DE1816903C3 - 0- [2-bromoethyl] - 0 - [2,2-dichloro-vinyl] phosphoric acid ester !! or amides, process for their production - Google Patents

Description

Br-CH ₂ -CH-O

0-CH = CCl ₂

in the

R for hydrogen, alkyl, haloalkyl,

Alkoxyalkyl or alkenoxyalkyl and
X for alkoxy, aryloxy, alkylaryloxy,

Alkyl mercapto, aryl mercapto,

Dialkylamino, dialkenylamino, diarylamino,

Alkylarylamino or

[1-Alkyl-2-alkoxy-carbonyl] -vinyloxy

stand

characterized in that there are 1,3,2-dioxaphospholanes of the general formula

, The present invention relates to O- [2-bromoethyl] -0- [2,2-dichlorovinyI] phosphoric acid ester or amides and a chemically peculiar process for their production.

These compounds are insecticidally active.

From the German patent specification 9 68 486 it is already known that 2-substituted dioxaphospholanes with Chloral to O- [2-chloroethyl] -O- [2,2-dichlorovinyl] phosphoric acid derivatives have it implemented. Furthermore, in the German Auslegeschrift 12 32961 a Process for the production of esters of some acids of phosphorus described, which among other things - but in a completely different way - to O- [2-bromoethyl] -

O- [2,2-dichlorovinyl] -O-methyl-phosphoric acid esters
leads.

It has now been found that the analogously constructed 0- [2-bromoethyl] -0- [2,2-dichlorovinyl] phosphoric acid compounds can be used the general formula

R-CH - O

CH ₁ -O

Br - CH, - CH - O

P-X

(D

in the

R and X have the abovementioned meaning, with bromodichloroacetaldehyde of the formula

Cl O

! 5 in the

0-CH = CCl,

Br-C-C

y N

Cl

implements.

2. The method according to claim 1, characterized in that the reaction in opposite to the Reaction partners inert solvents such as benzene, toluene, di-, tri- and carbon tetrachloride or Dietary ether makes.

3. The method according to claim 1 and 2, characterized in that the reaction is carried out at Temperatures between 0 and 100 ° C executes.

4.0- [2-bromoethy.! O- [2,2-dichlorovinyl] phosphoric acid ester or amides of the general formula

R.
Br-CH ₂ -CH-O O

R for hydrogen, alkyl, haloalkyl,

Alkoxyalkyl or alkenoxyalkyl and
X for alkoxy, aryloxy, alkylaryloxy,
Alkyl mercapto, aryl mercapto, dialkylamino,

Dialkenylamino, diarylamino, alkylarylamino or
[1 - alkyl-2-alkoxycarbonyl] vinyloxy

stand, can be produced in high yield and purity by adding 1,3,2-dioxaphospholanes of the general formula

R-CH-O

P-X

(H)

CH, —O

in which R and X have the abovementioned meaning, with bromodichloroacetaldehyde of the formula

Cl

I \

Cl H

(III)

X C) -CH = CCI,

in the

R for Ci-C ₄ -alkyl, Ci-Q-haloalkyl,

C 1-4 alkoxyalkyl or Ci-Ch alkenoxyalkyl
stands and

to react.

It can be described as extremely surprising and unexpected that only the bromine atom is the Cleavage of the dioxaphospholane ring causes and enters the newly formed side chain. Since chloral, as in of the cited German patent, the ring cleavage described with the same ease brought about in an exothermic reaction, one would have at

Use of bromodichloroacetaldehyde instead of chloral should expect a mixed product in which Bromine and chlorine atoms are randomly distributed between the haloalkyl and dihalovinyl groups. This is however not the case. The products of the invention Process are uniform and correspond to the general formula (I), as z. B. nuclear magnetic resonance spectroscopy can prove. The method according to the invention thus represents, compared to the state of the Technology represents progress.

If you use 2-methoxy-1,3,2-dioxaphospholane and bromodichloroacetaldehyde as starting materials, the course of the reaction can be shown in the following reaction scheme be reproduced:

CH ₂ -O

Cl O

PO-CH ₃ + Br-C -C

I \

CH ₂ -O Cl H

Br-CH ₂ -CH ₂ -OO

CH ₃ -O

0-CH = CCl ₂

The 1,3,2-dioxaphospholanes to be used as starting materials are generally defined by the above formula (II). In formula (II), R preferably represents alkyl or haloalkyl with 1-4 carbon atoms, furthermore for alkoxyalkyl with preferably 2-6 or alkenoxyalkyl with preferably 3 to 6 carbon atoms and X for alkoxy or alkyl mercapto with preferably 1 -4 carbon atoms, also for [1-alkyl-2-alkoxycarbonyl] -vinyloxy, preferably for [l-methyl-2-ethoxycarbonyl] vinyloxy, also aryloxy, preferably phenoxy, for alkylaryloxy, preferably lower alkylphenyloxy, for aryl mercapto, preferably phenyl mercapto, for dialkylamino with preferably 2-8 carbon atoms, for dialfcenylanvino with preferably 4-8 carbon atoms, for diarylamino, preferably Diphenylamines, for N-alkyl-N-arylamino, preferably N-lower alkyl-N-phenyl-amiiio.

Specific examples of the 1,3,2-dioxaphospholanes which can be used according to the invention are: 2-methoxy-1,3,2-dioxaphospholane 2-ethoxy-13,2-dioxaphospholane 2-1 sopropoxy-1,3,2-dioxaphospholane 2-butoxy-1,3,2-dioxaphospholane, 2-dimethylamino-1,3,2-dioxaphospholane, 2-diethylamino-1,3,2-dioxaphospholane, 2-diallylamino-1,3,2-dioxaphospholane, 2-diphenylamino-1, 3,2-dioxaphospholane 2-i (N, N-methyl-phenyl) amino-1, -1,2-dioxaphospholane
2- phenoxy-13 ^ 2-dioxaphor-pholane 2- (4'-tert-butyl) -phenoxy-13,2-dioxaphospholau
2-methylmercapto-1,3,2-dioxaphospholane 2-ethylmercapto-1,3,2-dioxaphospholane 2-buty! Mercapto-1,3,2-dioxaphospholane 2-phenylmeicapto-1,3,2-dioxaphospholane 2-vinyloxy- 1,3,2-dioxaphospholane 2- (1'-methyl-2'-ethoxycarbonyl) -vinyloxy-1,3., 2-dioxaphospholane
2-methoxy-4-methyl-1,3,2-dioxaphospholane, 2-methoxy-4-chloromethyl-1,3,2-dioxaphospholane, 2-methoxy-4-bromomethyl-1,3,2-dioxaphospholane, 2-kiethoxy-4 - (meihoxy) methyi-

13,2-dioxaphospholane
2-methoxy-4- (allylloxy) methyl-1,3,2-dioxaphospholane
2-Ä thylmercapto-4-chloromethyl-13,2-dioxaphospholane

The starting products (II) are known and can also be produced on an industrial scale.

All organic solvents which are indifferent to the reactants are used as diluents in question, preferably aromatic hydrocarbons such as benzene and toluene, chlorinated aliphatic Hydrocarbons such as di-, tri- and carbon tetrachloride and ethers such as. B. diethyl ether. In principle, the The reaction can also be carried out without a solvent.

The reaction temperatures can be varied over a wide range. Generally works between 0 and 100 ° C, preferably between 30 and 70 ° C. The temperature adjusts itself in the exothermic reaction and can through The addition of the aldehyde can be regulated.

To carry out the process according to the invention, the desired 1,3,2-dioxaphospholane (H) is dissolved optionally in one of the diluents mentioned and the equimolar amount of bromodichloroacetaldehyde is added dropwise (III) to.

For working up, the reaction solutions are washed neutral, dried and concentrated. Numerous the products thus obtained can be purified by distillation. Where this is due to the risk of decomposition is not possible, the crude products become low under greatly reduced pressure of residues exempt from boiling parts.

The substances of the general formula (I) obtained by the process according to the invention
in which

R for Ci-C ₄ -alkyl, C, -C4-haloalkyl,
C ₂ -C ₆ alkoxyalkyl or
Cs-Ce-alkenoxyalkyl and

X for CC ₄ -AIkOXy, Phenoxy,

Niederalkyiphenyloxy, Ci-C4-Alkylmercapto,

Phenylmercapto, Ca-Ce-Dialkylamino,

C4-Ce-dialkenylamino, diphenylamino,

N-lower alkyl-N-phenyl-amino or

[1-methyl-2-ethoxycarbonyl] -vinyloxy.

are new. They are also used as pesticides.
The following examples illustrate the process.

example 1

CH ₂ -CH ₂ -OO

CH ₃ -O

O - CH = CCl,

30.1 g (0.25 mol) of 2-methoxy-1,3,2-dioxaphospholane in 200 ecm of benzene are slowly mixed with 48 g (0.25 mol) of bromodichloroacetaldehyde while stirring. The temperature rises to 70 ^° C. during this process. The mixture is left to stir for two to three hours, during which the temperature drops back to normal. The reaction solution is washed neutral with water, dried over sodium sulfate, filtered off and concentrated. The oily residue can be distilled for cleaning. One receives O- [2-bromoethyl] -0- [2,2-dichlorovinylJ-0-methyl-phosphorus-

acid ester as a colorless oil with a boiling point of 110 ° C / 0.01 Torr and the refractive index η ft = 1.4876.
Yield: 60.4 g (77.0% of theory).

Analysis for C ₅ H ₈ BrCl ₂ O ₄ P (313.9):
Calculated: P 9.88%;
Found: P 9.77%.

Example 2

Br-CH ₂ -CH ₂ -OO

Example 5

1-C ₃ H ₇ -O

0-CH-CCl ₂

C ₂ H ₅ -S

O-CH = CCl ₂ Br-CH, -CH, -O

(CH ₃ I ₂ N

O - CH = CCl,

The compound is prepared analogously to Example 1 from 2-isopropoxy-1,3,2-dioxaphospholane and BromJichloracetaldehyd. O- [2-bromo-ethyl] -O- {2,2-dichlorovinyl] -O-isopropyl-phosphoric acid ester is obtained as a colorless oil with a boiling point of 115 ° ^{C./0.01 Torr and the refractive index π o 3} = 1.4773 .

Yield: 72.5% of theory.

Analysis for C ₇ H ,, BrCl ₂ O ₄ P (342.0):
Calculated: P 9.07%;
Found: P 9.27%.

Example 3

Br-CH ₂ -CH ₂ -OO

ίο The compound is prepared analogously to Example 1 from 2-dimethylamino-13,2-dioxaphospholane and bromodichloroacetaldehyde. O- [2-bromoethyI] -O- {2,2-dichlorovinyI] phosphoric acid-N, N-dimethylamide is obtained as a colorless oil from the boiling point 130 ^c C / 0.4 Torr and the

[5 refractive index η 'V " = 1.4951.
Yield: 56.4% of theory.

Analysis for C ₆ H _n BrCl ₂ NO ₃ P (327.0):

Calculated: N 4.28, P 9.48%;
Found: N 4.57, P 9.57%.

The compound is prepared analogously to Example 1 from 2-ethylmercapto-l, 3,2-dioxaphospholane and bromodichloroacetaldehyde. O- [2-bromoethyl] -O- [2,2-dichlorovinyl] -S-ethyl-phosphoric acid ester is obtained as a yellow oil with a boiling point of 140 ° C./0.3 Torr and a refractive index η " ⁵ = 1.5267.

Yield: 50.6% of theory.

Analysis for C ₆ H ₁₀ BrCl ₂ O ₃ PS (344.0):
Calculated: P 9.02, S 9.31%;
Found: P 9.23, S 9.80%.

Example 6

Br CH, CH, O

(CH ₂ = CH-CH ₂ ) ₂ N

O - CH = CCl,

The compound is prepared analogously to Example 1 from 2-diallylamino-1,3,2-dioxaphospholane and bromodichloroacetaldehyde. O- [2-Bromo-ethyl] -O- [2,2-dichlorovinyl] -phosphoric acid-N, N-diallylamide is obtained as a colorless oil with a boiling point of 132 ° C / 0.01 Torr and a refractive index π ^J o ⁵ = 1, 5021

Yield: 56.0% of theory.

Analysis for CiOHi ₅ BrCl ₂ NO ₃ P (379.0): Calculated: N 3.69, P 8.17%;
Found: N 4.12, P 8.04%.

Example 7

Example 4
CH ₃

Br - CH, - CH - O

CH ₃ O

O - CH = CCl,

The compound is prepared analogously to Example 1 from 2-methoxy-4-methyl-1,3,2-dioxaphospholane and bromodichloroacetaldehyde. One obtains 0- [2-bromo-1-me-

ethyl] -O- [2,2-dichlorovinyl] -O-methyl-phosphoric acid ester as a colorless oil with a boiling point of 110 ° C./0.1 Torr and a refractive index η "d = 1.4839.

Yield: 37.1% of theory.

Analysis for C ₆ H ₁₀ BrCl ₂ O ₄ P (328.0):
Calculated: P 9.45%;
Found: P9.56%.

Br-CH ₂ -CH ₂ -O
O

C-CH = C-O

C ₂ H ₅ O

0-CH = CCl ₂

The compound is prepared analogously to Example 1 from 2- (1'-methyl-2'-ethoxycarbonyl) -vinyloxy-1,3,2-dioxaphospholane and bromodichloroacetaldehyde. O- [2-Bromoethyl] -O- [2,2-dichlorovinyl] -O- (l -methyl-2-carboethoxy) vinyl phosphoric acid ester is obtained as a yellowish oil with a boiling point of 180 ° C / 0.1 Torr and the refractive Index π ξ, ⁶ = 1.4922.

Yield: 44.2% of theory.

Analysis for C ₁₀ H ₁₄ BrCl ₂ O ₆ P (412.0): Calculated: P 7.53%;
Found: P 7.61%.

B e i s ρ i c I 8

Br - CH, - CH ₇ - O

Example 10
CH ₂ O -CH, -CH = CH ₂

Bi- CH, (H

(CH ₃ ) ₃ C

y v

O-CH = CCI ₂

CH, - O

O -CH = CCI,

The compound is obtained analogously to Example 1 from 2- (4'-tert-butyl -) - phenoxy-l, 3,2-dioxaphospholane and Bromdichloracetaldehyd prepared, except that the stirring is carried out at 50 to 60 ⁰ C. O- [2-bromine-

ethyl] -O- [2,2-dichlorovinyl] -O- (4-tert-butyl) -phenylphosphoric acid ester as a yellowish oil with a refractive index / ?? = 1.5210.

Yield: 44.7% of theory.

Analysis for C ₁₄ HI ₈ BrCl ₂ O ₄ P (431.1): Calculated: P 7.18%;
Found: P 6.44%.

Example 9

CH ₂ Cl

i
Br - CH ₂ - CH - OO

/ \ CH ₃ - OO - CH = CCl ₂

The compound is prepared analogously to Example 1 from 2-methoxy ^ -chloromethyl-lS ^ -dioxaphospholane and bromodichloroacetaldehyde. 0- [1-Chloromethyl ^ -bromo / ethyl-O- ^ - dichlorovinyl / O-methylphosphoric acid ester is obtained as a yellow oil with a refractive index of nV = 1.5059.
Yield: 26.1% of theory.

Analysis for C ₆ H ₉ BrCl ₃ O ₄ P (362.4): Calculated: P 8.53%;
Found: P 9.01%.

The compound is prepared analogously to Example 1 from 2-Meth oxy-4- (allyloxy) methyl-1,3,2-dioxaphospholane to bromodichloroacetaldehyde. O- (l allyloxymethyl ^ -bromo / ethyl-Op ^ -dichlorovinyl / O-ismethyl-phosphoric acid ester is obtained as a yellow oil with a refractive index η 'i = 1.4909.
Yield: 44.0% of theory.

Analysis for C ₆ H ₉ BrCl ₂ O ₅ P (384.0):

Calculated: P 8.06%;
Found: P 8.25%.

The following examples explain the pesticidal use of the process according to the invention ren available known as well as the new connection 2s gen.

Example 11

LTioo test for Diptera

^ ⁰ test animals: Aedes aegypti.
Solvent: acetone.

2 parts by weight of active ingredient are in 1000 volumes share solvent added. The solution obtained in this way is added to the desired low concentrations.

2.5 ml of the active ingredient solution are placed in a Petri dish

pipetted. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The petri dish stays open for so long, bi; the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m ^{2 of} filter paper is different. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. The time is determined which is necessary for a 100% destruction is necessary.

Test animals, active ingredients, active ingredient concentrations and times at which there is 100% destruction can be seen from the following table 1:

Table 1

LT ₁₀₀ -Test for Diptera

Active ingredients

Active ingredient concentrations
% solution

LT _1n

CH,
Br-CH ₂ -CH-O O

P-O-CH = CCl ₂ CH ₃ O

0.2
0.02
0.002
0.0002

180 '

-continuation

ίο

Active ingredients

Wit kstolTkon / eiu rutile men

I l, "

CH ₂ Cl Br - CH ₂ - CH - OC)

PO-CH -CCl ₂

CH ₃ O

Br-CH ₂ -CH ₂ -O 0

Ml

PO-CH-CCl ₂ iC ₃ H, -O Br-CH ₂ -CH ₂ -O 0

P - O - CH = CCl ₂ C ₂ H ₅ - S Br-CH ₂ -CH ₂ -O 0

Ml

P - O - CH = CCl,

(CH ₃ J ₂ N 0.2

0.02

0.002

0.2
0.02

0.2

0.02

0.002

0.2
0.02

60 '120' 180 '

60 '120'

60 '

60 '

180 '

60 '120'

Example LTioo test for Diptera

Test animals: Musca domestica. Solvent: acetone.

2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The thus obtained The solution is diluted to the desired lower concentrations with further solvent.

2.5 ml of active ingredient solution are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m ^{2 of} filter paper is different. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. The time is determined which for a 100% destruction is necessary

Test animals, active ingredients, active ingredient concentrations and times at which there is a 100% kill, can be seen from the following table 2:

Table 2
LT ₁₀₀ -Test for Dipteras Active ingredients CH ₃ -CH = CCl ₂ Active ingredient concentrations
% solution LT ₁₀₀ Br - CH ₂ - CH - OO
Ml
PO
CH ₃ O CH ₂ Cl 0.2
0.02
0.002 15 '
40 '
130 ' Br-CH ₂ -CH-O _x O
PO
/ - CH = CCl ₂ CH ₃ O 0.2
0.02
0.002 50 '
50 '
8th*

11th

continuation

Active ingredients

Br-CH ₂ -CH ₂ -O

P-OCH = CCl ₂ iC ₃ H ₇ -O Br -CH ₂ -CH _{2 -O s}

P-O-CH = CCl ₂ C ₂ H ₅ S Br-CH ₂ -CH ₂ -O

P-O-CH = CCl ₂ (CH ₃ ) ₂ N 12

Act on indications
% ige 1 ösiinjj 1-T ₁₁₁₁ 0.2
0.02
0.002 30 '
55 '
8th" 0.2
0.02
0.002 55 '
3 ^h
8 ^h 0.2
0.02 75 '
210 '

example

LDioo test

Partial animals: Sitophilus granarius. Solvent: acetone.

2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The thus obtained The solution is diluted to the desired concentrations with additional solvent.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. On the bottom of the petri dish is

Table 3
LD ₁₀₀ -Test

a filter paper about 9.5 cm in diameter. The Petri dish remains open until the solvent has completely evaporated. The amount depends on the concentration of the active ingredient solution

3c active ingredient per m ^{2 of} filter paper of different heights. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The mortification is determined in%.

Active ingredients, active ingredient concentrations, test animals and results are shown in Table 3 below emerged:

Active ingredients

Active ingredient concentrations % iee solution

CH ₃ Br-CH ₂ -CH-O

P-O-CH = CCl ₂ CH ₃ -O CH ₂ -Cl Br-CH ₂ -CH-O

PO-CH = CCl ₂ CH ₃ -O Br-CH ₂ -CH ₂ -O

P-OCH = CCl ₂ 0.2
0.02
0.002
0.0002

0.2
0.02

0.2

Mortality in %

100

100

100

50

100 100

100

1-C ₃ H ₇ -O

13th

continuation

Active ingredients

Active ingredients in / cnlrüi ionen% iuc l.ösunp

Mortality!

Br-CH ₂ -CH ₂ -OO

P-O-CH ₂ = CCl ₂

Br-CH ₂ -CH ₂ -OO

P - O - CH = CCl ₂ (CH ₃ ) ₂ N CH ₂ - O - CH ₂ - CH = CH ₂

Br-CH ₂ -CH-O O

P-O-CH = CCl ₂ 0.2
0.02

0.2

0.2
0.02

100 30

100 90

100 100

CH ₃ -O

Example LTioo test for Diptera

Test: Musca domestica (resistant). Solvent: acetone.

35

2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The thus obtained The solution is diluted to the desired lower concentrations with further solvent.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. On the bottom of the petri dish is

Tabel

LT ₁₀₀ -Test for Diptera

Musca domestica (resistant) a filter paper with a diameter of about 9.5 cm. The Petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m ^{2 of} filter paper is different. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. The time is determined which for a 100% destruction is necessary.

Test animals, active ingredients, active ingredient concentrations and times at which there is a 100% kill, are shown in the table below:

Active ingredients

Active ingredient concentration
% ice solution!

LT. ,,,, in

Minutes II or hours (hl

Br-CH ₂ -CH ₂ -OO

P-O-CH = CCl ₂

CH ₃ -O (known from DT-AS 12 32 961, example 3)

CH, Br-CH ₂ -CH-O O

PO-CH = CCl ₂

CH ₃ -O (according to the invention, example 4) 0.2
0.04

0.2

0.04

0.008

150 '

6h = 70%

75 '150' 6h = 80%

Claims (1)

Patent claims: 1. Process for the preparation of 0- [2-bromoethyl] -0- [2,2-dichlorvin> ij-phosphoric acid esters or amides of the formula X for C ₁ -C ₄ alkoxy, phenoxy, Niederaikylphenyloxy.Ci-C ^ AIkylmercapto,
Phenylmercapto, C ₂ -Cg dialkylamino,
C4-C8 dialkenylamino, dipenylamino,
N-lower alkyl-N-phenyl-amino or
1- [methyl-2-ethoxycarbonyl] vinyloxy
stands.