DE1194852B - Process for the production of phosphonic acids or their salts with at least two phosphorus atoms in the molecule - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C07f

German class: 12 ο -26/01

Number: 1194 852

File number: H 50724IV b / 12 ο

Filing date: November 2, 1963

Opening day: June 16, 1965

For the production of organic acylation products of phosphorous acid there are a number of Procedure known. So you can, for example, phosphorous acid with carboxylic acid chlorides or Carboxylic acid anhydrides or with mixtures of both to produce such products. In order to obtain good yields, it has been found to be expedient to use an excess of acylating agents to work, d. That is, 1 to 2 moles of acylating agent are generally obtained per mole of phosphorous acid to use. Instead of carboxylic acid chlorides and phosphorous acid can also Phosphorus trichloride and carboxylic acids can be used in appropriate stoichiometric amounts.

In all of the manufacturing processes known to date, mixtures of different products are often produced, whose constitution has not yet been determined in detail. Chromatographic studies have, however show that some of the mixtures are very complex. Lots of these Mixtures are also produced in the form of oil during insulation. If you put these products in the appropriate salts transferred, even after spray drying, only hygroscopic products are generally obtained.

The production of uniform products from the reaction mixtures is either by a relative cumbersome and with high losses of substances associated crystallization process or by treatment the reaction mixture with water at elevated temperature and possible distillation of the volatile constituents possible. The latter process gives uniform compounds in good yields, when compounds derived from lower carboxylic acids are used as acylating agents. In the case of higher carboxylic acids, uniform compounds are also obtained, however the products to be separated off by distillation are only slightly volatile and therefore require a relatively long time Distillation times. Also occur even with distillation in vacuo at the required temperatures slight decomposition, associated with a darkening of the substance.

The invention now relates to a process for the preparation of phosphoric acids or their salts with at least two phosphorus atoms in the molecule from mixtures obtained in the reaction of acylating agents with phosphorous acid or of PCl ₃ with carboxylic acids, in particular aliphatic carboxylic acids. The process is characterized in that these mixtures with lower aliphatic alcohols are used in at least processes for the preparation of phosphonic acids
or their salts with at least two
Phosphorus atoms in the molecule

Applicant:

Henkel & Cie. G. m. B. H.,

Düsseldorf-Holthausen, Henkelstr. 67

Named as inventor:

Dr. Hans Günther Germscheid, Hösel (RhId.) - -

slight stoichiometric excess over the excess of used as the starting component Treated acylating agent and a) distilled off the volatile substances formed and, if appropriate the acids are converted into the salts in a manner known per se, or b) after the addition of bases, the separates alcoholic layer.

As has been found, largely uniform non-hygroscopic ones are obtained with this method of operation Links. According to previous investigations, the compounds correspond to the following formula

ORO

HO-P-C-P-OH

OH OH OH

where R is an aryl or alkyl radical which is one carbon atom less than that for the reaction used carboxylic acid.

The alcohols used are preferably methanol or ethanol. However, others can as well Lower alcohols, such as propanols, butanols or pentanols, are used. An excess of 5 to 20% of alcohol compared to the excess of acylating agent, which is used as the starting component used is sufficient.

In order not to unnecessarily increase the volume of the portions of the reaction mixture to be separated off later as a layer or distillate, it has proven to be proven expedient, not more than 5 times, preferably 1.1 to 3 times, in alcohol over the to use the stoichiometric proportion resulting from the excess of acylating agents.

509 580/436

3 4

When the reaction mixture was treated with, the mixture was heated to boiling and then refluxed

Alcohol, it is expedient to slowly increase the temperature to 110 ^° C. at an elevated temperature. After this

to work, since a better miscibility had been stirred for ^{2 hours at 110 0 C, was on}

is achieved and optionally ^{cooled for the subsequent 60 0} C and added 100 ml of ethanol.

Distillation requires less heating. 5 After thorough mixing, the volatile

If desired, however, the hand-held components can also be distilled off and the last remainder in the

Carry out treatment at room temperature. Vacuum removed at 100 torr. The residue was

To get to the free phosphonic acids, add a little water for crystallization

one works the alcohol-treated reaction brought. The Hydroxyäthandiphosphon-

Mix advantageously in such a way that all volatile io acids of the formula

Components distilled off. Distilling off the _Γ ττ rvnwvpn hi. ι u η

Volatile constituents can generally be CH ₃ C (UHXFU ₃ H ₂ J ₂ IH ₂ U

faster, more complete and at lower temperatures - is practically free of acetic acid. The yield was

Doors run as if after treatment with 90% of theory.

Water at elevated temperature the free carbon 15 R '' 1 2

acids must be removed or the reaction- ^J ^ ¹

mixture is simply subjected to a distillation. 50 kg of PCl ₃ became a mixture with stirring

Due to the low distillation temperatures, 35 kg of acetic acid and 9.2 kg of water are added,

decomposition largely prevented, and wherein the temperature is between 30 and 4O ⁰ C held

receive light colored products. The resulting Phos- 20 was. Then 2 hours at 100 ⁰ C.

Phonic acids can be stirred by known methods. The product was below the boiling point of the

Neutralization with aqueous or alcoholic methanol and then cooled with 25 liters of methanol

Alkalis, e.g. B. alkali, ammonia or tetra added. The volatile constituents were distilled off

alkylammonium hydroxide, converted into their salts and the last residues in vacuo at 100 Torr

will. However, it is not necessary to remove it for manufacture. The leftover syrup was in so much

of the salts first the pure phosphonic acids from water taken up that a 60% hydroxyl

and then convert them into the salts. Ethan diphosphonic acid was formed. The thus obtained

As has also been found, the salts obtained are practically free of acetic acid. Yield:

also in pure form, if you do that with alcohol 59 kg (94.5% of theory),
treated mixture mixed with bases and the 30

separating two layers. The lower aqueous example 3
Layer contains the phosphonic acid salt. The amount

of the bases added depends on which 1098 g of PCl ₃ were in each case a mixture with stirring

desired degree of neutralization of the present from 768 g acetic acid and 202 g water added,

Phosphonic acids. 35 with the temperature kept between 30 and 40 ° C

From the resulting aqueous solutions can became. Then it was first refluxed

boiled by crystallization, spraying or precipitation, then the temperature slowly to 120 ^° C

the solid salts are increased with organic solvents. After 1 hour stirring at 12O ⁰ C

be asked. However, this can also be achieved by cooling it to 30 ^° C. and adding 500 ml

Obtained from the outset that the bases are added in the form of 4 ° methanol. After thorough mixing it was

alcoholic solutions are added. Neutralized as bases with 800 ml of 40% sodium hydroxide solution, whereby

In particular, sodium hydroxide and potash formed two layers. The lower aqueous

Umhydroxyd or also alcoholates into consideration. Layer was separated and after concentration

The salts fall in a solid, non-hygroscopic manner, the sodium salt of the hydroxyethane diphosphonic

Shape. 45 acid of the formula

Compared to the known process, the conversion of the resulting reaction mixture into a (NaO) ₂ P (O) - C (CH ₃ ) (OH) - P (O) (OH) (ONa)
To undertake a uniform connection by the action of water 4 H ₂ O, the method of operation according to the invention offers the advantage of significantly shorter treatment times obtained in solid crystallized form. Yield: times. When working up without distillation 92% of theory,
volatile constituents can in the case of the invention B is η ie 1 4
the neutralization to the de-

Speaking salts immediately after the addition of the alcohol 90 g of acetic acid and 27 g of water were at 30 to

are connected, while when using 55 40 ⁰ C with stirring mixed with 137 g of PCl ₃ . Subsequent

of water for several hours until the end was heated to boiling under reflux and the

Achieving uniform products is necessary. Be temperature slowly increased to 110 ⁰ C. After this

the volatile constituents were distilled off so that the mixture had been stirred ^{at 110 ° C. for 2 hours, was on}

The distillation times ⁰ C cooled in the inventive 6O and mixed with 100 ml of methanol.

Less than half of those times, 60 after thorough mixing, concentrated

which neutralized upon treatment with water or steam ammonia, the ammonium salt

are required to be of the same purity as the hydroxyethane diphosphonic acid of the formula
achieve.

Example 1 (NH ₄ O) ₂ P (O) - C (CH ₃ ) (OH) - P (O) (OH) (ONH ₄ )

65 χ H ₂ O

90 g of acetic acid and 27 g of water were after

Mixing with 137 g of PCl ₃ , the temperature separating out in crystallized form. Yield: 82%

between 30 and 40 ⁰ C was kept. Then the theory.

Example 5

82 g of phosphorous acid were slowly ^{heated to 95 °} C. with 122 g of acetic anhydride and stirred at this temperature for 3 hours. After cooling to 50 ^° C., 100 ml of methanol were added and, after thorough mixing, the volatile constituents were distilled off. The last residues were removed in vacuo. The residue was crystallized with the addition of a little water. The crystals of hydroxyethane diphosphonic acid corresponded to the formula

CH ₃ -C (OH) (PO ₃ H ₂ ) ₂ · 1 H ₂ O
Yield: 88% of theory.

Example 6

Residue of hydroxyhexadecanediphosphonic acid that solidifies in the cold the formula

C ₁₅ H ₃₁ C (OH) (PO ₃ H ₂ ) ₂
weighed 400 g.

Example 10

427 g of stearic acid were melted with the addition of 27 g of water and 87.5 ml of PCl _{3 were} added.

ίο It was stirred for 20 hours at 160 ⁰ C., and the reaction mixture at 60 ⁰ C with 150 ml of ethanol ver. After thorough mixing in a vacuum at 0.1 Torr, the volatiles were removed by distillation up to a bottom temperature of 190 ⁰ C; what remained was a brownish syrup of hydroxyoctadecanediphosphonic acid of the formula that solidified in the cold

82 g of phosphorous acid were boiled with 118 g of acetyl chloride at reflux and the temperature slowly raised to 120 ⁰ C. After 1 hour stirring at 120 ⁰ C, was cooled to 8O ⁰ C and treated with 100 ml of butanol. After thorough mixing, all volatile constituents were distilled off ^{up to a temperature of 100 ° C. in vacuo at 14 torr.} Yield: 114 g of 85 ° / _o Hydroxyäthandiphosphonsäure strength (94% of theory).

Example 7

348.5 g of caproic acid were mixed with 54 g water and added at about 40 ⁰ C 175 ml PCl. ₃ The mixture was then ^{heated to 140 °} C. for 5 hours and, after cooling to 50 ^° C., 200 ml of methanol were added. After thorough mixing, the volatile constituents were distilled off in vacuo at 12 torr. The residue was dissolved in 200 ml of water and the content of hydroxyhexanediphosphonic acid was determined by titration (55%). The yield is quantitative. The solution contains less than 0.4% caproic acid.

Example 8

517 g of capric acid were mixed with 54 g water and added at about 5O ⁰ C 175 ml PCl. ₃ The mixture was then heated to 140 to 150 ° C. for 5 hours. After cooling to 6O ⁰ C 200 ml of ethanol were added, mixed well, and the volatile constituents in vacuo at 2 Torr up to a bottom temperature of 14O ⁰ C distilled off. The residue consisted of hydroxydecanediphosphonic acid of the formula

C ₉ H ₁₉ - C (OH) (PO ₈ EU,

Yield: 79.5% of theory.

35

40

55

example

769 g of palmitic acid were melted with the addition of 54 g of water and 175 ml of PCl _{3 were} added. It was then heated for 5 hours at 150 ⁰ C and, after cooling to 70 ° C with 200 ml of ethanol. After mixing, the volatiles were up to a bottom temperature of 160 ⁰ C distilled off in vacuum at 1 Torr. The yellow one, yield: 95.8% of theory.

Example 11

183 g benzoic acid and 27 g of water were added after mixing with 137 g of PCl _3, wherein the temperature between 40 and 50 ⁰ C. ⁰ C was then heated with stirring and left for 4 hours at this temperature to 14O. After cooling to 65 ^° C., 150 ml of methanol were added, mixed thoroughly and the methyl benzoate and the excess alcohol were removed in vacuo. The conversion was 95%. The phenyl-hydroxymethanediphosphonic acid of the formula

C ₆ H ₅ C (OH) (PO ₃ H ₂ ) ₂
still contained small amounts of benzoic acid.

Claims (3)

Patent claims: 1. A process for the preparation of phosphonic acids or their salts with at least two phosphorus atoms in the molecule from mixtures which have been obtained in the reaction of acylating agents with phosphorous acid or of PCl ₃ with carboxylic acids, characterized in that they are mixed with lower aliphatic alcohols in at least treated with a small stoichiometric excess over the excess of acylating agent used as the starting component and a) the volatile substances formed are distilled off and, if appropriate, the acids in an converted into the salts in a known manner or b) separating off the alcoholic layer after adding bases. 2. The method according to claim 1, characterized in that the mixtures with methanol and / or ethanol. 3. The method according to claim 1 and 2, characterized in that the bases in the form of alcoholic Solutions are added. Considered publications:
German interpretative document No. 1 148 551. 509 580/436 6.65 © Bundesdruckerei Berlin