DE1193044B - Process for making phosphorylated urethanes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

XIlU

V ^ Vl 4

German class: 12 ο -26/01

Number: File number: Filing date: Display date:

1193 F 40415IV b / 12 ο August 5, 1963 May 20, 1965

The invention relates to a process for the preparation of phosphorylated urethanes of the general formula

RiO
R ₂ Q

"P-CH-CCl ₃ O-C-NH ₂ O

in which Ri and R ₂ stand for lower alkyl radicals, preferably with 1 to 4 carbon atoms.

The process is characterized in that 1-hydroxy-2,2,2 - trichloroethylphosphonic acid Ö.O -diälkylester with isocyanate sulfohalides of the general formula

= C = N-SO ₂ X

converts and the resulting intermediates of the general formula
O

RiO _x II

; p-CH-CO ₃

R ₂ O / I

O-C-NH-SO ₂ -X

then saponified.

Process for the preparation of phosphorylated Urethanes

Applicant: Farbenfabriken Bayer Aktiengesellschaft, Leverkusen

Named as inventor: Dr. Helmut Timmler, Wuppertal-Vohwinkel; Dr. Richard Wegler, Leverkusen; Dipl.-Agr. Dr. Günter Unterstenhöfer, Opladen

II

p-C-CCi ₃ + O = C = N-SO ₂ X

I.
OH

The process according to the invention is explained in more detail using the following reaction scheme:

RiO _x II

* ^ P-CH-CCl ₃

R2O / I

O-C-NH-SO ₂ X

RiO _x II

P-CH-CCl ₃ + H ₂ O

O-C-NH-SO2 -X

Il ο

RiO _x II R ₂ O ^/

P - CH-CCl ₃ +. HO -SO 2 -X O -C-NH ₂ O

In the latter formulas, the symbols have Ri from U.S. Patent 3,069,312 are already

and R _{2 has} the meaning given above, while X 50 N-substituted l-carbamoyloxy-2,2.2-trichloroethyl

for a halogen, preferably a chlorine or fluorine atom Ο, Ο-dimethylphosphonic acid ester known. After the

stands. Information from the aforementioned patent specification will be

509 570/435

these compounds either by reacting 1 - hydroxy - 2,2,2 * - trichloroethylphosphonic acid O, O-dimethyl ester and isocyanates or by reacting the aforementioned phosphonic acid ester with an N-mono- or N, N- <lisubstituted carbamic acid chloride manufactured.

Phosphorylated ones that are not substituted on the nitrogen atom Urethanes, however, are neither in the description nor in the examples of the aforementioned USA. Patent as it is not described after either of the two in the cited USA. Patent Procedures are accessible. It is namely both in the implementation of 1-hydroxy-2,2,2 - tricbJoräthylphosphonsäure - O, O- dialkyl esters with isocyanic acid as well as with carbamic acid chloride not the expected reaction product, but that unchanged starting material obtained.

Furthermore, in a work by R. G r a f in "Chemical Reports", Vol. 96 (1963), pp. 56 to 67, including the addition of alcohols Isocyanate sulfochloride (N - carbomyl sulfamic acid chloride), which undergoes the formation of urethane N-sulfochlorides runs, described. According to Graf, the latter are compounds Easily hydrolyzed to urethane-N-sulfonic acids, which when left to stand in their aqueous solution or faster at. Heating will break down into the free urethanes and sulfuric acid. Carbamic acid esters of 1 - Hydroxy - 2,2,2 - trichloroethylphosphonic acid 0,0-dialkyl esters however, are not disclosed in the aforementioned publication.

The implementation of the l-hydroxy ^^ - trichloräthylphosphonsäure-O, O-diaIkylester is preferably carried out in the presence of inert organic solvents. These have proven useful for this purpose especially optionally chlorinated aliphatic or aromatic hydrocarbons such as methylene chloride, Chloroform, carbon tetrachloride, benzene, chlorobenzene, toluene, xylene.

The reaction proceeds smoothly and with sufficient speed even at low temperatures (-5 to +10? G, preferably Of to +5 ^{0 C).} After the reaction has ended, the solvent is distilled off, if appropriate under reduced pressure at room temperature or slightly elevated temperature, and the residue is saponified, preferably also in the heat. A particularly suitable saponifying agent is water.

The resulting mineral acid is expediently caught by adding mild acid binders z. B. sodium bicarbonate, so as to exclude the possibility of ester saponification.

To complete the reaction it has to be furthermore proven to be advantageous, the mixture for some time (30 minutes to 2 hours) with stirring reheat on the water bath.

The phosphorylated urethanes that can be produced in accordance with the present invention mostly fall in shape crystalline substances with a sharp melting point, which are recrystallized from the common Allow solvents or solvent mixtures to be easily cleaned further.

The process products are characterized by excellent pesticidal, especially insecticidal properties and are therefore used as pesticides mainly used in crop protection. The superiority of the process products results from a comparison with the compounds known from US Pat. No. 3,069,312

Comparative experiments

O Application against Insecticidal effectiveness Kill in% after 24 hours link
(Constitution) CHsOsJI Active ingredient
concentration 3 days / P-CH-CCl ₃ in «/ ο CHsO / I Caterpillars 100 0-C-NH ₂ (Plutella maculipennis) 0.1 100 Il
O 0.02 80 Beetle 0.004 100 (according to the procedure, example 1) (Phaedon cochleariae) 0.1 100 0.02 30th 0.004 100 To fly 100 (Drosophila melanogaster) 0.1 100 O 0.02 100 CH ₈ O _x H 0.004 ; p-0-CH-eels 0.0008 CH ₈ O / I
0 -C-NHCH ₃ Caterpillars 15th O (Plutella maculipennis) 0.1 0 (known from USA patent specification Beetle
(Phaedon cochleariae) 0.02 25th
0 60 3069 312, example 2) To fly 0.1
0.02 0 (Drosophila melanogaster) 0.1 0.02

continuation

O
CH ₃ O _x H Application against Insecticidal effectiveness Kill in% after 24 hours link
(Constitution) ; p-o-CH-CCi ₃
CH ₃ O / I
0 -C -NHC2H5 Active ingredient
concentration 3 days O Caterpillars in "/ ο 25th (known from USA patent specification (Plutella maculipennis) 0.1 0 3 069 312, example 2) Beetle
(Phaedon cochleariae) 0.02 10
0 70 To fly 0.1
0.02 0 (Drosophila melanogaster) 0.1 0.02

The examples explain the claimed process:

For example

CH ₃ O _x I '

CH ₃ O '

; p-CH-CCi ₃

Ο —C-NH ₂

256 g of l-hydroxy ^^^ - trichloroethylphosphonic acid O, O-dimethyl ester are dissolved in 1 liter of chloroform, and 141 g of isocyanate sulfochloride are added dropwise to this solution while cooling gently with ice. After stirring the mixture for 1 hour at room temperature, the chloroform is distilled off and the residue is heated with 1.5 liters of water on the water bath for ¹ ^ hour. The reaction mixture is then allowed to cool and the precipitate which has separated out is filtered off with suction. The compound of the above structure melts after recrystallization from aqueous methanol at 131 ^° C. The yield is 210 g (70% of theory).

Example 2 O

C ₂ H ₅ O _x II

C ₂ H ₅ O '

: ρ — CH-CCi ₃

Ο —C-NH ₂ O

240 g of the compound of the above structure are obtained in the form of colorless crystals with a melting point of 138 ^° C.

Claims (1)

Claim: Process for the production of phosphorylated urethanes, characterized in that that one in each case known per se 1-hydroxy-2,2,2-trichloroethylphosphonic acid O, O-dialkyl ester with isocyanate sulfohalides of the general formula O = C = N-SO ₂ X converts and the resulting intermediates of the general formula 284 g of l-hydroxy ^^^ - trichloroethylphosphonic acid-Ο, Ο-diethyl ester are, as described in Example 1, reacted with 141 g of isocyanate sulfochloride. That The reaction mixture obtained is treated with 1.5 l of warm after removal of the chloroform Water, the solution being neutralized by adding appropriate amounts of sodium hydrogen carbonate will. After the mixture has cooled down RiO _x Il
; p- R ₂ O ^X CH-CCl ₃ O - C - NH - SO ₂ - X
O then to compounds of the general formula RiO _x Il ; p-CH-CCi ₃ R ₂ O / I O — C — NH ₂ saponified, where in the aforementioned formulas Ri and R _{2 are} lower alkyl radicals, preferably having 1 to 4 carbon atoms, while X is a halogen, preferably chlorine or fluorine atom. Considered publications:
U.S. Patent No. 3,069,312;
Chemical Reports, 96, 1963, pp. 56-67. 509 570/435 5.65 Bundesdruckerei Berlin