DE930210C - Process for the preparation of sultam-N-phosphoric acid dialkyl esters or sultam-N-thiophosphoric acid dialkyl esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED JULY 11, 1955

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 12p GROUP 4

R 11947 IVc 112 p

Dr. Hans Feichtinger, Duisburg-Beeck and Dr. Hans Tummes, Duisburg-Meiderich

have been named as inventors

Ruhrchemie Aktiengesellschaft, Oberhausen (RhId.) - Holten

Process for the preparation of Sultam-N-phosphoric acid dialkyl esters or Sultam-N-thiophosphoric acid dialkyl esters

Patented in the territory of the Federal Republic of Germany on June 23, 1953

Patent application published January 20, 1955

Patent issued June 16, 1955

It has been found that compounds of the general formula

SO,

! Ν —P ^ OR 'resp.
OR '

so"

N - Ρς-OR '
^X OR '

in which R is a straight-chain or branched saturated hydrocarbon bridge of 3 to 6 carbon atoms and R 'is a methyl or ethyl group, can be prepared if the

Alkali salts of the sultams of the general formula

NMe

with chlorophosphoric acid dialkyl esters or chlorothiophosphoric acid dialkyl esters the formula

Cl-P —OR '

OR '

converts, where R 'and R have the above

have meaning, Me represents an alkali metal and the oxygen atom doubly bonded to the phosphorus atom can be replaced by a sulfur atom.
The reaction proceeds according to the following equation:

: NMe

SO ₂

I - P. ^ OR 'OR'

^R \ y °,

SUN ₉

+ MeCl

OR '

The SuItarne suitable for the procedure can from derivatives of substituted alkanesulfonic acids by a Cyclisiemngsreaktion, z. B-. the end the aminoalkanesulphochloride hydrochlorides by alkali, from chloralkanesulphonamides by heating and from oxyalkanesulfonic acid by the action of ammonia. As an an example let y-propanesultam, <5-butanesultam and a-methyl-y-propane results, called.

The conversion of the sultams into the alkali salts is generally carried out by the action of a equivalent amount of alkali alcoholate to an alcoholic solution of the sultame and evaporation the reaction solution in vacuo. The N-alkali ultams are obtained in solid form.

To react with the chlorophosphoric acid esters, the alkali sultam is in an inert Solvent, such as benzene, ether or dioxane, suspended and stirring with the equivalent Amount of chlorophosphoric acid dimethyl or ethyl ester added.

The reaction temperature can be between 20 and 80 °. The reaction is over when that basic Alkalisultam is completely consumed, which can easily be recognized by the fact that the suspended Precipitation of the reaction mixture no longer reacts as a base after the addition of water. In general, this takes 2 to 3 hours Response time required.

The isolation of the sultamphosphorsäuredimethyl- or -äthylester takes place by evaporation of the Reaction solution in vacuo, the reaction product usually being obtained in sufficient purity will. If necessary, it can be further purified by high vacuum distillation.

The Sultamphosphorsäuredimethyl- or -äthylester are colorless oils that with water as well as the most organic solvents are miscible. They can use as a pesticide Find.

The process is also suitable for the preparation of sultam-N-thiophosphoric acid dialkyl esters. The sultams are used instead of dialkyl chlorophosphoric acid esters with chlorothiophosphoric acid

alkyl esters implemented. In this case, compounds of the general formula are formed

^ N— P ^ - OR 'oJ ^0R '

B-ei game i

67.5 g of α-methyl-γ-propanesultam were added to a solution of 37 g of sodium methylate in 1000 cm ^{3 of} absolute methanol, and the solvent was evaporated off in vacuo until the sodium sultam remained as a solid white residue. After addition of 1000 cm ³ of absolute benzene was suspended finely as possible the Natriumsultam by vigorous stirring, followed by g in the 50 ⁰ 86 Chlorphosphorsäurediäthylester heated mixture was slowly added dropwise. After two hours of stirring, the benzene was evaporated on a water bath and then heated for so long in a high vacuum at 150 ⁰ until nothing passed more. The distillation residue weighed ίβΟΐδ S ^{was un} d ^e i ⁿ weak smelling, colorless oil. Density d f = 1.2689, refractive index η * ° = 1.4665.

The analysis showed the composition of an α-methyl-γ -propanesultam-N-diethoxy-oxyphosphine of the formula

HoC - CHo

, 0

CH, -HC N - Pr-I

SO,

OC ₉ H,

Formula: C ₈ H ₁₈ O ₅ NSP, Molecular Weight: 271.28. Calculated:

C 35.42%, H 6.69%, N 5.16%, S 11.82%, found:

C 36.04%, H 6.59%, N 4.74%, S 11.20%.

Example 2

17.2 g of diethyl chlorophosphorate were slowly added at 35 ° to a well-stirred suspension of 15.7 g of N-sodium-o-butanesultam in 200 cm ^{3 of benzene.} After 1 hour, the i ™ reaction solution was evaporated in vacuo on a water bath and heated the residual colorless oil in high vacuum at 150 ⁰ until no more distilled over. This left 25 g of one. colorless oil, which due to the chemical supply ¹¹ S composition substantially pure (5-Butansultam-N-diethoxy-oxyphosphin the following formula was:

CH,

H ₂ C.
i \ /
SO ₂ CH ₂ / ° H ₅ H ₂ C. N - -OC ₂ H ₅ ^v oc ₂

Claims (1)

Claim: Process for the preparation of Sultam-N-phosphoric acid dialkyl esters or Sultam-N-thiophosphoric acid dialkyl esters of the general formula O R Γ - P ς— OR 'or
^ 0R ' SUN ₉ SO, in which R is a straight-chain or branched saturated hydrocarbon bridge from 3 to 6 carbon atoms and R 'denotes a methyl or ethyl group, characterized in that that the alkali compounds of the sultams of the general formula SO ₂ with CMorphosphorsäuredialkylestern or Chlorothiophosphoric acid dialkyl esters of the formula Cl-P ^ - in which Me represents an alkali metal and the one which is double-bonded with the phosphorus atom Oxygen atom can be replaced by a sulfur atom, R and R 'those given above Have meaning, expediently in an inert organic solvent such as benzene, ether or dioxane. © 509 525 7.55