SU1546459A1 - 1,8-bis-/2-(4-antipyriliminomethyne) phenoxy/-3,6-dioxaoctane as electrode-active substance of ion-selective electrode for determining activity of lead in aqueous solutions - Google Patents

Abstract

The invention relates to derivatives of dibenzopolyoxyethylenes, in particular, 1,8-bis [2- (4-antipyrilyminometin) phenoxy] -3,6-dioxooctane, which can be used as an electrode active substance to determine the activity of lead ions in aqueous solutions. The purpose of the invention is to create more effective electrodeactive substances of the specified class. The synthesis of the target compound is carried out by the reaction of 4-aminoantipyrine with 1,8-bis- (benzaldehydeoxy) -3,6-dioxooctanate in ethanol at boiling / 15 min /. The yield is quantitative, mp 153-154 ° С, gross formula C ₄₂ H ₄₄ N ₆ O ₆ . The new compound as an electrode-active substance of the ion-selective electrode has a high sensitivity to changes in the concentration of lead ions in the range of 1.10 ^-6 -1.10 ^-2 mol / l. The operation of the electrode is not affected by hydrogen ions 0.1-0.5 wt.% From the initial mixture, the mixture is calcined at 1300-1375 ° C for 20-45 minutes. The whiteness of the resulting product 85-95% MGO. 5 table.and.g.vedeneeva.yu.zubietova546.28-71621.382

11 194354 Leningrad

Description

for the same purpose, GTnvKTvnHbiMH analogues.

Example 1. Synthesis of 1, 8-bis- - Ј2- (4-antipyrilyminometin) phenoxy - -3,6-dioxooctane (I).

To 3.66 g (0.018 mol) of 4-amino-anantipirin, 3.22 g (0.009 mol of 1,8-bis- (benzaldehydeoxy) -3, 6-dioxa octane) was added and dissolved at 350 ml of boiling point. ml of ethanol. A yellow precipitate formed on cooling to 18-206C is filtered and crystallized from ethanol, mp 153-154 ° C., MB 728.

Found,%: C 69.15; H 6.15; N 11.53.

Calculated,%: C 69.23; H 6.04; N 11, 54.

Electronic absorption spectrum TUaKc nm (,): 299 (6.23), 333 (6.31), 342 (6.33).

In order to confirm the structure of compound (I), its IR spectra were taken on a UR-20 instrument in a paste of liquid paraffin and KI tablets. The presence of aromatic nuclei is manifested by absorption bands in the region of 750 cm (Ar-H ortho-substituted benzene). E-LIR bonds are detected at 1050, 1250 cm (Sar-0-Sal and 1003, 1150 cm-m (Salk-0-Salk). The bonds appear at 1650 and 1643 with C-CH at 2715 and 1379 cm. N-groupings SN are found at 1460 and 1450 cm, С-Н in СН5 are found at 1425 and 1412.

Example 2. An ion-sensitive membrane for an ion-selective electrode is prepared from a compound of formula (I) by mixing compound (I) with a solution of polyvinyl chloride (PVC) in tetrahydrofuran (THL)} dibutyl phthalate () as a plasticizer. Membrane composition: Compound (I) 2%; PVC 30%; DVF 68%; THF rest. The resulting solution is drunk in a Petri dish and dried for 1 day at room temperature. Then, the resulting membrane membrane is kept at 1 h 10 mol / l lead nitrate solution for 1 day.

EMF measurements are carried out on an Orion-901 ionometer. The silver chloride EVL-1MZ electrode is used as a reference electrode.

To conduct quantitative determinations of lead ion activity, the ion-selective electrode is placed in the analyzed solution a couple of times

g 5

0

using a reference electrode, for example, chloride-silver, and measure the EMF in mV. Measuring cell layout:

Ag, AgCl HC1 us. KMOE us. membrane analyzed solution KNOa us. KC1 us. AgCl, Ag.

For compound (I), the electrode has a linear electrode function within a concentration of lead ions of -1-10 mol / l in the pH range of 3.5-5.5 and has an angular coefficient of the electrode of 22-24 mV. The expansion of the linear response of the electrode leads to an increase in sensitivity and an increase in the detection limit of lead ions.

The table presents the main characteristics and selectivity coefficients of the electrode based on compound (I) and known film electrodes: on the basis of podand with thioureid groups (II) and crown ether 1.7-diazo-8.9-17,18-dibenzo-18 - -crown-6 (III).

As can be seen from the table, the work of the electrode with compound (I) is not affected by hydrogen ions at a pH of from 3.5 to 5.5, while the electrode has a higher sensitivity to lead and allows you to determine the activity of lead ions. C high degree of selectivity in the presence of alkali, alkaline earth metals, cadmium, nickel, cobalt, zinc.

Formula of invention.

1, 8-Bis .- (4-antipyrilliminometin) phenoxy-3,6-dioxoctane

g g

-0000

sh -

II

H,

3 I I

H4C-N C 0

3

I

C6H5

HC II N-C C-CH3

I I 3

0 C N-fiH, 4NX

C6H5

as an electrode-active substance of an ion-selective electrode for determining the activity of lead ions in aqueous solutions.

II III

    3-10 3,6 ,, 3

1-105 -5-10 2-10 -3-10

1-10 2-10

one( .

1.6-10 5 -10

10+

ten

1.6-10 5 -10

10+

II - dibenzopolyoxyethylene formula

.t

NH HN

I

H3CO- Q -HN-C $ C-NH Q -OCH3

where n 1,2.

Claims (1)

Claim. 1, 8-Bis- £ 2— (4 — antipyryliminomethine) phenoxy ^ -3,6-dioxoctane R ~ \ r \ r ~ \ o o NA II NC = C-CH ₃ II ³ 0 = C N-6H, W with ₆ n ₅ as an electrode-active substance of an ion-selective electrode for determining the activity of lead ions in aqueous solutions. Connection based electrode The concentration area of the electrode, mol / l Selectivity factors Cd Ni With Zn Si Ag Zi, Na, | K, Rb, Cs. Ca, Sr Ba ^Μβ I 1 I 10 ^{and <} -1CG ¹ 3-1 O ' ³ 7 · 10 ^And 5 Yu ' ³ 3rd ³ 3.6.YU 10' 6.4 S * 2.3-S ⁴⁵ II * 1 · 10 ' ^s -5-10 1-10 '’ 2-y ' ¹ 1.6-10 '* III 2-U ' ⁶ -3 -10' * 16 ¹ - 3'10 ' ¹ 5-10 ’ w ⁴ ' II - dibenzopolyoxyethylene of the formula where η = 1,2.