1-13c-caprylic acid synthesis method

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of 1-13C-caprylic acid which is used as a diagnostic preparation when diagnosing motor-evacuation functions of the stomach. The method involves hydrocarboxylation reaction of 1-heptene with carbon monoxide 13CO and water at temperature 100-170C and pressure not above 5 MPa, in the presence of a solvent and a catalyst system which contains a complex compound of palladium and triphenylphosphine in ratio ranging from 1:2 to 1:100, where the solvent used is dioxane and/or aromatic hydrodrocarbon.

EFFECT: obtaining 1-13C caprylic acid with high isotope purity, increased cost-effectiveness of the process owing to increased degree of utilisation of isotope material.

5 cl, 9 ex

 

The invention relates to organic chemistry, in particular to methods for saturated aliphatic carbolic acid containing stable carbon isotopes13With, and in particular 1-13With Caprylic acid. This compound is used as a diagnostic drug for the diagnosis of motor-evacuation function of the stomach.

Analysis of scientific literature shows that there is a method of obtaining enanthic acid containing a radioactive isotope of carbon14In position 1 the molecules of acid (carbonyl carbon atom) (see, for example, Ammara, Delwilliams. "Syntheses of organic compounds with carbon isotopes". M., 1961, p.39). The known method is a multistage process of interaction of methyl iodide-14With dihydroisoquinolin potassium with the formation of 2-methyl-14C-dehydroretinal and then restoring it with a solution containing sodium hydroxide, diethylene glycol and 85%hydrazinehydrate with the formation of the 114With-enanthic acid with access to 39.6%, based on methyl iodide-14C.

Unfortunately, there is a method of obtaining carboxylic acids is complicated by the fact that consists of several stages, and also the use of compounds with radioactive isotope of carbon14C. Another disadvantage of this method is low Ihad target product isotope raw materials.

Previously we have proposed a method of obtaining the 113With Caprylic acid (U.S. Pat. RF 2311402, MKI7SS 51/14, 2007) reaction hydrocarbonsoluble 1-Heptene - its interaction with carbon monoxide13And water at a temperature of 100-170C. and a pressure of not more than 5.0 MPa, in a mixed solvent - propionic acid and o-xylene in the presence of a catalytic system containing a compound of palladium in the form of a complex PdCl2(PPh3)2and triphenylphosphine h3taken in the ratio range of from 1:2 to 1100 respectively. Selectivity for Caprylic acid is 98%. Output 1-13With Caprylic acid in the calculation of the absorbed13WITH 100%. At the same time, the degree of isotopic enrichment was 80%, so the yield of the desired acid13WITH at 78.4% of theoretical.

It is known that carboxylic acids in the conditions of the carbonylation of olefins in solution complexes of palladium and rhodium may be subject to decomposition (decarbonylation) with the release of carbon monoxide (J.Tsuji. Palladium. Reagents and Catalysts. Chichester: John Wiley & Sons: 1998, p.385, 537). In this case formed WITH unlabeled will also interact with the original olefin with the formation of the corresponding carboxylic acid, which could cause a reduction in the degree of isotopic enrichment (isotopic purity) in the pre is its us the way. The yield of 1-13With Caprylic acid source13WITH will be lower due to the decline in the share of initial reagents into the target 1-13With Caprylic acid.

Thus, the disadvantage of this method is the low degree of isotopic enrichment of the 113With Caprylic acid.

In the framework of the present invention solves the task of developing a one-step method of obtaining Caprylic acid with a stable isotope of carbon13In position 1 the molecules of acid (carbonyl carbon atom) with isotopic purity not less than 98%, increased yield of the desired acid in the calculation of the isotopic raw materials, improve the economic efficiency of the process.

The problem is solved in that Caprylic acid stable isotope of carbon13In position 1 is obtained by reaction of hydrocarbonsoluble 1-Heptene - its interaction with carbon monoxide13And water at a temperature of 100-170C. and a pressure of not more than 5.0 MPa, in the solution of a catalytic system containing a complex compound of palladium and triphenylphosphine h3taken in the ratio range of from 1:2 to 1:100, using as solvent dioxane, or aromatic hydrocarbons - benzene, toluene, xylene or their mixtures with dioxane.

The problem is solved also by the fact that the use of giving is giving 13WITH from 0.5 to 1.0 MPa.

The problem is solved by using the temperature from 140 to 160C.

The problem is solved also by the fact that use of the catalytic system with a ratio of complex compounds of palladium and triphenylphosphine in the range from 1:10 to 1:40.

The task is solved in that the reaction mixture is further added hydrochloric acid.

When carrying out the process at temperatures below 140C, the reaction proceeds slowly, and at temperatures above 160C breaks down complex compounds of palladium with separation of metallic palladium.

At pressures below 0.5 MPa decreases the speed of the process, and when the pressure is higher than 1.0 MPa decreases the selectivity of the process.

When the ratio of the complex compound of palladium:triphenylphosphine less than 1:10 decreases the stability of the catalyst, and when the ratio is about 1:40 decreases the speed of the process.

The invention is illustrated by the following examples.

Example 1

In a stainless steel autoclave with a volume of 200 ml, placed on the table of the magnetic prevented, put 0.07 g PdCl2(PPh3)2, 2,62 g PPh3and 5.7 ml of 1-Heptene, 0,36 ml of N2O. as solvent a mixture consisting of 9.6 ml of o-xylene and 4.7 ml of dioxane. The autoclave is pressurized, vacuum, fill with carbon monoxide13CO and heated on the temperature of 150C. Then bring pressure to work (0.5 MPa) and constant support during the whole experience. After 3 hours, turn off the stirring and heating, the autoclave is cooled to room temperature and relieve pressure. The autoclave unload and analyzing the reaction mixture by gas chromatography (GC).

Chromatographic analysis of the products of the synthesis is performed on a gas chromatograph with a flame ionization detector; use metal column size 3 m3 mm, filled with Chromaton N-AW-DMCS (0,16-0,20 mm) with 3% H3RHO4soaked in 10% polyethyleneglycoladipinate. As an internal standard using hexadecane.

To determine the isotopic purity of the 113With Caprylic acid it is recovered from the reaction mass by vacuum distillation and analyzed by the method of NMR nuclei13With (25C, the solution in CDCl3). Use the NMR spectrometer AM-360 (Bruker) with an operating frequency of 360 MHz.

The selectivity of the reaction by Caprylic acid was 95.5%, while the degree of transformation13WITH close to 100%. The isotopic purity of the target 1-13With Caprylic acid is 99%, and its yield per absorbed13CO - 94.5% of theoretical. During the reaction the catalyst is stable and is not destroyed with the release of metallic palladium.

Example 2

The reaction is carried out in the same way as the example 1, however, in the original mixture of 0.02 ml of Hcl conc. and conduct a reaction for 4 hours.

The selectivity of the reaction by Caprylic acid were 96.7%. The isotopic purity of the obtained 1-13With-Caprylic acid - 99%, and its output at full conversion13CO - 95,7% of theoretical. The catalyst is not destroyed.

Example 3

The reaction is carried out as in example 1, however, the operating pressure of carbon monoxide13WITH is 1.0 MPa.

The selectivity of the reaction by Caprylic acid increased by 91.9%. Output 1-13With Caprylic acid per13CO - 90,1% of theoretical, its isotopic purity 98%. In the process, the catalyst is stable.

Example 4

The reaction is carried out as in example 1, but in the solvent used to 14.3 ml of dioxane, and conducting the reaction for 6 hours.

The selectivity of the reaction by Caprylic acid amounted to 94.5%. The isotopic purity of the obtained 1-13With Caprylic acid is 99%, and its output at full conversion13CO - 93.6% of theoretical. The catalyst is stable and is not destroyed with the release of metallic palladium.

Example 5

The reaction is carried out as in example 1, but in the solvent used to 14.3 ml of o-xylene and conducting the reaction for 11.5 hours.

The selectivity of the reaction by Caprylic acid was 81.0%. Output 1-13With Aprilovo acid per 13WITH no absorption - 79,4% of theoretical, its isotopic purity 98%. During the reaction the catalyst is stable.

Example 6

The reaction is carried out as in example 1, but in the solvent used to 14.3 ml of benzene and conduct a reaction for 8 hours.

The selectivity of the reaction by Caprylic acid amounted to 92.2 per cent. The isotopic purity of the obtained 1-13With Caprylic acid is 99%, and its output per13CO - 91,3% of theoretical. The catalyst is stable.

Example 7

The reaction is carried out as in example 1, but in the solvent used to 14.3 ml of toluene and conduct a reaction for 5 hours.

The selectivity of the reaction by Caprylic acid amounted to 94.8%. Output 1-13With Caprylic acid per13WITH no absorption - 92.9% of theoretical, its isotopic purity 98%. During the reaction the catalyst is stable.

Example 8

The reaction is carried out as in example 1, but in the solvent used to 14.3 ml of n-xylene and carry out reaction for 10 hours.

The selectivity of the reaction by Caprylic acid was 81,5%. Output 1-13With Caprylic acid per13WITH no absorption - 80.7% of theoretical, its isotopic purity 99%. The catalyst is not destroyed during the process.

Example 9

The reaction is carried out in the same way, to the to in example 1, however, as the catalytic system using 0.07 g of the complex PD(SLA)2(h3)2and 1.31 g h3and conduct the reaction at a temperature of 110C for 4 hours.

The selectivity of the reaction by Caprylic acid made 94.0%. The isotopic purity of the obtained 1-13With Caprylic acid is 99%, and its output at full conversion,13CO - 93.1% of from theoretical. The catalyst is stable and is not destroyed with the release of metallic palladium.

The advantage of this method is that it allows a single stage, and in a fairly mild conditions (0.3 to 1.0 MPa) to obtain 1-13With Caprylic acid with high isotopic purity of 98-99% is due to the replacement of propionic acid used as a component of the solvent, dioxane, or an aromatic hydrocarbon from a number of: benzene, toluene, xylene, or a mixture of dioxane. The method allows to increase the economic efficiency of the process of obtaining the 113With Caprylic acid by increasing the degree of usage (output) isotopic raw13WITH. Furthermore, the method allows to obtain isotopic diagnostic preparations, not containing dangerous radioactive isotopes.

1. The method of obtaining Caprylic acid with a stable isotope of carbon (1-13C) reaction of hydrocarbonsoluble 1-Heptene with carbon monoxide13 And water at a temperature of 100-170C. and a pressure of not more than 5 MPa, in the presence of solvent and catalyst system comprising a complex compound of palladium and triphenylphosphine in the value taken from the range from 1:2 to 1:100, characterized in that the solvent used dioxane and/or aromatic hydrocarbon.

2. The method according to claim 1, characterized in that the process is carried out at 140-160C.

3. The method according to claim 1, characterized in that the process is performed under a pressure of 0.5-1.0 MPa.

4. The method according to claim 1, characterized in that the ratio between the complex compound of palladium and triphenylphosphine taken from the range from 1:10 to 1:40.

5. The method according to claim 1, characterized in that the reaction mixture is further added hydrochloric acid.



 

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5 cl, 1 tbl, 14 ex

FIELD: organic chemistry, chemical technology.

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7 tbl, 3 ex

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FIELD: chemistry.

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10 ex, 1 tbl

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13 cl, 10 dwg, 12 ex

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2 cl, 19 ex

FIELD: chemistry.

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9 ex

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6 cl, 3 dwg, 1 tbl, 68 ex

FIELD: chemistry.

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6 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention is related to improved method for preparation of manganese oxalate (II) by means of direct interaction of metal with acid in bead mill in presence of liquid phase, in which manganese and oxalic acid are loaded into bead mill in stoichiometric ratio in amount of 0.75-2.4 mole/kg of load at mass ratio of load and glass beads of 1:1.2, liquid phase dissolvent used is water or organic substance, or mixture of organic substances; loading is carried out in the following sequence: liquid phase dissolvent, acid, then metal; process is started at room temperature and is carried out under conditions of forced cooling in the temperature range of 18-39C with control over procedure by sampling method to practically complete spend of loaded reagents for product making, afterwards mixing and cooling are terminated, suspension of reaction mixture is separated from glass beads and filtered, salt deposit is sent for product cleaning from traces of non-reacted metal, and filtrate is returned into repeated process.

EFFECT: method makes it possible to produce target product in absence of manganese dioxide and stimulating additive at temperatures close to room temperature.

2 cl, 13 ex, 2 tbl

Catalyst system // 2372989

FIELD: chemistry.

SUBSTANCE: present invention relates to a new catalyst system, a new carbonylation reaction medium and to a method of carbonylation of ethylene-unsaturated compounds using the new catalyst system. The catalyst system, which is capable of catalysing carbonylation of an ethylene-unsaturated compound, can be obtained by combining: a) group VIIIB metal, or its compound, b) bidentate phosphinic or arsinic ligand and c) acid, where the said ligand is present in molar excess of at least 2:1, compared to the said metal or said metal in its compound, and the said acid is present in molar excess ranging from 5:1 to 95:1, compared to the said ligand. In another version the catalyst system, which is capable of catalysing carbonylation of an ethylene-unsaturated compound, can be obtained by combining: a) group VIIIB metal, or its compound, b) bidentate phosphic or arsinic ligand and c) acid, where molar ratio of the said ligand to the said metal or said metal in its compound lies in the range greater than 5:1 to 750:1, and the said acid is present in molar excess of at least 2:1, compared to the said ligand.

EFFECT: invention also relates to a method of carbonylation of an ethylene-unsaturated compound, a reaction medium, use of catalyst a system and a complex, which is capable of catalysing carbonylation of an ethylene-unsaturated compound.

39 cl, 35 ex, 9 tbl, 3 dwg

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