Crown-ethers used as active ingredients of ionselective membrane electrodes

专利摘要:
Crown ether derivatives of the general formula I …<CHEM>… wherein… Z<1> is a group of the general formula …<CHEM>… (in which Ra represents an alkyl group having 1-4 carbon atoms and Rb represents an alkyl group having 1-20 carbon atoms) are useful in the preparation of ion-selective electrodes having a long lifetime.
公开号:SU1257071A1
申请号:SU833622807
申请日:1983-07-22
公开日:1986-09-15
发明作者:Токе Ласло；Агаи Бела；Биттер Иштван；Пунгор Ерне；Сепешвари Клара；Линднер Мариа Хорват Ерне；Хабаш Йене
申请人:Мадьяр Трудоманьош Академиа (Инопредприятие)；
IPC主号:

专利说明:

The invention relates to new chemical compounds - crown ethers, which have complexing ability with metal cations and can be used as active ingredients of ion-selective electrodes for measuring various cations (alkali, alkaline earth ions and heavy metals).
The purpose of the invention is to increase the selectivity factor of ion-selective membranes with respect to alkali metal ions having a large volume.
Example 1. Getting the original isocyanates. According to this example, 0.1 mol of the amino compound characterized by the general formula (II) is dissolved in 500 ml of chlorobenzene. To the resulting solution, 150 ml of chlorobenzene, saturated with phosgene, are added at room temperature, while the phosgene is continuously stirred. The reaction mixture thus obtained is then slowly heated to the boiling point. The release of gaseous hydrogen chloride is then stopped by stopping the input of phosgene and the excess amount of phosgene is introduced at boiling with nitrogen and gaseous argon (approximately 1.5-2 h). Chlorobenzene is distilled off under vacuum. The residue is subjected to purification, as indicated in the table. one.

X NH
R
about
OF, (i) o
Compounds of formula (Na) and (116)
obtained in accordance with the specified method:
(11a), - 2-nitro-4,5 / 1, 4, 7,, 10, 1 -3-pentaoxacacyclopentade-2 - -ene / phenyl isocyanate - the starting compound for the preparation of the compound (1a) and (16). ,,,, (PB) - 4- (1, 4, 7, JO, 13) pentaoxacyclopentadec-2-ene / phenyl isocyanate is the starting compound for the preparation of compound (16).
Example 2. Preparation of urethanes characterized by the formula (CG),
(1W


where R is alkyl, benzyl or
phenyl.
According to this example, 0.5 mol of the amine is dissolved in 200 ml of chloroform, and 0.1 mol of chloroformate is added to the solution thus obtained at room temperature and with constant stirring. After 10 minutes, 10.1 g of triethylamine was added and the resulting mixture was further stirred for 30-45 minutes. The reaction mixture is subjected to evaporation and the residue is subjected to purification, as indicated in the table. one .
Preparation of bis-crown compounds characterized by formula (I).
Example 3 (option process a). A solution containing 0.2 mol of isocyanate (Na, b) in 500 ml of absolute dioxane or absolute chloroform is subjected to stirring from 0.1 mol of schenglycol 6.2 g (thioethylene 12.2) and 2.2, -bis α-oxyethyl pyroketachine 19.8 g for 1-2 hours at room temperature. In those cases where oxides are used, 0.005 mol of the triethylamine catalyst is used.
Branch
If the product precipitates, it is filtered, washed with dioxane or chloroform and recrystallized from the solvent, as indicated in the table. 2. If the product does not precipitate, the solvent is distilled off in vacuo and the precipitate is recrystallized from the solvent, as shown in the table below. 2
Example 4 (process variant; Ca 0). 20 mmol of urethane is dissolved in 50 ml of chloroform (or dioxane, toluene or chlorobene ash) and the solution thus obtained is subjected to stirring for 3-4 hours at 60-100 ° C with 10 mmol of ethylene glycol 0.62 g (distetilen glycol 0.62 g) and 2,2-bis-oxystilpyrocatechin 1.98 g at 30-80 ° C for 0.5-1 h if X is NOj. In those cases when the oxy compounds are used, it is necessary
add 1 drop of triethylamine catalyst.
Branch This operation is carried out analogously to example 3. The products thus obtained are identical to the compounds obtained in accordance with the process of example 3 (i.e., according to the infrared spectrum, melting points and melting points of the mixture).
Yield 40-90%; When X NH output 75-90%; when X About the output of 40-60%.
Example 5. A solution containing 10 mmol of bis-urethane characterized by the general formula (I), where Y corresponds to the above values and X ×)) in 50 ml of toluene or chlorobenzene, chloroform or di-nor-β-butyl ether is subjected to stirring with 10 mmol alpha, omega-polymethylenediamine (ethylenediamine-0.6 g; 1,3-propylenediamine-0.74 g; 1,6-hexamethylenediamine 1.16 g at 80-100 ° C, at X H and at BS) -VO at X NOj for 2-4 hours
The separation is carried out similarly to option a. The yield is 50-82% of theoretical. The products obtained according to a variant of the process are identical products obtained in the process according to the variants of examples 3 and 4 (according to the data of the infrared spectrum, melting points, melting points of the mixture and chromatographic data in thin layers).
Example 7. In accordance with this embodiment, 10 mmol of a bis-crown compound characterized by the general formula (I) (where Y corresponds to the above mentioned values. X H) is dissolved in 25 ml of chloroform, then 10 ml with constant stirring of the solution and adding dropwise a solution containing 3 ml of 65% nitric acid in 3 ml of acetic acid. The reaction mixture thus obtained is stirred at room temperature for 10 minutes and then for 30 minutes. The mixture is cooled and poured onto crushed ice (50 g). The two layers formed are separated and the aqueous layer is extracted with chloroform four times in 0 ml. The combined organic layer was washed with 30 ml portions of water, and the chloroform was distilled off under distillation.
vacuum and the residue is subjected to recrystallization of the solvent. The yield is 55-78%.
The nitro derivatives thus obtained are identical to those obtained in accordance with the process of examples 3 and 4 (according to the infrared spectrum, melting points and melting points of the mixture).
Increase in complex formation (complex stability constants). in the case of specified cations, it depends not only on the geometric characteristics of the crown ether, such as the number of the ring element, the number of the heteroatom, but also the type of solvent used in this process. The stoichiometry of the resulting complex is determined by the ratio between the diameters of the crown ether ring and the cation ring. All of these factors justify the use of crown ethers as active ingredients of ion-selective membrane electrodes.
Different electrodes have different active ingredients, are characterized by mechanical and dynamic properties, and differ in selectivity factors. In the field of biochemical processes, these electrodes are particularly important because they are suitable for conducting ionic processes of cellular metabolism in the body. When it is necessary to use electrodes as sensors suitable for measuring biological important ions, electrodes suitable for measuring cations selected from the group including sodium, potassium, calcium and magnesium are of great importance. Measurement of potassium ions is especially necessary in vital processes. The best electrodes selective for potassium ions are ion-selective electrodes containing valinomycin as the active ingredient.
For use in biological research, the main feature is the selectivity factor for sodium ions (Kj), which is about 3x10. Potassium electrode, obtained on the basis of valicomycin, has a higher selectivity or equal to
51
with respect to large alkali metal ions (Rb, Cs) of the selectivity of the K 5 ion, i.e. The electrode provides measurement of these ions with greater or same selectivity as in the measurement of potassium ions. Since alkali metal ions are often found in nature, such a coincidence of selectivity factors may be undesirable in the case of a potassium electrode intended for purposes other than biochemical studies. These drawbacks can be eliminated without a significant decrease in selectivity with respect to other ions in cases where bis-crown compounds linked by an aliphatic chain are used as ion-selective substances. .
A large number of compounds of formula (I) are suitable for. using electrodes selective for potassium ions. The electrodes obtained from the new compounds have the same sensitivity with respect to the concentration of potassium ions as the sensitivity with respect to the concentration of potassium electrodes prepared on the basis of valinomycin, and their selectivity factor with respect to alkali metal ions having a large volume is better (from 0.1 to 0.01) than the analogous parameter of electrodes obtained on the basis of valinomycin, the selectivity factors of which vary in the range of 0.5, and at the same time the selectivity factor with respect to alkaline ions ze metals elnyk is samm ones as for the electrode obtained on the basis of valinomycin.
The compounds of formula (I) are used as active ingredients of ion-selective electrodes as follows.
The compound of formula (I) is introduced into the carrier phase, polyvinylchloride 1, in an amount of 0.2-3%, using suitable plasticizers, for example, phthalic acid esters, sebacic acid esters or opto-nitrophenyl-octil ether. The compound of formula (I) is introduced into silicone rubber or into another polymer, for example, polyamide, polyvinyl chloride, polyethylene, the dielectric constant of which is
71a
in the range of 2-30. The compounds of formula (I) are applied to a porous membrane dissolved in a suitable solvent, preferably in the plasticizers mentioned above in section a.
The resulting membranes are inserted into a suitable electrode and connected together with a suitable reference electrode of an analytical measuring device.
The preparation of a potassium ion-selective membrane using a crown compound characterized by the general formula (I) is carried out as follows.
20-60, preferably about 35 parts by weight, powdered polyvinyl chloride are dissolved in 2-3 ml of tetrahydrofuran and the solution thus obtained is poured into a container containing 0.2-10 mg, preferably 1-5 parts by weight . active ingredients (i.e. compounds selected from the group of compounds characterized by the general formula (I) or mixtures of such compounds), and 60-120 mg, preferably 65 parts by weight a plasticizer (organic solvent with a dielectric constant of 2-30, for example, phthalic acid ester or ester: Pa of sebacic acid). The mixture is stirred by shaking to obtain a hemogenic mixture.
On a glass plate located under a glass ring with a height of 10 mm and a diameter of 25-35 mm, fixed with a rubber ring having a flat surface, 3 ml of the mixture was poured and the ring was covered with filter paper. The tetrahydrofuran is evaporated at room temperature for 1-2 days through filter paper, while on the surface of the glass plate inside the ring an elastic membrane with a thickness of 0.1-0.5 mm is formed as a residue that can be easily removed from the TOY glass surface .
2-10 mg, preferably 1-10 weight .h of the active ingredient and 50-200 mg, preferably 90-99 weight.h. dimethyl polysiloxane is dissolved in 2-4 ml of carbon tetrachloride. The required amount is added to the solution obtained in this way.
v
a crosslinking agent. Each cold curing catalyst suitable for crosslinking, for example T-37, can be used for this purpose. The mixture thus obtained is then poured into a glass ring mounted on a glass plate. 2-10 mg, preferably 1-10 weight.h. the active ingredient is subjected to grinding in a mortar made of agate, and then dispersed in 50-20 mg, preferably 90-99 weight.h. dimethylpolysiloxane. This process is continued until a statistically homogeneous suspension is obtained. The crosslinking agent is added in an amount necessary for curing (e.g., 1 part by weight of dibutyl-3n-dilaurate and 2 parts by weight of hexaethoxysiloxane). Then, the resulting mixture was applied to a plastic plate with a layer of equal thickness of 0.01-1 mm. After curing which occurs within a few hours. the elastic plate is removed from the surface of the plastic plate.
1-20 weight.h. active ingredient is dissolved in a solvent immiscible with water (whose dielectric constant is 2-30), such as, for example, phthalic acid esters, sebacic acid esters, ortho-nitro p ,, AgCl, 0.01 M KCl Ion Selective Membrane
  -.,
Ion-selective electrode
0.1 LOOCCH, 0.1M KC1
Dual connected reference electrode,
The EME-Ig d calibration dependencies for the KC1 range of 10 -10 M, using these potentials, are measured using the indicated measuring cell (Compounds 1a, 16, IB are used as active ingredients). The selectivity factors of these electrodes are determined using the method of separating solutions using solutions having a concentration of 10 M.
In tab. A presents data on the selectivity factors of a potassium selective electrode with respect to various ions in order to compare
,
12570718
phenyl octyl ether. The porous membrane is moistened with the solution obtained.
The tetrahydrofuran solution obtained 5, containing the plasticizer and the active ingredient, or the resulting solution of dimethylpolysiloxane in carbon tetrachloride, containing the active ingredient and the catalyst, 10 or dimethylpolysiloxane suspension, containing the active ingredient, including a crosslinking agent and / or a catalyst, is applied to the elec - a conductive surface, preferably (metallic silver, silver, silver chloride wire, platinum or gold thread, graphite rods, etc.
The electrochemical properties of the selected active ingredients, characterized by the general formula (l) and used as a potassium ion-selective membrane electrode, are listed in Table. 3
A membrane prepared on the basis of a carrier, a polyvinyl chloride phase, is prepared similarly to the active Hbw ingredients, such as 1a, 16, IB, which are combined with suitable
an electrode, such as a liquid membrane electrode developed by Philips, LS-561. The following measuring cell:
Sample solution
as an electrode obtained on the basis of valinomycin, and an electrode containing as active ingredient new compounds characterized by the formula (I): la-ethylene-1,2-. -bis-M- / 2 -nitro-4, 5 - / l, 4, 7, 10, 13 -pentaoxacyclopentadec-2 - -en / -phenyl / -carbamate; -Tb-diethyl sulfide-2,2-bis-H- / 2 | -nit-4, 5- / 1
ten
13-pentaoxa-cyclopentadec-2-en / -phenyl / -carba-55 mat; 1c- / 1,2-phenylenedioxy / -diethyl- -2, 2 -bis-H- / 3, 4 ,, 10, 13-pentaoxycyclopentadec-2 - -en / -phenyl / -carbamate.
(I EG S
h about
n
with
but
S
t; Yu
se
n
15
The logarithm of the potentiometric selectivity factor of bio-crown compounds of formula (1),
-3,1-2,0
-3.6-2.0
-2.7-1.6
-4.2-1.8
-4.1 -4.6
-4.9 Compiled by I. D chenko Editor T. Parfenova Tehred L. Serdyukova
Order 4880/19
Circulation 379
VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
Production and printing company, Uzhgorod, st. Project, 4
1257071
16 Table 4

-1.3 -2.3
-1.3 -2.2 -1.0 -1.9 -0.4 -0.4
-4.1 -3.7
-3.9
-3,8
-4.9
Proofreader M, Demchik
Subscription

权利要求:
Claims (1)
[1]
Crown ethers of the formula
as active ingredients of ion-selective membrane electrodes.
Memory .... 1257071
(111)
1257071

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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HU811999A|HU186777B|1981-07-09|1981-07-09|Process for producing complex-forming agents of crown-ether base and ionoselective membranelektrodes containing them|

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