DE1299290B - Process for the preparation of salts of phosphoric acid esters of sugar or polyhydric alcohols - Google Patents

Description

The invention relates to a process for the production. It has been found that by using the of salts of phosphoric acid esters of sugars or stoichiometric amount of calcium oxide, calcium polyvalent Alcohols by converting a hydroxide or calcium carbonate instead of an excess water Solution of the sugar or polyvalent shot the need of treating the Alcohols in the presence of calcium oxide, calcium hydroxide 5 Filtrate with carbon dioxide to remove excess or carbonate is switched off with calcium in chlorinated hydrocarbons. Furthermore, dissolved phosphorus oxychloride. when carrying out the reaction under these conditions

A wide variety of processes are used to produce salts of phosphoric acid formations, the yield of calcium salts of sucrose esters of sugars and of polyhydric alcohols monophosphates of about one third of the yield. Thus io weight of the sucrose used in the prior art there is already a process for the preparation of procedures ₀ of the theoretical amount of glucose and Saccharosemonophosphorsäureestern increased up to 90 ° /. Similar increases in product yields through the action of phosphorus oxychloride on water are achieved if other sugars or polyvalent solutions of the sugars (German patents alcohols phosphorylated under these conditions 247 809 and 484 356, German Auslegeschrift 1011 870 15).

and "Biochemische Zeitschrift", February 1910, p. 515 When using trichlorethylene for dissolution

to 517). of phosphorus oxychloride and use of these

In one of the known processes, the ice-cold solution of 180 g of sucrose in 21 water is used as a solution for the phosphorylation reaction, according to the known process in which 115 g of freshly calcined calcium oxide are suspended in addition to alcohol-free dry chloroform, slowly a solution of 77 g phosphorus oxy-switched; In addition, this results in a chlorination in alcohol-free chloroform (250 cm ³ ) simplifying the process and increasing the output. After several hours of stirring, the solution is boiled and a facility in the recovery of the filtered and carbon dioxide passed into the filtrate to remove solvent.

Excess calcium oxide to be removed as carbonate. 25 The following reaction conditions have been eliminated. The filtered solution is then concentrated and lasts:
calcium sucrose phosphate containing calcium chloride

precipitated with alcohol. To obtain a calcium chloride % sugar concentration in the reaction mixture:

To obtain free product, the product is five or ¹² > ° S ( ¹ OO g water,

dissolved six times in water and precipitated with alcohol. 30 ²⁴ > ° S / ¹⁰⁰ S water.

The yield of calcium sucrose monophosphate 2nd reaction temperature:

according to the known methods was about one third 0 ° C,

the weight of the sugar used. The equation 15 ° C.

for the reaction is indicated as follows: "_. , _,. ,, ..., _, m _n ^

^{s &&} 3. Composition of the chloroethylene / POClg-

2 C ₁₂ H ₂₂ O ₁₁ + 2 POCl ₃ + 5 CaO ³⁵ mixture:

-> - 3 CaCl ₂ + H ₂ O + 2 C ₁₂ H ₂₁ O ₁₀ - OPO ₃ Ca 1 part by weight Morethylene / part by weight POCl. ,,

, .. ,, "" .j _JD , .. ". . 1 part by weight of trichlorethylene / 0.2 part of POCl ₃ .

whereby it is stated that it is expedient '

Calcium oxide in excess over the duration of the addition of the trichlorethylene-POClg-

to use the specified stoichiometric amounts. 40 mixture:

The invention is based on the object of a 3 hours,

improved method of making salts from 8 hours.

Phosphoric acid esters of sugars or polyvalent 5, degree of stirring:

To create alcohols of the type mentioned at the beginning, about 10 PS / 45461.

which leads to particularly good yields and the 45 slow stirring, less than 1 PS / 45461. Obtaining the salts of phosphoric acid esters in pure

Simplified shape. These areas have been tested in a number of trials

The method according to the invention for production determined which were carried out to determine the main of salts of phosphoric acid esters of sugars and their influence on the quality of the monohydric or polyhydric alcohols by reacting a 50 prepared calcium sacchaxose phosphate, aqueous solution of the sugars or polyvalent die in these reactions products obtained were alcohols in the presence of calcium oxide, hydroxide to that of example 1 and similarly passed 80 to or with carbonate in a chlorinated hydrocarbons 90 ° / ₀ of sucrose monophosphates. The main substance dissolved phosphorus oxychloride is characterized by the fact that the reaction between the products is characterized by the fact that the reaction is carried out with 1 mole of phosphorus of the inorganic phosphorus oxychloride present in the end product and 2.5 moles of the calcium compound calcium phosphate. This amount was between 1 and per mole of sugar or polyhydric alcohol at 0 to 4.5 ° / _0, calculated as phosphorus and based performs at 15 ° C and with vigorous stirring, the total weight of the product, then the calcium salt of Phosphorsäureesters Factors influence the amount of inorganic calcium phosphate present from the calcium chloride formed in a known manner, in particular by repeated precipitation with - ^ ₁ . - ^. ·, · Alcohol, or in a manner known per se by ^L Reaction temperature: A low temperature

Gel filtration or ion ^{displacement separated and from} ° 9 J errm F ^rt t. § ^{the eblldete Men} S ^{e of} optionally calcium salts obtained or inorganic phosphate. Phosphoric acid ester converted in a known manner into the salts 65 2. Concentration of the trichlorethylene-POCls-other metals. Mixture: As the concentration of POCl ₃ decreases, in the case of the trichlorethylene according to the invention, the amount of process formed, the conversion in trichlorethylene, is preferably carried out. inorganic phosphate.

3 4

3. Purity of the POCl _{3 used} : Is obtained by Redestil- lum percent ethanol. The calcium ions of the POCl ₃ before use, the sucrose phosphate is precipitated as a fine, white powder formed amount of inorganic phosphate. After stirring for 30 minutes, decrease. this product filtered off and dried. In this

4. If the movement of the reaction mixture containing the product ⁵ moment about 12 Gewichtsabgeschwächt was the amount increased gebil- P ^{r (? Ze} ^ Calaumchlond. To a DETEM Calcmmchlorid of inorganic phosphate considerably. To obtain J ^rei f product, this precipitation must still

repeated five or six times.

The process can be batch or continuous. Calcium chloride can be removed borrowed. Regardless of whether io also by extraction of the in the first precipitation

is worked batchwise or continuously, is obtained calcium sucrose phosphate with 70 to

vigorous agitation during the reaction, precipitation and 80% ethanol instead of the one described

Carry out multi-stage precipitation for good yields of pure salts extraction. To do this, the solid

essential. Product 30 minutes vigorously at 2 to 5 times

The extraction of the calcium salt of phosphorus stirred up its weight in aqueous ethanol. Five

acid esters from the reaction medium can be found in ver extractions to be sufficient to obtain one of

can be done in different ways. The calcium chloride-free product is suitable to obtain. Of the

German Patent 247 809 described method efficiency of calcium chloride removal was

precipitation with alcohol followed by renewed use of more dilute ethanol solvents Dissolution in water and precipitation in alcohol, ao gen and larger quantities increased for each extraction.

On a large industrial scale, it is an economy- this leads to too much loss More extensive use of alcohol by countercurrent organic phosphates and excessive ethanol extraction of the product with alcohol or a consumption. The final yield of calcium sucrose aqueous The alcohol solution for removing the calcium phosphate is about 80 to 90% of theory, chloride possible. »5 Instead of the reaction mixture before the first

Furthermore, the separation of the calcium salts of the precipitation stage has to be restricted if the product can be removed

Phosphoric acid esters of calcium chloride also precipitate through the reaction mixture by taking under

Gel filtration or ion displacement possible. vigorous stirring of ethanol to a final concentration

From the calcium salt can tration of 80 percent by volume to the reaction mixture in a known manner there are other salts of the 30 prepared by this process.

Phosphoric acid esters can be prepared by The calcium salt obtained can be prepared in the following manner

E.g. an aqueous solution of the calcium salt can be converted into the sodium salt:

a cation exchange resin in the hydrogen form A 2% solution of calcium sucrose phosphate

directs. The calcium is retained on the resin, and phats were replaced by a cation exchange

the phosphoric acid ester running through the column is passed resin-filled column. The expiration from this

can with a suitable base, which was the desired column with sodium carbonate in the light

Metal, e.g. B. Sodium hydroxide, contains, neutralized, excess neutralized,

will. The solution was then concentrated and the sodium

The method according to the invention is particularly good salt of sucrose phosphate by slow addition applicable for the preparation of the calcium salts of 40 precipitated from ethanol. The product was out Phosphates of mannitol, sorbitol, dihydroxyacetone, aqueous ethanol reprecipitated, leaving a white powder Glycerin, galactose, arabinose, ribose, xylose, obtained from pure sodium sucrose-maltose, Lactose, raffinose and glucose. phosphate.

The process of the invention is illustrated by the following examples Examples explained. The sugars were twisting the invention to some other sugars and 45 before their use 24 hours in a vacuum- polyhydric alcohols.

oven dried at 80 ° C. The last stage of the process, i. H. the separation of the

Ester, was carried out in these examples to that in Example 1

Example 1 described way and is therefore no longer

50 described.

This example was found suitable for the preparation of calcium sucrose monophosphates. Example 2
Sucrose (350 g, 1.02 mol) is distilled in 1.51

Dissolved in water. Calcium oxide (140 g = 2.5 mol) or maltose monophosphate

Calcium hydroxide (180 g = 2 5 mol) is in the 55 _{L 3} 50 g maltose (1.02 mol),

Suspended solution, which is cooled to 0 ° C. A _{140 Ca0} «5 mol) and

Solution of phosphorus oxychloride (153.4 g = 1.0 mole) _2,000 cc of water

in 150 cm »trichlorethylene is slowly mixed with and cooled to ^{0 0 C,}
vigorous stirring of the reaction mixture in one

Cooling bath that keeps the temperature at around 0 ° C, 60 Π. 153.4 g POCl ₃ (1.0 mol) and

admitted. A time of around 290 g trichlorethylene (or chloroform) is required for the addition

3 hours required. were mixed and added to I at 0 ° C, and

After the reaction has ended, the reaction is carried out with stirring on the described in Example 1

mixture centrifuged or filtered and the filtrate in the same way,
concentrated to a solids content of about 60%. The 65th

Product is isolated by taking this concentrate The yield of maltose monophosphates

slowly with vigorous stirring to as much ethanol 60% of the maltose used, d. i.e., about 65% of the

is given that a final concentration of 80 Vo phosphorus in the phosphorus oxychloride were in maltose

implemented monophosphate. The final product contained 2 ° / ₀ phosphorus as an inorganic calcium phosphate.

Example 3 and 4

5 mannitol or sorbitol phosphates

I. Anhydrous mannitol

(or sorbitol) 9.1 g (0.036 mol)

CaCO ₃ 10.0 g (0.1 mol)

Water 100 ecm

were mixed and cooled ^{to 0 ° C.}

II. POCl ₃ 7.6 g (0.05 mol)

Trichlorethylene 15 g

were mixed and added at 0 ° C with stirring as in Example 1 to _ig I.

The yield of sorbitol or Mannitphosphaten was about 70 ° / _0, based on the alcohol used. The final product contained 2 ° / ₀ phosphorus as inorganic calcium phosphate.

Example 5 Lactose Phosphate “ ₅

I. Lactose 350 g (1.02 moles)

CaO 140g (2.5 moles).

Water 3000 g

were mixed and cooled to 0 ° C.

II. POCl ₃ 153.4 g (1.0 mol)

Trichlorethylene 290 g

were mixed and added ^{to I at 0} ° C. with stirring as in Example 1. The addition took place within 3 hours.

35

The yield of Lactosemonophosphaten was about 50 ° / _0, based on the amount of lactose. The final product contained about 2 ° / ₀ phosphorus as an inorganic calcium phosphate.

Example 6
Galactose monophosphates

I. Galactose 180 g (1.0 mole)

CaO 140 g (2.5MoI)

Water. 1500 cm ³

were mixed and cooled to 0 ° C.

II. POCl ₃ 153.4 g (1.0 mol)

Trichlorethylene 290 g

were mixed and at 0 ° C with stirring as in Example 1 within 3 hours to I given.

55

The yield of Galactosemonophosphaten was about 20 ° / _0, relative to the employed galactose. The final product contained about 3% phosphorus as inorganic calcium phosphate.

Example 7 Arabinose monophosphates

I. Arabinose 12.0 g (0.08 mol)

CaO 11.2 g (0.20 mol)

Water 200 ecm

were mixed and cooled to 0 ° C.

II. POCl ₃ 12.2 g (0.08 mol)

Trichlorethylene 37 g

were mixed and added ^{to I at 0} ° C. with stirring as in Example 1 within one hour.

The yield of arabinose monophosphates was 75% of the arabinose used. The end product contained 2% phosphorus as inorganic calcium phosphate.

Example 8 Fructose Phosphoric Acid Ester

I. Fructose 180 g (1.0 mole)

CaCO ₃ 250 g (2.5 mol)

Water 1500 ecm

were mixed and cooled to 0 ° C.

II. POCl ₃ 153.4 g (1.0 mol)

Trichlorethylene 290 g

were mixed and added to I at 0 ° C. with stirring as in Example 1. The encore required 3 hours.

The yield of fructose phosphates, which consisted mainly of fructose diphosphate, was about 50% of the fructose used.

Claims (2)

Patent claims: 1. Process for the preparation of salts of phosphoric acid esters of sugars or polyvalent ones Alcohols by reaction of an aqueous solution of sugar or polyhydric alcohol in the presence of calcium oxide or calcium hydroxide or carbonate with phosphorus oxychloride dissolved in a chlorinated hydrocarbon, characterized in that the Reaction with 1 mole of phosphorus oxychloride and 2.5 moles of the calcium compound per mole of sugar or polyhydric alcohol at 0 to 15 ° C and with vigorous stirring, then the calcium salt of the phosphoric acid ester of the calcium chloride formed in a known manner, in particular by repeated precipitation with alcohol, or in a manner known per se Separates gel filtration or ion displacement and optionally the calcium salts obtained Phosphoric acid ester converted into the salts of other metals in a known manner. 2. The method according to claim 1, characterized in that one carries out the reaction in trichlorethylene performs.