoryl chloride and 1.6 g of pyridine is added 150 g of p-tert-butylphenol for 2 hours at a temperature of 100 ⁰ C to. The temperature is then increased to 110 ⁰ O and maintained for 2 hours, after which it is stripped off and cooled. The distillation of the reaction mixture yields 94.3 Jq of p- tert -butylphenyldichloric and 2.5 % di-p- tert- butylphenyl chlorophosphoric acid.

Example 6

115 g of phosphoryl chloride and 0.8 g of pyridine are placed in a reaction vessel. After 1 hour a total amount of 64 g £ is added and -0hlorphenol increased from 100 to 110 ⁰ C and maintained at this temperature for 1 hour and then gradually leave the pot temperature allowed to cool to room temperature. The reaction mixture is stripped and is obtained 108 g of product, from which, after distillation 93.7 $ o _- receives -ChIorphenyldiohlor- and 7.3 i <> Di-o.-chlorphenylchlorphosphorsäureester.

Example 7

^{94 g of phenol are added at 95 °} C. over 1 hour to a mixture of 225 g of phosphoryl chloride and 1.6 g of isoquinoline. The temperature is then increased to 105 ° C. and maintained for 2 hours. The reaction mixture is distilled off, whereupon 97 $> Phenyldiohlor- and 3 # Diphenylchlorphosphorsäureester get,

-27- ' 209831/1081

Example 8

225 g of phosphoryl chloride, 1.6 g Pyridine and 55 g of m-hydroxyphenol introduced and the pot temperature gradually increased to 115 ° Q and maintained for 3 hours. Vacuum is used and distillation of the reaction mixture yields 92.2 $ m-phenylenetetrachlorodiphosphoric acid ester.

Example 9 "

72 g of alpha- naphthol are added to a mixture of 113 g of phosphoryl chloride and 0.8 g of pyridine in the course of 1.5 hours at a temperature of 100 ^° C. The temperature is kept at 105-110 ° C. for 1½ hours and then stripped. The distillation yields 94.6 $ Baphthyldichlor- and 3.4 1 "Dinaphthylchlorphosphorsäureester.

Example 10

A mixture of 225 g of phosphoryl chloride, 1.6 g of pyridine and 114 g of 4,4'-isopropylidenediphenol is at 100-105 ° C 3 Heated for hours. The reaction mixture is allowed to come to room temperature cooling down. 4,4'-Isopropylidenediphenyltetrachlorodiphosphoric acid ester is obtained by distillation.

Example 11

225 g of phosphoryl chloride and 1.6 g of 2,6-lutidine are mixed in a reaction vessel. The addition of 94 g of phenol is made

209831/1081

started at a temperature of 95 ° C and carried out the total addition over 3 hours, during which time the temperature is increased to 105 ° C. The reaction is then further 1 V2 hours at 105 - 110 ⁰ C held, then is stripped and cooled. Distillation 91.7 receives i <> Phenyldichlor- and 5.2 $ Diphenylclilorphosphorsäureester.

Example 12

With a mixture of 225 g of phosphoryl chloride and 94 g of phenol, 1.6 g of quinaldine are added at 105 ° C. over 1 hour. The temperature is then 105 - 110 ⁰ C and increased obtained 2 hours, then stripped off the reaction mixture. After distillation, 76.7 fo phenyldichloro and 4.2 ^ diphenylchlorophosphoric esters are obtained

Example 13

(1) 188 g of phenol are added to 315 g of phosphoryl chloride and 3 »2 g of pyridine over a period of 2 hours at a temperature of more than 105 ° C. The temperature is maintained for 2 hours at 11O ⁰ C and then allowed to cool. The reaction mixture consists mainly of phenyl dichlorophosphoric acid ester.

(2) To the reaction mixture of (1) is added 188 g of phenol, and the temperature was raised for 2 hours at 150 ⁰ C. It is allowed to cool, and stripping the reaction mixture Phenyldichlorphosphor- säureester from. Distillation of the residue mainly supplies Diphenylchlorphosphorsäureester.

209831/1081

The following table explains further examples of the Reaction of phosphorus halides with an alcohol or trial alcohol in the presence of an amine catalyst.

Tabel

209831/1011

Tabel

ro ο co α> α »

Example phosphorus halide

14 phosphoryl bromide

15 thiophosphoryl chloride

16 phenyl dichlorophosphoric acid ester

17 o-methoxyphenyldichlorophosphoric acid

ester

18 phenyl dichlorophosphonic acid

19 chloromethyldibromophosphonic acid

20 phenyldichlorothiophosphonic acid

21 Phenyldichlorophosphonic acid ester

22 O-Phenyldichiorthi © phosphoric acid ester

23 S-phenyldibromothiophosphoric acid ester

24 p-Chlorophenyldibromophosphoric acid ester

25 Cresyl dichlorophosphoric acid ester

26 nonylphenyl dichlorophosphoric acid ester

27 Cumylphenyldibromophosphoric acid ester

28 Naphthyl dichlorophosphoric acid ester

29 phenyl dichlorophosphonic acid

30 cumyl dichlorophosphoric acid ester

31 Phenyldichlorophosphoric acid ester

alcohol

o-, m-, p-cresol o-ethylphenol xylenol
Nonylphenol

Thiophenol
o-methoxyphenol phenoxyphenol

4,4'-isopropylidenediphenol

Hydroquinone resorcinol

p-cumylphenol p-tert.amylphenol Pentachlorophenol phenoxyphenol p-bromophenol Nitrophenol nonylphenol fluorophenol

catalyst

Triethylamine hexadecylamine 3-amino-1-pentene 8-amino-1-nonadecene

Cyclopropylamine Cyelohexalamin 2-amino-4-cyclohexene Fixrfurylamine

6-amino-1-hexene

Phenylamine

Naphthylamine

Tribenzylamine

Imidazole

Ethylenediarain

p-phenylenediamine

Diallylamine

Ghloraniline

Aminobenz ophenon

Example 32

(1) To a mixture of 225 g of phosphoryl chloride and 1.6 g

1-methylimidazole is added to 109 g of Gresol over a period of 2 hours at a temperature of 105 g. The temperature is ^{kept at 105-110 0} O for 2 hours, whereby cresyldichlorophosphoric acid ester is obtained.

(2) The temperature of the reaction mixtures obtained according to (1) is increased to 135 ° Q and 109 g Gresol supplied to the reaction vessel over 2 hours "The temperature is maintained for a further 1 V2 hours at 150 ⁰ G, yielding Dicresylchlorphosphorsäureester get

Example 53

(1) To a mixture of 225 g of phosphoryl chloride and 2 g Diäthylaminhydrοchlorid is added during 2 hours at a temperature of 105-110 ⁰ G 94 g of phenol to. The temperature is kept at 110-115 ° C. for 2 hours, whereby phenyldichlorophosphoric acid ester is obtained.

(2) The temperature of the reaction mixture from (1) is increased to 135 ° C. and 109 g of Gresol are added to the reaction vessel over 2 hours. The temperature is maintained for a further 2 hours at 150 ⁰ C, thereby obtaining Greeylphenylohlorphosphorsäureester ·

Example 34

(1) To a mixture of 920 g of phosphoryl chloride and

1.5 g of methylamine are added to a mixture of 614 g of umylphenol

209831/1081

and 794 g of nonylphenol for 2 hours "at one temperature from 105 - 110 C to, whereby a mixture of cumylphenyldichloro- and nonylphenyldichlorophosphoric acid ester,

(2) The temperature of the reaction mixture obtained according to (1) is increased to 135 ° C. and 564 g of phenol are added over 2 hours. The temperature is kept at 150 ⁰ G for a further 1 * - / 2 hours, whereby a mixture of Cümylphenylphenylchlor- and Nonylphenylphenylchlorphosphorsäureester is obtained,

Example 35

(1) To a mixture of 225 g of phosphoryl chloride and methylamine 109 g of cresol are added over the course of 2 hours at a temperature of 105.degree. The temperature is 2 hours at Maintained 105-110 ° C, whereby cresyldichlorophosphoric acid ester is obtained.

(2) The temperature of the reaction mixtures obtained according to (1) is increased to 135 ⁰ G, and 94 g phenol is added during 2 hours at a temperature of 15O ⁰ C and this temperature was maintained for another 2 hours, thereby obtaining Cresylphenylchlorphosphorsäureester "

Claims : -33-

209831/1081

Claims (1)

Patent claims: Ii process for the preparation of organophosphoric acid esters, characterized in that one uses a phosphoric acid halide and an alcohol or thioalcohol reacts in the presence of an amine catalyst at a temperature of up to approximately 165 ° C » 2. Process for the preparation of organophosphoric acid esters according to claim 1, characterized in that that one is a phosphoric acid halide of the general formula Il Y - P - Z ^ m η wherein X oxygen or sulfur, YR or R ¹ X, R alkyl, alkenyl, alkynyl, cycloalkyl _? Cycloalkenyl, cycloalkynyl, heterocyclic or aryl, R ^{1 is} alkyl or aryl, m is 1 when η is 2 and m is 2 when η is 1, η 1 or 2 and Z is chlorine or bromine with a compound of the general formula R ¹¹ XH wherein R "is aryl and X is oxygen or sulfur at a temperature up to about 165 ° C in the presence of a catalytic amount of an amine reacts ₉ , this containing a nitrogen atom, which is responsible for compleac formation 209831/1081 with the phosphoric acid part of the phosphoric acid halide is suitable β 3. The method according to claim 2, characterized in that a compound is used in which R "phenyl, cresyl, gumylphenyl, nonylphenyl, xylyl, is tert-butylphenyl, phenylyl, isopropylphenyl and / or chlorophenyl, 4ο A process for the preparation of an organodihalophosphoric acid ester, characterized in that a phosphoric acid halide according to claim 2 with an approximately equimolar amount of a compound of the formula R ¹¹ XH according to claim 2 at a temperature of up to about 135 C in the presence of a catalytic amount of an amine which is reacted Contains nitrogen atom which is suitable for complex formation with the phosphoric acid part of the phosphoric acid halide, 5. The method according to claim 4, characterized in that a compound is used in which R "is phenyl, gresyl, cumylphenyl, nonylphenyl, xylyl, tert -butylphenyl, phenylyl, isopropylphenyl, and / or chlorophenyl» 6. The method according to claim 4, characterized that the organodihalophosphoric acid 209831/1081 is ester Phenyldichlorphosphorsäureester, Phenylyldichlorphosphorsäurester, Gresyldichlorphosphorsäureester, tert Butylphenyldichlorphosphorsäureester, Gumylphenyldichlorphosphorsäureester, Uonylphenyldichlorphosphorsäureester, Xylyldichlorphosphorsäureester, Isopropylphenyldichlorphosphorsäureester and / or Ghlorphenyldichlorphosphorsäureester. 7 β process for the preparation of diorganohalophosphoric acid esters, characterized in that an organodihalophosphoric acid ester with approximately the equimolar amount of a compound of the formula R ¹¹ XH according to claim 2 at a temperature of up to about 165 ° O in the presence of a catalytic amount of an amine is reacted Contains nitrogen atom that is suitable for complexing with the phosphoric acid part of the organodihalophosphorus ester " 8ο method according to claim 7 characterized in that the Diorganohalogenphosphorsäureester Nonylphenylphenylchlorphosphorsäureester and / or Gumylphenylphenylchlorphosphorsäureester ₀ 9. A process for the preparation of organophosphoric acid esters, characterized in that one in the presence of a catalytic amount of an amine containing a nitrogen atom capable of complexing with the '· -36- 209831/1081 Phosphoric acid part is suitable, (1) a phosphoric acid halide according to claim 2 with an approximately equimolar amount of a first compound of the formula R ¹¹ XH of claim 2 at a temperature of about 85-135 ° C to form an organodihalophosphoric acid ester, and (2) an approximately equimolar amount of a second compound of the formula R ¹¹ XH according to claim 2 is added to the reaction product of (1) at a temperature of about 130-165 ° C to form a diorganohalophosphoric acid ester. 10. The method according to claim 9, characterized in that the compound of the formula R ¹¹ XH is phenol, Cr es oil, curaylphenol, nonylphenol, xylene, tert-butylphenol, phenylphenol, isopropylphenol and / or chlorophenol. 11. Process for the preparation of organophosphoric acid esters according to claim 1, characterized that one is a phosphoric acid halide of formula ' ^Y m - ^P - ^Z n where YR or R ¹ O, R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclic or aryl, R ^{1 is} aryl, m is 1 when η is 2 and m is 2 when η is 1, η 1 or 2 and Z is chlorine or bromine 209831/1081 ~ ³⁷ " with an approximately n molar amount of a compound of the general formula R ¹¹ XH wherein R "is aryl and X is oxygen or sulfur is reacted at a temperature up to about 165 ⁰ O in the presence of a catalytic amount of an amine which is suitable for complex formation with a phosphoric acid moiety 12. Process for the preparation of organophosphoric acid esters according to claim 1, characterized in that that you have a phosphoric acid halide of the formula Y ^ -PZ _n m η YR or R ¹ O, R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclic or aryl, R 'is aryl, m is 1 when η is 2 and m is 2 when η is 1, n 1 or 2 and Z Is chlorine or bromine with an approximately η molar amount of a compound of the general formula R ¹¹ OH R "is aryl at a temperature of up to 165 ° C in the presence of a catalytic 209831/1081 table amount of an amine, which is suitable for complex formation with the phosphoric acid part, converts, 13. The method according to claim 12, characterized in that the compound of the formula R "is phenyl, cresyl, gumylphenyl, nonylphenyl, xylyl, tert- butylphenyl, phenylyl, isopropylphenyl and / or chlorophenyl. 14 «Method according to claim 12, characterized in that the amine is imidazole, 1-methylimidazole, diethylamine, pyridine, Ν, Ν-dimethylaniline, isoohinoline, 2,6-lutidine, quinaldine and Ieoquinoline and / or their salts, _% 15. Process for the preparation of organophosphoric acid esters according to claim 1, characterized in that a phosphoric acid halide is used formula Y - P - Z m η wherein YH or R ¹ O, R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocyclic or aryl, R ^{1 is} aryl, m is 1 when η is 2 and m is 2 when η is 1, η is 1 or 2 and Z is chlorine or bromine 209831/1081 - 59 - with an approximately η molar amount of a compound of the general formula HO - R ¹ "- OH
wherein R ¹ "Isopropylidendiphenyien -Bhenylen or at a temperature up to about 165 ⁰ O in the presence of a catalytic amount of an amine which is suitable for complex formation with the phosphoric acid part, transposed 16 “Process for the production of organophosphoric acid esters according to claim 12, characterized in that phosphoryl chloride is reacted with an approximately dimolar amount of a phenol at a temperature of up to 165 ⁰ C in the presence of an amine catalyst which is suitable for complexing with the phosphoric acid part. 17. The method according to claim 12 characterized in that the organophosphoric Diphenylchlorphosphorsäureester, Dicresylchlorphosphorsäureester, Cumylphenylphenylchlorphosphorsäureester, Cresylphenylchlorphosphorsäureester and / or _e is Wonylphenylphenylchlorphosphorsäureester 18. Process for the preparation of organophosphoric acid esters, characterized in that that (1) a phosphoric acid halide according to claim 12 with an approximately equimolar amount of a first compound 209831/1081 Formation of the formula R ¹¹ OH according to claim 12 at a temperature of 85-135 C, and (2) an approximately equimolar amount of a second compound of the formula R ¹¹ OH according to claim 12 to the reaction product of (1) at a temperature of 130 165 ^° C. in the presence of 0.001 to 2.0 mol based on the phosphoric acid halide, an amine with a nitrogen atom content that is suitable for complex formation with a phosphoric acid part. 209831/1081