DD238980A1 - METHOD FOR THE PREPARATION OF CHLORIDES OF THE TETRAKOORDINATED PHOSPHORUS - Google Patents

Abstract

The invention relates to a process for the preparation of chlorides of the tetracoordinate phosphorus of the general formula R1 (R2) P (O) Cl. Such compounds are widely used as important intermediates in the chemical and laboratory industries. They are used, inter alia, for the synthesis of highly refined biocidal phosphorus organics. The preparation of the compound is achieved by direct reaction of trivalent phosphorus compounds R1 (R2) (R3O) P with organic ammonium halides and a phosphorus hydrocarbon.

Description

Field of application of the invention

The invention relates to a process for the preparation of chlorides of tetracoordinated phosphorus of the general formula .1

where R ¹ , R ² = organic radicals, such as alkoxy, alkylthio, arylthio, Aroxygruppen, ring systems, dialkylamide, Diarylamid- and / or Alkylarylamidgruppen may be

Such compounds are widely used as important intermediates in the chemical and laboratory industries. They are used, inter alia, for the synthesis of highly refined organophosphorus biocides, medicines, lubricant additives and flame retardants.

Characteristic of the known technical solutions

Compounds of the above formula are shown so far:

1. by reaction of POCl ₃ with the corresponding HO, HS or HN nucleophiles (alcohols, phenols, amines, mercaptans, thiophenols, etc.).

(HOUBEN / WEYL, Methodend.Org. Chemie., 4th ed. 1964, Georg Thieme Verlag, Stuttgart, Vol. 12/2 /)

2. by reaction of trialkyl phosphites with elemental chlorine

 (H.McCOMBIE, B.C.SAUNDERS, J.Chem.Soc., 1945, 380)

The disadvantages of just listed methods consist in the fact that during the reaction strongly corrosion-promoting and polluting substances arise (hydrogen chloride, Verf. 1) or are used (chlorine, Verf. 2).

Object of the invention

The aim of the invention is to enable a new, economically favorable synthesis of the title compound under mild conditions in high yield.

Explanation of the essence of the invention

The object of the invention is to obtain the title compound in high yields in a process step without formation or use of hydrogen chloride or elemental chlorine.

As organophosphorus starting materials are to serve mainly compounds that are accessible in one step from elemental phosphorus.

It has been found that chlorides of tetracoordinated phosphorus of the general formula

where R ¹ R ² = can be organic radicals, such as, for example, alkoxy, alkylthio, arylthio, aroxy groups, ring systems, dialkylamide, diarylamide and / or alkylarylamide groups

by direct reaction of trivalent phosphorus compounds R ¹ (R ² ) (R ³ O) P, where R ¹ and R ^{2 may be} the above-mentioned and R ³ = alkyl groups, with an organic ammonium halide R ⁴ R ⁵ R ⁶ NHX, where R ⁴ " ⁶ = alkyl, aryl groups or ring systems and X = Cl, Br, I can be obtained and a Polychlorkohlenwasserstoff C _m H _n CIk be obtained with or without solvents in high yields

 The general reaction equation is:

R ¹ (R ² KpA)) P + "R ⁴ R ⁵ R ⁶ ITHX + CHCL - R ¹ (R ² ) P (y) Cl

J JjL iv

⁺ ' ^C m ^H n ₊ 1 ^Cl k-1 + A ⁵ * ⁶ N + A

The resulting by-products can be easily separated from the reaction mixture, so that isolation of the synthesized title compound is easily possible. The process according to the invention has the following decisive advantages:

1. The reaction takes place in one process step under mild conditions

2. The organophosphorus starting materials are largely accessible to LEHMANN (WP 127188 DD) directly from elemental phosphorus

3. There is no polluting and corrosive hydrogen chloride

4. No expensive and toxic chlorine is needed

5. The method is applicable to a large range of compounds

6. It can be used as a by-product in many organic syntheses resulting Aminhydrohalogenid as a reactant

embodiments

The preparation of the target compound is carried out according to the following general rule: A mixture in molar ratio

R ¹ IR ² KR ³ O) PiR ⁴ R ⁵ R ⁶ NHXiC ₁ H _n CU = 1: (> 1): (> 1)

is reacted with exclusion of air and moisture with constant stirring. The chlorohydrocarbon, for example CCI ₄ , is added slowly while the remaining reactants are preferably initially charged in an inert, polar solvent, for example acetonitrile. To accelerate the reaction it is possible to work at a slightly elevated temperature.

Example 1:

Preparation of phosphoric acid diethyl ester chloride (C ₂ H ₅ O) ₂ P (O) Cl

To a mixture consisting of 0.03mol triethyl phosphite, (C ₂ H ₅ O) ₃ P and 0.04mol trimethylammonium, (CH ₃ J ₃ NHI in 35ml dry acetonitrile, with constant stirring at 45 ° C 0.03 mol of carbon tetrachloride , CCI _4. The mixture is stirred for a further hour at the same temperature and the yield of (C ₂ H ₅ O) ₂ P (O) Cl determined by ³¹ P-NMR is

Example 2:

Preparation of phosphoric acid dibutyl ester chloride (C ₄ H ₉ O) ₂ P (O) Cl

To a mixture consisting of 0.03mol tributyl phosphite, (C ₄ H ₉ O) ₃ P and 0.045mol triethylammonium, (C ₂ H ₅ I ₃ NHI in 40 ml acetonitrile, 0.031 mol CCI _{4 are} added dropwise with constant stirring at 50 ° C. The mixture is subsequently stirred for a further 4 hours and the yield of the target product determined by means of ³¹ P-NMR spectroscopy is 70%.

Claims (4)

Invention claim: 1. A method for the preparation of chlorides of tetracoordinated phosphorus of the general formula P-Gl ₂ ^ I! where R ¹ , R ² = organic radicals, such as alkoxy, alkylthio, arylthio, Aroxygruppen, ring systems, dialkylamide, Diarylamid- and / or Alkylarylamidgruppen may be characterized in that in a single process step, a trivalent phosphorus compound R ¹ (R ² ) (R ³ O) P, wherein R ¹ and R ^{2 may be} the above and R ³ = alkyl groups, with organic ammonium halide R ⁴ R ⁵ R ⁶ NHX, where R ⁴ " ⁶ = alkyl, aryl groups or ring systems and X = Cl, Br, I can be reacted and a Polychlorkohlenwassersoff C _m H _n CL _k reacted with or without solvent. 2. The method according to item 1, characterized in that is used as the organic ammonium halide predominantly TrialkylammoniumiodidoderTrialkylammoniumbromid. 3. The method according to item 1, characterized in that is used as the polychlorinated hydrocarbon predominantly carbon tetrachloride. 4. The method according to item 1, characterized in that the reaction is carried out predominantly in an inert, polar solvent, for example acetonitrile.