DD301663A7 - Process for the preparation of pseudohalides of the tetracoordinate phosphor - Google Patents

Abstract

The invention relates to a process for the preparation of pseudohalides of the tetracoordinate phosphorus of the general formula R exp 1 (R exp 2) P (Y) Z. Such compounds are widely used in the field of biology, medicine, agriculture and forestry and in industry as biocides, drugs and valuable intermediates in organophosphorus chemistry. The preparation of a broad range of the title compound is possible by direct reaction of trivalent phosphorus compounds R exp 1 (R exp 2) (R exp 3 Y) P with trialk (ar) ylsilyl pseudohalides R exp 4 R exp 5 R exp 6 SiZ and a polyhalocarbon C Ind m H ind n X ind k R under mild conditions in high yield.

Description

Field of application of the invention

The invention relates to a process for the preparation of pseudohalides of the tetracoordinate phosphorus of the general formula

R ¹ , R ² = any organic radicals, eg. B. alkyl, alkoxy, alkylthio, Aroxygruppen, ring systems, dialkylamide, Diarylamidu nd / or Alkylarylamidgruppen,

Y = O, S,

Z = pseudohalogen groups can be.

Such compounds are widely used in the field of biology, medicine, agriculture and forestry and in industry as biocides, drugs and as valuable synthetic building blocks in organic phosphorus chemistry.

Characterization of the known technical solutions

The following methods are known for the preparation of pseudohalides of the tetracoordinate phosphorus:

1. Reaction of Phosphoric Chlorides of Phosphoric, Phosphonic, or Phosphinic Acids with Ionic Pseudohalides (G. I. KATSCH, Z. Chem., 9, 369 (1969); Ang. Chem. 81, 407 [19691]).

2. by reaction of compounds having a PH bond with free pseudohalogen, in particular with (SCN) ₂ (J. MICHALSKI, ROCZNIKI, Chem., Ann. Soc. Chim. Polonorum, 31, 585 (1957))

3. by cleavage of pyrophosphoric acid esters with alkali metal pseudohalides (G.W.KENNER, J. Chem. Soc. 1953,673).

The technical solutions listed under 1-3 require without exception as organophosphorus starting materials compounds which can not be obtained in one step from elemental phosphorus, but only over multi-stage processes usually from expensive phosphorus halides. The ionic pseudohalides used are poorly soluble in organic solvents and lead to the heterogeneity of the reaction, which has a negative effect on reaction time and yield.

Object of the invention

The aim of the invention is to find a new, economically favorable synthesis of a wide range of title compound under mild conditions with high yield.

Explanation of the essence of the invention The object of the invention is to triple said title compound while improving the economic parameters

coordinated phosphorus compounds, many of which are accessible by direct synthesis of elemental phosphorus, obtained.

It has been found that pseudohalides of the tetracoordinate phosphorus of the general formula

"^ * P-Z

R ', R ² = any organic radicals, for example alkyl, alkoxy, alkylthio-.Aroxygruppen, ring systems, Dialkylamid.Diarylamid- and / or Alkylarylamidgruppen,

Y = O, S,

Z = pseudohalogen groups

may be by direct reaction of trivalent phosphorus compounds R ¹ IR ² I (R ³ Y) P, where R ¹ and R ^{2 may be} the above-mentioned and R ³ = alkyl groups, with trialk (ar) ylsilyl pseudohalides R ⁴ R ⁶ R * SiZ, wherein R ⁴ "* may be alkyl or aryl groups and Z = pseudohalogen groups, and a polyhalocarbon compound C _m H _n X _k R, where X =» halogen and R = any organic radical, halogen or hydrogen, with or without Solvent can be obtained at a reaction temperature of -10 ° C to 8O ⁰ C in high yields.

In addition to the title compound, a halohydrocarbon and a Trialk (ar) ylsilylhalogenkohlenstoffverbindung. The general reaction equation is

S ^3- (S ² J (R ³ Y) P +, 1 ⁴ R ⁵ Il ⁵ SiZ + CH X. R

J Il /

m η

>, T ^. P - Z + .1C HX ",, SiR ⁴ R ⁵ R ⁰ + Λ

_R 2 ^ "m η KI

The method according to the invention has the following decisive advantages

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

2. The organophosphorus starting materials are largely accessible to LEHMANN (DD-WP 127187 and DD-WP 127188) directly from elemental phosphorus.

3. The procedure is applicable to a wide range of connections.

4. In contrast to ionic pseudohalides (alkali, alkaline earth or silver salts), the Trialk (ar) ylsilylpseudohalogenide are liquid and miscible with organic solvents in any ratio, so that the reaction proceeds in a homogeneous phase, which has a positive reaction time, yield and Purity of the reaction products affects.

5. The resulting halohydrocarbon and the trialk (ar) ylsilyl halocarbon compound can be easily removed from the reaction mixture. The latter, as refined Si specie, can otherwise only be synthesized in a complex way via organometallic compounds.

embodiment

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

R ¹ IR ² HR ³ Y) PiO _n H _n X ₁₁ RiR ⁴ R ⁵ R ⁶ SiZ = 1: 1: | S1)

is reacted with exclusion of moisture, optionally with constant stirring. To accelerate the reaction can be carried out in an inert, preferably dipolar aprotic solvent.

example Preparation of DlethoxYphosphorylisothlcoxryanate O.OSmol triethylphosphite are mixed with 0.06mol CCI ₄ and 0.065mol trimethylsilyl isothiocyanate Me ₃ SiNCS in 10-15ml dry Acetonitrile for 6 hours at room temperature. After removal of the solvent and the ethyl chloride formed on Rotary evaporator is precipitated by cooling with dry ice, the trimethyltrichloromethylsilane Me ₃ SiCCI) and filtered off. It leaves behind Diothoxyphosphorylisothiocyanat, which can be further processed without further purification. The ^{3 l} P-NMR spectroscopy determined yield of the target compound is 80%.

Claims (4)

1. A process for the preparation of pseudohalides of the tetracoordinate phosphorus represented by the general formula PZ
Y R ¹ , R ² = any organic radicals, eg. B. alkyl, alkoxy, alkylthio, Aroxygruppen, ring systems, dialkylamide, Diarylamid- and / or Alkylarylamidgruppen, Y = O, S, Z = pseudohalogen groups be characterized in that compounds of the trivalent phosphorus R ¹ IR ² KR ³ Y) P, wherein R ¹ , R ^{2 may be} the above and R ³ = alkyl groups, with Trialk (ar) ylsilylpseudohalogeniden R ⁴ R ⁶ R ⁶ SiZ, where R ⁴ " ^{6 may be} alkyl or aryl groups and Z = pseudohalogen groups, and a polyhalocarbon compound C _m H _n X | (R, where X = halogen and R = any organic radical, halogen or hydrogen, with or without Solvent be reacted at a reaction temperature between -10 ⁰ C and 80 ⁰ C. 2. The method according to item 1, characterized in that as Trialk (ar) ylsilylpseudohalogenide predominantly trimethylsilyl pseudohalides, z. B. Me3SiNCS, Me ₃ SiNCO, Me ₃ SiN ₃ , Me ₃ SiCN, Me ₃ SiC (CN) ₃ or Me ₃ SiN (CN) ₂ , can be used. 3. The method according to item 1, characterized in that is used as the polyhalocarbon compound mainly carbon tetrachloride CCI ₄ , 4. The method according to item 1, characterized in that the reaction predominantly in a dipolar aprotic solvent, such as. For example, acetonitrile is performed.