DE1918204C - Process for the preparation of derivatives of 1,2 Diphosphacyclopenten (5) one (4) - Google Patents

Description

The compound derived from pentavalent phosphorus Triphenylphosphine dichloride reacts with compounds that contain an activated methylene group, to stable derivatives of triphenylphosphine dimethylene. In each case, 1 molecule of the phosphorus compound settles with 1 molecule of the methyl component. The methylene compounds are malonic esters, Cyanoacetate, malonic acid dinitrile and bisbenzenesulfonyl-methane (bisphenyisulfon-methane) in Consideration. So z. B. the reaction of triphenylphosphine dichloride with malonic acid diethyl ester triphenylphosphine - dicarbethoxymethylene. This connection is through a double bond between the pentavalent phosphorus atom and a carbon atom characterized (cf. Hörne r, Oediger. Chem. Ber., 91 [1958], p. 437ff.).

It has been found that, for the preparation of derivatives of 1,2-diphosphacyclopenten- (5) -one- (4), one works in such a way that in the presence of an amount of a base which is at least sufficient to bind the hydrogen halide formed during the reaction Malonic diester reacts with compounds of trivalent phosphorus of the general formula

P (A) _n R

where X denotes identical or different halogen atoms, R represents an aliphatic, cycloaliphatic, heterocyclic or aromatic radical which may have substituents which cannot react with the halogen atoms bonded to phosphorus, A are bridge atoms which are optionally oxygen, sulfur, nitrogen or phosphorus and for η the values 0 or 1, in the case of sulfur, nitrogen or phosphorus as bridging atom for η also the value 2 can stand.

Surprisingly, 2 molecules of the compound des occur at the same time in this reaction trivalent phosphorus with 2 molecules of the ester in reaction to form a five-membered heterocyclic ring system. This mode of reaction stands in contrast to the behavior of the corresponding compounds of pentavalent phosphorus, in which 1 molecule of the phosphorus compound with 1 molecule of the malonic acid diester to form derivatives of the Dicarbäthoxymethylene converts.

Examples of phosphorus compounds which can be used by the process according to the invention are phenylphosphine dichloride, butylphosphine dibromide, phenoxyphosphine dichloride, N-methylaniline-N-phosphine dichloride.

The reaction between the reactants takes place at room temperature or at a slightly elevated temperature. It is expedient to work at 40 to 60 ° C. In special cases, for example in the case of sterically hindered reactants, however, higher temperatures may also be required. The reaction is expediently carried out in the absence of moisture and in an inert gas atmosphere.

The addition of a base to the reaction mixture serves to continuously remove the hydrogen halide formed during the reaction. Accordingly the base is used in at least an amount sufficient to bind 2 moles of hydrogen halide sufficient. Used according to a preferred embodiment of the method of the invention as base tertiary amines, especially triethyl

ij amin.

The work-up of the reaction product depends on whether a solvent was used and the physical state of the heterocyclic phosphorus-containing compound.

ίο If the reaction medium used is an inert one Solvent from which the heterocyclic phosphorus-containing compound precipitates during the reaction, it is expedient to filter off after the reaction has ended and the pure substance is recovered by extraction from the residue.

If the organic phosphorus-containing compound is soluble in the reaction medium, came z. B., optionally after filtering off insoluble by-products, the solvent is distilled off and the the resulting compound by recrystallization or distilling.

When carrying out the reaction in the absence

a solvent is the organic phosphorus containing compound expediently from the implementation product obtained by extraction with an inert organic solvent and after removal of the extraction medium also represented in pure form by recrystallization or distillation. Due to the presence of a phosphorus atom with a lone pair of electrons are the compounds Electron donors and therefore capable of complexing with transition metals and their compounds.

The accessible by the method of the invention

Borrowed compounds have been used as pesticides, as part of catalysts as well as proven intermediates for technical syntheses.

Examples

The compounds listed in the table below were made by the following procedure manufactured:

For each 0.1 mol of the reactants indicated in column 1, which are approximately 5 times the weight amount of benzene were dissolved, 0.2 mol of triethylamine were added dropwise ^{in a nitrogen atmosphere at 50 0 C with stirring.} The mixture was then stirred for 2 hours and precipitated triethylammonium halide was filtered off. The solvent was distilled off and the remaining reaction product either washed with ether and removed from absolute methanol recrystallized or, if it was a liquid, distilled for purification.

Tahclle

Persimmon parincr

Phein lplu ^ phiiulkhlorid
• Ma Ii infill re-dial h> tester

2. p-chloro-phen \ lphosphine dichloride i-malonic acid dietester

3. p-ToUl-pheinlpluisphine dichloride - Malonic acid diet ulcsicr

4. p-Dimclhjiamino-phesylphosphine dichloride
+ Malonic acid diethyl ester

f. p-Huor-phenylphosphine dichloride + Malonic acid dietary ester

6. o-tert-Butyl-phenoxypliosphine dichloride
+ Malonic acid diethylesi ^ r

2.5-dimethyl-phenyl-

phosphine dichloride

-t- malonic acid diethylcler

K. N-methylaniline-N-phosphine dichloride
+ Malonic acid diethyl ester

9. Phylphosphine dichloride
+ Malonic acid dimer

K). Phenylphosphine dichloride
+ Malonic acid di-tert-butyl ester

II. P-Dimethylamino-phosphine dichloride
+ Malonic acid c-di-tert-butyl-cyst

SumnienforiTiel

C, "ll _{: s} O" P, CI,

C ₃₁₁ H ₁₄ O,

C ₂₆ H, ₈ O _S P, F,

C ₃₄ H ₄₆ O _1n P,

C ₁₈ Hj ₆ O ₈ P ₂ N ₂

C ₂₂ H ₂₂ O ₈ P ₂

CuH ₄₆ O ₈ P ₂

C ₃₈ H ₅₆ O ₈ P ₂ N ₂

here.

here. uei.

ran here

ber. gcf.

ber. set.

ber. uef.

ber. gcf.

bcr. gcf.

ber. gcf.

ber.

bcr.

gcf.

5S.fi 5X.2

51st ^l > ! 5 (1.6 ')

6 (ul

58.25 58.55

54.93 54.45

60.4 61.2

61.2 61.4

56.9 56.1

55.45 55.0

63.4

62.7

62.47 62.46

Claims (3)

Patent claims: 1. Process for the preparation of derivatives of l ^ -Diphosphacyclopenten-iSVon-H), thereby characterized in that one is in the presence of one to bind the formed in the reaction Halogen hydrogen at least sufficient amount of a base malonic acid diester for the reaction brings with compounds of trivalent phosphorus of the general formula -R where X are identical or different halogen atoms Reaction products analyzes P 5.64 5.42 4.66 4.72 11.93 I. 6.07 and 11th OS 6.27 HKSS ' 6.47 6.82 4.93 4.6 6.8 6.65 6.46 6.55 6.10 7.14 4.c'2 4.8 7.14 7.34 7.67 July 8 55 6o N Cl MG 532
532 11.8
12.2 601
558 560
5OS 4.53
4.69 618
578 568
530 676
508 588
496 4.75
4.5 590
543 476
476 644
593 3.84
4.40 730
638 Chemical name l-ethoxy-l.2-diphenyl- [1.2-diphospha-c) clopenlen-l5 | - on- (4 |] ricarboxylic acid 3.3.51-ethyl ester I-Atho. \ Y-1.2-di- [4'-chlorophen> l} - [1,2-diphosphacyclopenien- (5l-one- | 4 |] -dicarboxylic acid- (3.3.5 | -trialylylcr l-ethoxy-I.2-di- | 4'-meth \ lphenvll-f 1,2-diphosphacyclopentene-15) -un-14 |] -ricarboxylic acid- (3,3,5) -triethyl ester 1-ethoxy-1,2-di-14'-dimethylamine> -phenyl) - [1.2-diphosphacyclopenten- (5) -one- (4)] -tricarboxylic acid- (3,3.5) -triethv tester -Athoxy-1,2-di- (4'-fluorophynyl I- [1.2-diphosphacyclopenten- (5) -one- (4)] - tricarboxylic acid- (3,3,5) - triethyl ester l-Ethox> -1.2-di- (2-tert-butylphynoxy | - [1.2-diphosphacyclopcntcn- (5) -one- (4)] -tricarboxylic acid-l 3.3.5) -Iriälhylestcr 1-ethoxy-1,2-di- (2'.5-dimethylphenyl I- [1.2-diphosphacyclopemen-15) -one- <4)] - tricarboxylic acid (3.3.5) methyl ester -Ethoxy-1,2-di- (N-methylanilino | - | 1.2-Hiphosphacyclopenten- (M-one- (4 |] -ricarboxylic acid- (3.3.5) -trieth) tester Methoxy 1,2-diphynyl [1,2-diphospha-cyclopenylcn- (5) -one- (4)] tricarboxylic acid (3.3.5) trimethyl ester l-lcrt.-Butoxy-l ^ -diphcnyl- [1.2-dipho <ipha-cyclopcnten- (5) -on- (4)] -tricarboxylic acid- (3.3.5) -tri-tcrt butylcstcr l-tert-butoxy-1.2-di- (4'-dimethylamino-phenyl) - [ 1.2-diphospha-cyclopcnten- (5) -on- (4)] -tricarboxylic acid- (3,3.5) -Iri-tcrt -bulylcslcr means, R is an aliphatic, cycloaliphatic ^ heterocyclic or aromatic radical which optionally carries those substituents which cannot react with the halogen atoms bonded to phosphorus, A are bridge atoms which optionally represent oxygen, sulfur, nitrogen or phosphorus and for η the values or 1, in the case of sulfur, nitrogen or phosphorus as bridging atom for η the value can also stand. 2. The method according to claim 1, characterized in that that tertiary amines, especially triethylainin, are used as bases. 3. The method according to claim 1, characterized in that one malonic diester and Phosphorus compound in a molar ratio of about 1: 1 applies.