DE1568202B2 - PROCESS FOR THE PRODUCTION OF UREIDOALKYLPHOSPHONIC ACID DERIVATIVES - Google Patents

Description

R ² -N
R ¹

R ⁴ O OR ⁵

II /

N-CH-P

IO

(D

R ³

OR ⁶

in which R ^{1 is} a hydrogen atom, a low molecular weight alkyl radical, together with R ^{3 an} ethylene or 1,3-propylene ^{radical or with R 4} an ethylene radical, whereby these alkylene radicals can each be substituted by low molecular weight alkyl radicals, R ^{2 is} a hydrogen atom, a low molecular weight alkyl radical or a remainder of the formula

Has the abovementioned meaning with dialkyl phosphorous esters of the formula

O OR ⁵

II /

Η — Ρ

OR ^h

(Hl)

in which R ⁵ and R ^{6 have} the abovementioned meaning, optionally with the addition of basic or acidic catalysts and / or a solvent or diluent at a temperature of 20 to 150 ° C, low molecular weight alkyl radicals being understood to mean those with 1 to 4 carbon atoms.

2. The method according to claim 1, characterized in that instead of the substances of the formula II Urea of the formula

-CHOIR

10

-CH ₂ - P

O OR ⁵

II /

OR ⁶

R ^{3 is} a hydrogen atom, a low molecular weight alkyl radical or together with R ¹ an ethylene or 1,3-propylene ^{radical, R 4 is} a hydrogen atom or together with R ^{1 is} an ethylene radical, the alkylene radicals in turn being substituted by low molecular weight alkyl radicals, R ⁵ and R ^{6 being} low molecular weight Alkyl radicals, R ¹⁰ denotes a hydrogen atom or a low molecular weight alkyl radical and X denotes an oxygen or sulfur atom, characterized in that urea derivatives of the general formula

X C.

R ⁴

R ⁸ -N
R ⁷

-CHOIR

¹⁰

(II)

R ⁹

in which R ^{7 is} a hydrogen atom, a low molecular weight alkyl radical or, together with R ^9, an ethylene or 1,3-propylene ^{radical or with R 4} an ethylene radical, the alkylene radicals in turn being substituted by low molecular weight alkyl radicals, R ⁸ a hydrogen atom, a low molecular weight alkyl radical or a radical of the formula -CH ₂ -OR ¹⁰ , R ^{9 is} a hydrogen atom, a low molecular weight alkyl radical or, together with R ^7, an ethylene or propylene radical optionally substituted with low molecular weight alkyl radicals, R ^{4 is} a hydrogen atom or together with R ^{7 is} an optionally equally substituted ethylene radical , R ¹⁰ denotes a hydrogen atom or a low molecular weight alkyl radical and X denotes R ¹² —N

R ¹

Ν — Η

(IV)

13th

and formaldehyde is used, where R ¹¹ and R ^{13 are} hydrogen atoms, low molecular weight alkyl radicals or together an ethylene or 1,3-propylene radical which can be substituted by low molecular weight alkyl radicals, R ^{12 is} a hydrogen atom, a low molecular weight alkyl radical and X is an oxygen or sulfur atom, and the substances of the formula II can be formed as an intermediate in the reaction mixture, low molecular weight alkyl radicals containing 1 to 4 carbon atoms.

45 The invention relates to a process for the production of ureido-alkylphosphonic acid esters which are suitable as flame retardants for textiles.

It has been found that new a-ureido-alkylphosphonic acid derivatives can be used the general formula

Il

CR ⁴ O OR ⁵

/ \ I II /

R ² -NN-CH-P

R ¹ R ³ OR ⁶

in which R ¹ is a hydrogen atom, a low molecular weight alkyl radical, together with R ³ a Äthylenoder 1,3-propylene radical or an ethylene radical R ^4, said alkylene may be substituted by low molecular weight alkyl radicals, R ² a

Hydrogen atom, a low molecular weight alkyl radical or a radical of the formula

-CH ₇ -OR

10

-CH ₂ -P

O OR ⁵

II /

OR ⁶

R ^{3 represents} a hydrogen atom, a low molecular weight alkyl radical or, together with R ^1, an ethylene or 1,3-propylene ^{radical, R 4 represents} a hydrogen atom or, together with R ^1, an ethylene radical, where the alkylene radicals can in turn be substituted by low molecular weight alkyl radicals, R ⁵ and R. ⁶ low molecular weight alkyl radicals, R ^{10 is} a hydrogen atom or a low molecular weight alkyl radical and X is an oxygen or sulfur atom, if you can produce urea derivatives of the general formula

R ⁴

R ⁸ -N
R ⁷

N-CH-OR

R ⁹

ίο

(Π)

in which R ^{7 is} a hydrogen atom, a low molecular weight alkyl radical or, together with R ^9, an ethylene or 1,3-propylene ^{radical or with R 4} an ethylene radical, the alkylene radicals in turn being substituted by low molecular weight alkyl radicals, R ⁸ a hydrogen atom, a low molecular weight alkyl radical or a radical of the formula —CH ₂ -OR ¹⁰ , R ^{9 is} a hydrogen atom, a low molecular weight alkyl radical or, together with R ^7, an ethylene or propylene radical which is optionally substituted with low molecular weight alkyl radicals, R ^{4 is} a hydrogen atom or, together with R ^7, an optionally equally substituted ethylene radical , R ¹⁰ denotes a hydrogen atom or a low molecular weight alkyl radical and X has the abovementioned meaning with phosphorous acid dialkyl esters of the formula.

H-

O OR ⁵

OR ⁶

(III)

in which R ⁵ and R ^{6 have} the abovementioned meaning, optionally with the addition of basic or acidic catalysts and / or a solvent or diluent at a temperature of 20 to 150 ° C., low molecular weight alkyl radicals being understood to mean those having 1 to 4 carbon atoms are.

Starting materials of the formula II are, for. B. Mono- and di-N-hydroxymethyl compounds and -N-alkoxymethyl compounds with a low molecular weight alkoxyl radical of open-chain ureas, such as urea itself, monomethylurea, monopropylurea, asymmetrical dimethylurea, symmetrical dimethylurea, N-methyl-N'-ethylurea, symmetrical and asymmetrical dibutylurea , Ν, Ν, Ν'-trimethylurea, of cyclic ureas, such as imidazolidone-2, 4-methylimidazolidone-2, N-methylimidazolidone-2, hexahydropyrimidone-2, 4-hydroxyhexahydropyrimidone-2, 5-hydroxyhexahydropyrimidone -Ethoxy-hexahydropyrimidone-2, 4-methyl-hexahydropyrimidone-2, N-methyl-hexahydropyrimidone-2, 4-hydroxy-5,5-dimethyl-hexahydropyrimidone-2 and 4-methoxy-5-ethyl-5-butyl-hexahydropyrimidone -2, as well as corresponding open-chain and cyclic thioureas. Also, as starting materials of the formula II are, for example, 1,3 - dimethyl -A- methoxy hexahydropyrimidon - 2, 1,3-dimethyl - 4 - hydroxy - 6 - isopropyl - hexahydropyrimidon-2 and 4-hydroxy- and 4-methoxy-1 , 3, 5,5-tetramethyl-hexahydropyrimidon-2 into consideration.

The starting materials of the formula II are known or can be obtained by known processes.

For carrying out the process according to the invention it is generally sufficient to mix the starting materials of the formula II with the Phosphorigsäuredialkylestern of formula III and to act on one another at a temperature of 20 to 15O ⁰ C, preferably 40 to 8O ⁰ C. It is advantageous to use them in the theoretically required molar ratio which results from the fact that each hydroxyl group or alkoxyl group in the substances of the formula II which is separated from an amide nitrogen atom by a carbon atom can react with a molecule of a substance of the formula III. It is not necessary to allow all reactive hydroxyl or alkoxyl groups in the substances of the formula II to react with the substances of the formula III. If you want to convert all the reactive hydroxyl and alkoxyl groups in the substances of the formula II, it is often expedient to use the substances of the formula III in a slight excess. In principle, it is also possible to use the substances of the formula III in an amount less than that required for the conversion of a reactive hydroxyl or alkoxyl group, but this generally has no particular advantages.

Sometimes it is advantageous to start the reaction by adding small amounts of acidic or basic To support catalysts, for example of hydrogen chloride or triethylamine. Besides, it is In some cases it is advisable to add solvents or diluents, such as low molecular weight, to the reaction mixture Alcohols and dioxane, or add the components to be converted from the outset to solve such means.

According to a particular embodiment of the present process, it is possible to use starting materials of the formula II not to be used in preformed form, but rather they are intermediate in the reaction mixture to have formed. To do this, ureas of the formula are used instead of substances of the formula II

X C.

R ¹² -N
R ¹¹

Ν — Η

(IV)

13th

and formaldehyde, where R ¹¹ and R ^{lJ are} hydrogen atoms, low molecular weight alkyl radicals or together

an ethylene or 1,3-propylene radical which can be substituted by low molecular weight alkyl radicals, R ^{12 is} a hydrogen atom, a low molecular weight alkyl radical and X is an oxygen or sulfur atom. Otherwise one works in the same way as described above. Examples of ureas of the formula IV include urea itself, mono-, di- and trimethylurea, imidazolidone-2, N-methylimidazolidone-2, 4-methylimidazolidone-2, hexahydropyrimidone-2, N-ethylhexahydropyrimidone-2, 5.5- Dimethyl-hexahydropyrimidone-2 and 4-isopropyl-5,5-dimethyl-hexahydropyrimidone-2.

The formaldehyde can be in free form or in the form of formaldehyde-releasing substances, such as paraformaldehyde, insert.

The ureidoalkylphosphonic acid esters obtainable by the present process have carbon-phosphorus bonds, which are unusually stable to acids, alkalis and oxidizing agents. The phosphonic acid ester groups can however, saponify very easily in a manner known per se to give free phosphonic acid groups.

: 'The substances of the formula and their saponification products are valuable flame retardants.

The parts mentioned in the examples are parts by weight.

Example i

In a stirred reactor with reflux cooling, the mixture of 66 parts of Ν is Ν'-dimethyl-N-methoxymethyl-urea and 100 parts Phosphorigsäurediäthylester, 1 hour at 100 to 110 ⁰ C, with stirring, heated. When the mixture is heated up, a temporary precipitate occurs, which, however, goes back into solution at 80 to 90 ° C.

: A conversion occurs according to the following equation:

U _v UL ₂ H ₅

II /

CH ₃ -N-CO-NH-CH ₃ + HP

CH ₂ OCH ₃ OC ₂ H ₅

-> CH ₃ -N-CO-NH-CH ₃ + CH ₃ OH
CH ₂

OC ₂ H ₅

O = P

OC ₇ H,

Analysis for QH ₁₉ O ₄ N ₂ P (238):

Calculated ... C 40.3. H 8.0, N 11.8, P 13.0:
found .... C 40.8. H 8.2. N 11.5. P 12.6.

Example 2

86 parts of 4-hydroxy-1, -3,5,5-tetramethyl-hexahydropyrimidone-2 and 100 parts of phosphorous acid diethyl ester are heated in a stirred apparatus for 2 hours at 90 to 100 ° C. with stirring. A clear solution appears after about 10 minutes.
The reaction proceeds according to the following equation:

O OC ₂ H ₅

II /

CH ₃ -N N-CH ₃ + HP

CH ₂ N

2 ^U 5

+ .H ₂ O

The water and the excess phosphorous acid diethyl ester are evaporated off under reduced pressure.: Zur Purification, the product is distilled in a high vacuum. The main faction shows a boiling point of 89 to 92 ° C at a pressure of 2 torr. 152 parts of liquid, .water clear .2-oxo-.1,3.5,5-tetramethylhexahydropyrimidyl - 4 - Phosphonic acid diethyl ester obtained.

Analysis for C ₁₂ H ₂₅ O ₄ N ₂ P (292):

Calculated ... C 49.3; Ή x 8; 5, N 9.6, P 10.6;
found .... C 48.9, H 8.6, N 9.2, P 10.1.

Example 3

After evaporation of the excess phosphorous acid diethyl ester and the split off methanol under reduced pressure becomes the liquid residue fractionally distilled in a high vacuum. The reaction product has a boiling range of 144 to lSl '.' C at a pressure of 0.5 torr. There are 48 parts of N.N'-dimethyl-N-ureidomethylphosphonsäurcdiäthylstcr obtained as a water-clear liquid.

The mixture of 88 parts of symmetrical dimethylurea, 30 parts of paraformaldehyde, 80 parts of phosphorous acid diethyl ester and 100 parts of ethanol is heated in a stirred apparatus with reflux cooling for 3 hours at reflux temperature. After the ethanol and the excess phosphorous acid diethyl ester have been evaporated off under reduced pressure, the liquid residue is distilled in a high vacuum. In the boiling range between 143 and 150 ° C., 79 parts of N ₁ N '- dimethyl ureidomethylphosphonic acid diethyl ester distill at a pressure of 0.5 torr. The reaction product is identical to the product obtained according to Example 1.

Analysis for C "H ₁₉ O ₄ N ₂ P (238)

Calculated ... C 40.3, H 8.0, N 11.8, P 13.0:
found .... C 39.8, H 8.1. N 11.6. P 12.3.

7 8

Example 4

C ₂ H ₅ OCH ₂ -HNCONH-Ch ₂ OC ₂ H ₅ + 2HP (OC ₂ Hs) ₂ OO

Il il

> (C ₂ H ₅ O) ₂ P-CH ₂ -HNCONH-CH ₂ -P (OC ₂ H ₅ ) ₂ + 2C ₂ H ₅ OH

176 parts of Ν, Ν'-diethoxymethyl urea will hold. This corresponds to a yield of 78% of the

Dissolved in 300 parts of phosphorous acid diethyl ester and theory. Stirred at 90 to 95 ° C. for 90 minutes. After evaporation

of the excess phosphorous acid diethyl _{ester and, 5} analysis for ^ ,, Η ₂₆ υ _{7 ΙΝ 2} Ρ ₂ (36υ):

of the ethanol split off in the reaction under Calculated ... C 36.7, H 7.2, N 7.8, P 17.2;

280 parts of the liquid are found under reduced pressure: C 36.6, H 7.3, N 7.6. P 17.0.

Ureido bis [methylphosphonic acid diethyl ester]

B is ρ ie 1 5 f OO

! Il Il

CH ₃ OCH ₂ -HNCSNH-CH ₂ OCH ₃ + HP (OQH ₅ ) ₂ ^ CH ₃ OCH ₂ -NHCSNH-CH ₂ -P (OC, Hs) ₂

164 parts of N ₅ N '- dimethoxymethyl - thiourea product obtained, corresponding to a yield of

90% of theory are in a stirred apparatus with reflux cooling,

138 parts of phosphorous acid _{diethyl ester are added to 30 n cv D} , _m

and heated to 70 to 75 ° C for 2 hours. Among ^{other analyzes for} C ₈ H ₁₉ O ₄ SN ₂ P (270):

The methanol split off is calculated under reduced pressure ... C 35.6, H 7.0, S 11.9, N 10.4, P 11.5;

evaporated. 244 parts of a syrupy one are found ... C 35.4, H 7.1, S 11.5, N 10.1, P 11.3.

Claims (1)

Patent claims: 1. Process for the preparation of u-ureidoalkylphosphonic acid derivatives the general formula Il c