DEF0000719MA - Process for the preparation of organic chlorine-containing phosphoric acid derivatives - Google Patents

Description

PROCESS FOR MANUFACTURING / 'yj> rr phosphoric acid

The present invention relates to a process for the production of chlorine-containing phosphoric acid derivatives of the general formula

Z = P-OY

\ b.

In this formula, X denotes an alkyl, cycloalkyl, aralkyl or aryl radical which is bonded directly or via oxygen to the phosphoraton, Y denotes an alkyl, cycloalkyl, aralkyl or aryl radical, and Z denotes oxygen or sulfur, with at least one of the ⁵ best X and Y is substituted by chlorine.

'' "an arrives at such compounds through condensation of compounds of the formula

- X

Z = P ^ - Cl

^ns CI

With hydroxyl group-containing compounds of the formula Y - OH and subsequently saponification of the condensate products obtained to the free ester acids.

Examples of phosphorus phosphonic dichlorides which can be used are alkyl, cycloalkyl, aralkyl or Ar: 1 phosphonic acid dichlorides H-POCl ₂ , for example ethyl propyl, butyl aryl, hexyl, acetyl, dodecyl, hexadocylphosphonic acid dichloride or Gex. isehe these compounds as aliphatic technical Gecischen K srwassex-stoXfe ¹ Zl are obtainable by simultaneous action '' of phosphorus and oxygen, ferrer Cyclohexy -, benzyl, phenyl or Tolylphosphonsäurechl ORID the halosen ^ ^ e alxi descendants of these £

Series, such as those obtained, for example, by direct chlorination from the aforementioned chlorides or starting from halogen-containing Hydrocarbons are available, e.g.

Chlorobutylphosphonic acid dichloride _{CH 0 Cl.POCl n} -or ~~? 4 8 2-

p-ChlorphenyLphosphoRsäuredichlorid CGH ₄ Cl.POCl ₂ · It can be PO (OR) Clg, such as Ph ο ο s ph e rs CDCR no no ät hy 1 on the other hand also of Phosphorsäurenonoalkyl-, cycloalkyl -j aralkyl or aryl ester chlorides - ρ ro py 1 -, b ut y j - amyl, hexyl, octyl, eyelohexy1-, benzyl, phenyl-esterdiehlorid, or the corresponding ^ f in Kohlenwasserstof rest ha logenierten compounds such as _{s-zBPhosphorsäure} ehloräthyl-. Use, p-ehlorphenyl2, 4-dichlorphenylfesterdi chi or id.

The hydroxyl-containing components are the monohydric alcohols of the fatty series, cyclic alcohols and phenols, such as ethyl, propyl, butyl, amyl, HexyX, octyl, dodecyl, benzyl alcohol, cyclohexanol, methyl TeiSio hexanol, phenol ₅ cresol, naphthol or the halogen substitution products such as _i Glykolchlorhydrin, Chlorcyclohe χ anol, p-chlorine "phenol, 2 _s 4-dichloro / phenol, inter alia, applicable.

The following products, for example, can be manufactured using the process:
Butylphosphonic acid p-chlorophenyl ester

C ₄ H ₉ -PO (OC ₀ H ₄ Cl) - OH, ρ-chlorophenylphosphonic acid chloroethyl ester acid

ClC ₆ H ₄ . PO (OC ₂ H ₄ Ol) - CR, phosphoric acid p-chlorophenyl-isdhexyl ester acid

PO (OC ₆ H ₄ Cl) (OC ₆ H ₁₃ ) _ _0H?

Chlorcyelohexyl-phosphonic acid-phenylester acid

Cl, C ₆ H ₁₀ .PO (OC ₆ H ₅ ) - OH ₅

Phosphoric acid dichlorophenyl butyl ester acid

PO (OC ₆ H ₃ Cl ₂ ) (OC ₄ H ₉ ) (OH), doaecylphosphonic acid p-chlorophenyl ester acid C ₁₂ H _25i PO (OC ₆ H ₄ Cl) (OH).

The condensation is expediently carried out with equimolecular mencenes of the phosphorus-containing acid chloride and the Components containing hydroxyl groups through: the use of a solvent and diluent such as carbon tetrachloride, ali ph s t iic carbon w a se rst o ff e «τ, α — d-e-rg-1. is not required in most cases.

The information to be with elimination of hydrochloric acid-binding Konaensation can by additive viie example, ammonia, Dirriethylanilin _s pyridine, jab4- ■ de-pg-l. influence favorably.

In most cases it is advisable to accelerate the reaction by heating or at a higher temperature to finish. In general, the condensation can be carried out within the temperature range from + 20 ° to 250 ° perform and easily determine the most favorable temperature for the specific implementation. This is due to the condensation of acid chlorides with phenols and halogen-containing osy compounds are higher than with alcohols and halogen-free ones Hydroxyl compounds.

The reaction products obtained are either hydrolyzed directly to give the free ester acids, for example by stirring with water, if necessary at elevated temperature, or men saponified with dilute alkalis or Carbonates of the alkalis or alkaline earths to the. corresponding salts, which are broken down with dilute kineralsic acids.

The compounds can be used as acids or in the form of their water- or oil-soluble salts, e.g. as alkali, ammonium, Calcium, barium, zinc and tin salts or as salts of higher molecular weight aliphatic or cyeloaliphatic bases are used for a variety of purposes, e.g. as a pesticide, for corrosion protection and as additives to improve the properties of lubricating oils.

Examples

1.) 175 parts by weight of butylnhosphonic acid dichloride are mixed with 126 parts by weight of p-chlorine / phenol for 6 hours, increasing from 180 ° -250 ° _? heated until the evolution of hydrogen chloride has ceased. Fractionation in vacuo gives 140 parts by weight of butylphosphonic acid p-chlorophenyl ester chloride C ₄ H ₉ . PO (OC ₆ H ₄ Cl) C1 with a boiling point of 145 ° -149 ° at 0.6 mm Hg. The ester chloride is saponified with a solution of 42 parts by weight of caustic soda in 250 parts by weight of water, and the free butylphosphon-p-chlorophenyl _{ester acid C 4} H ^ PO (OCgH ₄ Cl) OH is precipitated from the resulting solution as an oil which is solidly insoluble in water. The acid is taken up in an inert solvent, v / ie, for example, methylene chloride, the solution is washed with water, dried and the solvent is evaporated. The acid forms a light yellow syrup and, like suitable salads, such as the stearylainine salt ₉ , is easily soluble in mineral oils.

2.) In 245 parts by weight phosphoric acid p-chlorophenyl ester

dichloride lets 74 parts by weight of n-butanol flow in over the course of 2 hours while stirring and cooling. The mixture is stirred for 1 hour at room temperature and heated to 40 ° for 2 hours. The exposure product freed from the dissolved hydrogen chloride by blowing out with air, which essentially represents phosphoric acid D-chlorophenyl-n-butyl ester-eh] oride PO (OC ₆ H ₄ Cl) (OC ₄ H ₉ ) Cl, is saponified with dilute sodium hydroxide solution, and from the solution of the sodium salt obtained, by adding hydrochloric acid, ^{precipitated the free phosphorus 1} -P-chlorophenyl-n-butyl ester acid PO (OC ₆ H ₄ Cl) (OC ₄ H 4) OH as an oil which was almost insoluble in water. The product, purified as in Example 1), forms a straw-colored, thin syrup that is soluble in mineral oil.

3 ») In 245 parts by weight of phosphoric acid p-chlorophenyl ester dichloride PO (OC ₆ H ₄ Cl) Cl _2, while stirring and cooling at 20 °, 102 parts by weight of deformed 2-ethyl-n-butanol are run into Luftstrones and heating to 40 ° for a further 2 hours after lan & to about 36 parts by weight of hydrogen chloride escaped. the Realitionsprodulct then provides ir. substantially PTfOCgH Phoäphorsäure-p-chlcrphenyl-2-äthylbutylester-ehlorid ₄ Cl) (OCH ₂ CH (C ₂ H ₅ ) ₂ ) C- _dar ^ _{dgs dlirch Vei.seifeE Qit dilute sodium hydroxide solution and disintegration of the} sodium salt obtained with hydrochloric acid as in Example 1) is further processed to the free ester acid. The acid, as well as suitable salts, for example Stearylainine salt _{9 is} easily soluble in mineral oils.

Claims (1)

Claim: Process for the preparation of ¹ ₁ chlorine-containing phosphoric acid derivatives, characterized in _{that 3} compounds of the formula Z = ρ - Cl wherein / x denotes an alkyl, cyeloalkyl, aralkyl or aryl radical which is directly or via oxygen to the Phosphoratorr. May be bound, rit connections of the Forrael Y - OH, in which Y denotes an alkyl, cycloalkyl, aralkyl or aryl radical, at least one of the radicals 7 and Y being substituted by chlorine, condensed and the fondensation products saponified to give the free esthetic acids.