DE1049372B - Process for the production of acidic esters of phosphonic acids or their salts - Google Patents

Description

INTERNAT KL

C07f

PATENT OFFICE

H 29321 IVb / 12 ο

REGISTRATION DATE FEBRUARY 14, 1957

NOTICE
THE REGISTRATION
AND ISSUE OF THE
DESIGN STEP

January 29, 1959

It has been found that acidic esters of phosphonic acids are used or ihie salts thereby in a simple manner can produce that one a-halogeniei te Carboxamides with dialkyl phosphites in such Temperatures / ur reaction limits at which a The alkyl halide is split off and, if appropriate, the acidic esters obtained are known Wise converts these compounds into their salts several located in the α-position to carbonamide groups Containing halogen atoms in the molecule, according to the invention brought to implementation with one or with several molecules of a dialkyl phosphite will

The inventive reaction, which in general smoothly and with good yields is, probably proceeds according to the following general formula

R ₁ O

R ₂ O

R ₃ -CCN

¹ Il

Halo

HO

RO,

-P - C - C-

OR ₄ O

+ R ₁ shark

In this formula, Hal denotes a halogen atom, R ₁ and R ₂ mean identical or different aliphatic or cycloaliphatic hydrocarbon radicals with preferably fewer than 8 carbon atoms R ₃ , R ₄ R,

R ₁ O,

R ₂ O '
HO

R ₂ O '

Process for the production of acidic esters of phosphonic acids or their salts

Applicant

Henkel & Cie. G.m.b.H., Dusseldorf-Holthausen, Henkelsti. 67

Dr Wilhelm Jakob Kaiser, Dusseldorf-Holthausen has been named as the inventor

and R ₆ can mean hydrogen or identical or different aliphatic, cycloaliphatic or aromatic hydrocarbon radicals. The radicals R ₁ to R ₆ , insofar as they mean hydrocarbon radicals, can be straight-chain or branched. They can also be substituted, ζ B by halogen atoms be interrupted

Used as a starting material for the inventive Process a connection with 2 halogen atoms in the α-position to form cahonamide groups in the molecule, for example that made from ethylenediamine and 2 moles of chloroacetic acid Diamide, is formed by reaction with 2 moles of Di alkyl phosphite in an analogous manner according to the following formula a 2basischei acidic ester

CI-CH ₂ -CO-NH-CH ₂ -Ch ₂ -NH-CO-CH ₂

OH

CH ₂ -CO-NH-CH ₂ -CH ₂ -NH-CO-Ch ₂ -P

-Cl

+ 2R ₁ Cl

The two reactants are preferably used in such a quantitative ratio that on one located in the α-position to the carbonamide group Halogen atom encompasses about 1 mole of dialkyl phosphite in excess of one or medium component however, it is not harmful Γη some cases it may be useful to wait an organic solvent or diluent

The reaction ei takes place at such temperatures in which an elimination of alkyl halide takes place preferably at Ternpei breathe above 100 ° C The alkyl halide distills, if heated of dialkvlphosphite a medermolekulaiei Alcohol was used during the reaction from the reaction mixture from Wuide z.111 To prepare the dialkyl phosphite a high molecular weight alcohol is used, the alkyl halide can be used or distilled off in vacuo after the reaction will

809 747/451

Those obtained after the reaction according to the invention acidic esters of phosphonic acids can be easily converted into their salts, e.g. B. the alkali salts, convict. They can be used in the form of acid esters or in the form of salts as corrosion protection agents Find use. Furthermore, with a suitable molecular size, they can be used as capillary-active agents for the most diverse purposes, e.g. B. can be used as a cleaning agent or for textile finishing.

Those from compounds with several halogen atoms in the α-position to the carbonamide groups Acid esters of di- or polyphosphonic acids that can be prepared can also be prepared with polyhydric alcohols be converted to acidic or neutral polyesters of various molecular sizes.

Reactions of dialkylphosphene with compounds which contain a CO group are already under way has been described several times. However, this well-known reaction is not dependent on the presence of one in the α-position to the CO group dependent and does not take place with cleavage by L-Jalogcnid. There are no acidic esters, but rather neutral esters.

A mixture of 104.6 g of monochloroacetic acid dodecylamide and 55.2 g of diethyl phosphite was under Stirring heated to 140 to 145 ° C until a weight decrease of 26.3 g as a result of the cleavage of Ethyl chloride had entered. The reaction product was a viscous liquid of strongly acidic reaction represent.

1 g of this product was dissolved in 3 cm ^{3 of} alcohol and 3 cm ^{3 of} 10% sodium hydroxide solution were added. It was then diluted to 1 l with water. A clear, strongly foaming solution was obtained which showed a good wetting effect.

In the same way, 94 g of monochloroacetic acid tert-octylamide were obtained reacted with 63.1 g of diethyl phosphite. It became a reaction product of the like Properties obtained as above.

Example 2

.OC

2 H ₅

NH-CO-CH ₉ -P

A u u u η g s b e i s ρ ι e 1 1

OC, H _S

-NH - CO - CH, - P '

OH

as a mixture of 52.4 g of the p-chloroanilide of Chloroacetic acid and 35.4 g of diethyl phosphite were stirred at 140 to 145 ° C. for 24 hours. Here stepped a weight reduction of 16.85 g as a result of the elimination of ethyl chloride. The residue formed a viscous oil with a strongly acidic reaction.

Embodiment 3

C ₂ H ₆ O.

HO '

-P-CH ₂ -CO-NH- (CH ₂ ) _e -NH -CO -CH ₂ -P;

OC ₉ H,

OH

A mixture of 54.5 g of hexamethylene di (monochloroacetamide) and 55.8 g of diethyl phosphite was heated to L30 ° C with stirring until development of ethyl chloride had caused a decrease in weight of 26.4 g. What remains in the flask almost colorless, viscous product with water gave clear solutions of a strongly acidic reaction.

Under the same reaction conditions, a mixture of 39.8 g of tetramethylene di (monochloroacctamide) and 44.9 g of diethyl phosphite, a readily water-soluble, viscous, practically colorless one Product obtained from acidic reaction.

A u u u η g s b e i s ρ i e 1 4

A mixture of 41.9 g of chloroacetyl-l ^ .S ^ -tetra.-hydroquinoline and 38.8 g of dibutyl phosphite was heated to a temperature while bubbling nitrogen heated from 140 to 145 ° C until the weight loss caused by the splitting off of butyl chloride Was 18.7 g. The residue was a viscous, red-brown liquid which was acidic Reaction exhibited and dissolved in dilute sodium hydroxide solution. The solution thus obtained foamed strong.

Claims (1)

Claim: 45 Process for the production of acidic esters of phosphonic acids or their salts, characterized in that that one-halogenated carboxamides with dialkyl phosphites at such temperatures brings to reaction, in which an elimination of alkyl halide takes place and optionally the acidic esters obtained are converted into their salts. Considered publications:
German Auslegeschrift No. 1 000 364;
U.S. Patent No. 2,485,573;
Chemical Abstracts, 1954, column 10,542 (Gil'ni Kamai and VA Kukhtin). © 809 747/451 1.59