SU1359737A1 - Method of group analysis of neutral terpenoids - Google Patents

Abstract

The invention relates to analytical chemistry and is used for the group separation and quantitative determination of terpene compounds in natural resins and their processing products, such as turpentine, neutral resins and oils, neutral part of rosin. The invention makes it possible to reduce the analysis time to 3-4 hours and simplify the process due to the fact that the group analysis of neutral terpenoids in natural resin processing products is carried out by selectively separating them into fractions using organic solvents ... in a chromatographic column with a sorbent, the quality of which is alumina of the 11th degree of activity with a water content of 3%, the pH of the water Vytyazh1Sh 6.9-7.1 and a specific surface of 100-200 In this case, hexane or n are used to isolate the hydrocarbon fraction ether ether, to isolate a fraction containing the sum of oxides, aldehydes, ketones and ethers, use a mixture of hexane or petroleum ether and diethyl ether in a ratio of 85: (13-17), to isolate the fraction of alcohols using a mixture of hexane or petroleum ether with isopropyl ether - sawn or ethyl alcohol in the ratio of 95: (4.5-5.5), isopropyl or ethyl alcohol is used to isolate polyfunctional oxygen-containing compounds. 4 tab. S

Description

The invention relates to analytical chemistry and can be used for group separation and quantitative determination of terpene compounds in natural resins and products of their processing (resin, neutral resins and oils, neutral part of rosin, etc.). The method is intended to assess the quality of neutral resins and oils and allows neutral terpenoids to be divided into the following hydrocarbons; the amount of oxides, aldehydes, ketones and esters; alcohols (the sum of primary, secondary and tertiary alcohols) and polyfunctional oxygen-containing compounds.

The aim of the invention is to reduce the time and simplify the analysis.

As the sorbent, aluminum oxide of the 11th degree of activity according to Brockman (3% water), neutral (pH of the aqueous extract 6: 9-7.1), with a specific surface area of 100–200 m / h, is used. A pore size of 6–15 nm and a specific gravity of 0.9 g / cm. The neutrality terpenoid is eluted from the C alumina chromatography column by a stepwise change in the polarity of the solvents, which ensures a clear separation of the various groups of compounds. Hydrocarbons are eluted from the chromatographic column with hexane or petroleum ether, the sum of oxides, d-dON, ketones and sufters is a mixture of hexane (or petroleum ether) and diethyl ether, taken in a ratio of 85: 13-17, alcohols - a mixture of hexane (or petroleum ether) and isopropyl or ethyl alcohol, taken in the ratio of 95: 4.5-5.5; polyfunctional oxygen-containing compounds are eluted with isopropyl or ethyl alcohol. The volume of fuels is 2.5-3 volumes of sorbent, the ratio of sorbent is the analyte 40: 1,

After selection of the fraction, the solvent is evaporated on a vacuum rotary evaporator and the mass of the fraction is determined gravimetrically. Since using the proposed system of zluents, selective selection of neutral substances into hydrocarbon fractions, the amount of hydroxides, aldehydes, ketones and ethers, the amount of alcohols and polyfunctional oxygen-containing compounds is achieved, it is not necessary to analyze each fraction using thin layer chromatography.

Separation control is carried out only with each new batch of alumina and is carried out using IR spectroscopy or thin layer chromatography.

0 In the IR spectrum of the hydrocarbon fraction there should be no bands characteristic of carbonyl compounds (1800-1650 cm) and alcohols (3600 cm) in the IR spectrum of the fraction containing

5 oxides, aldehydes, ketones and ethers are bands characteristic of alcohols (3600 cm-).

Example 1 Glass column (height 25 cm, internal diameter

0 20 mm) filled with alumina

dry method: 40 g of sorbent is weighed on a technical scale with an error not exceeding 0.1 g, and poured into a column with a bottom of porous

5 stekld (pore 100) in small portions mI; compacted by tapping it with a wooden stick.

1,0005 g neutral larch gum is weighed into a cup

0 with a capacity of 50 ml on an analytical balance with an error not exceeding 0.0002 g, dissolved in 10 ml of hexane and carefully transferred with a glass rod into a glass column with alumina on a dry sorbent, with a second portion of hexane ( 10 ml) quantitatively transfer sample residues to the column,

After the solution containing the neutral terpenoids is absorbed into the column, hexane is added, which is necessary for the removal of the first 4 mixture of carbon from the hydrogen, - 80 ml; (80 ml + 20 ml, which went to dissolve a sample of 100 mp). The solvent fills the upper part of the column, which is not occupied by the sorbent, and under the action of gravitational forces flows into the tank to collect the fraction. Capacity (flask)

0 pre weighed. The solvent (in this case, hexane) is distilled off at 60 ° C and a residual pressure of 5-10 mm Hg. After cooling, the flask is weighed, the fraction of the fraction is determined by the difference, Hexane is desorbed from the column only hydrocarbons. After the selection of the first fraction is completed, 100 mp of the solvent necessary for the elution of the second fraction (sums of oxides, aldehydes, ethers) is poured into the column. The composition of the eluent: a mixture of hexane and diethyl ether (ratio 85:13 for example 1). The mass of the second fraction is determined after removal of the solvent at 60-90 ° C and a residual pressure of 5-10 mm Hg, st. The third fraction (the sum of primary, secondary and tertiary alcohols) is eluted with a mixture of hexane - isopropyl or ethyl alcohol (for example 1, the ratio of hexane to isopropyl alcohol is 95: 5.5). Strong polyfunctional compounds (for example, ketospirits, compounds containing epoxy) and oxo groups, several hydroxy groups, products of deep oxidation) can be desorbed from the column using highly polar eluent ethyl alcohol and isopropyl alcohol. The volume of e-luent for the isolation of both the third and fourth fractions is 100 ml. Mass. fractions are determined by difference after removal of the solvent.

The volume of eluent and the ratio of the components were determined experimentally. The ratio of the mass of the sample - the mass of the sorbent is 1:40 is common in the separation of substances by the method of column chromatography.

The result of the determination of the group composition,%: hydrocarbons 3,4; the amount of oxides, aldehydes, ketones, esters 21.1; alcohols 68.2; polyfunctional oxygen-containing compounds 4.7, Separation time 4 h.

Example 2. Neutral spruce oil (0.4065 g) is weighed with an error of no more than 0.0002 g and dissolved in 10 ml of hexane and quantitatively transferred to a glass column with a dry alumina 20 cm in height and an inner diameter of 1.8 cm The amount of sorbent is 20 g. Hydrocarbons elute 50 MP of petroleum ether, the sum of oxides, ketones, aldehydes and ethers - 60 ml of a mixture of petroleum ether - diethyl ether in a ratio of 85:17, alcohols - mixtures of 60 mm petroleum ether - ethyl alcohol in a ratio. 95: 4,5 and polyfunctional oxygen-containing compounds - 50 ml of ethyl alcohol. The solvents are distilled off in a water bath at 60-90 ° C and a residual pressure of 5-10 mm Hg, one hundred. The results of the determination of the group composition,%: hydrocarbons 35.4, the sum

oxides, ketones, aldehydes and esters 8.4; alcohols 46.7; polyfunctional oxygen-containing compounds

4.0, Split Time 3 h,

 Table 1 shows the implementation of the proposed method in comparison with the known.

The total volume of eluents in the known

1500 cm, in the proposed

method - 400 The reproducibility of the results of the analysis by the proposed method is 5% (SP 0.05), the relative determination error (correctness) is 2%. The total time of the analysis for a known method is 2-3 days, for the proposed method is 3-4 hours ,

. , .

. TabLo2 shows the results that characterize the correctness of the method of group separation of neutral substances, established by adding individual substances of different classes to the neutral leaf resin.

Table 3 shows the results characterizing the reproducibility of the method, determined by repeated analysis of resin and oil samples,

Table 4 presents the results of the determination of the group composition of the neutral-ix substances in various products: oils, resins, neutral substances of fir balsam and pine gum rosin.

Claims (1)

Formula The method of group analysis of neutral terpenoids in natural resin processing products by selectively separating them into fractions using organic solvents in chromatographic column with a sorbent, characterized in that, in order to reduce the time and simplify the analysis, alumina 11 is used as the sorbent degrees of activity with a 3% to 7% content of the water, pH of the aqueous extract from 6.9 to 7.1, and a specific surface area of 100–200 m / g; hexane or petroleum ether is used to separate the hydrocarbon fraction to separate the fraction containing the sum of oxides, aldehydes, ketones and esters, use a mixture of hexane or petroleum ether with diethyl ether in a ratio of 85: 131359737. 95: 4.5 - 5., 5, for the isolation of polyfunctional oxygen-containing compounds, isopropyl or g ethyl alcohol is used. Table 1 Conditions for chromatographic separation of neutral terpenoids 17, to isolate the alcohol fraction, use a mixture of hexane or petroleum ether with isopropyl or ethyl alcohol in the ratio Hydrocarbons Petroleum ether Ummah oxides of firs, ketones, ldegidov pies A mixture of diethyl ether (2.5 - 7.5%) and petroleum ether 2.5% diethyl ether + 97.5% petroleum ether 5% diethyl ether + 95% petroleum ether  7.5% diethyl ether and 92.5% petroleum ether at According to the TLC analysis, the fractions can be combined or used to isolate individual compounds using other columns. A mixture of diethyl ether and petroleum, containing 10-80% diethyl ether 10% diethyl ether and 90% petroleum ether 15% diethyl ether and 85% petroleum ether 20% diethyl ether and 80% petroleum ether Hexane or petroleum ether A mixture of diethyl ether (15%) and hexane or petroleum ether (85%) A mixture of isopropyl or ethyl alcohol (5%) and hexane or petroleum ether (95%) Tertiary alcohols of various structures are eluted 25% diethyl ether and 75% petroleum ether secondary alcohols and part of the primary alcohols 50% diethyl ether and 50% petroleum ether olifuikation compounds Primary alcohols and part of diols 75% diethyl ether and 25% petroleum ether - diols and partly polyfunctional compounds Depending on the results of the analysis, the fractions of the alcohols are combined or, when identifying the predominant components, they are used for their cleavage. Diethyl ether To allocate 1 oxides, ethers, aldehydes, an eluent can be used, containing 13-17% diethyl ether in hexaium or petroleum ether. To isolate alcohols, an eluent containing 4.5–5.5% of isoprotool Shch1I ethyl alcohol in hexane or petroleum ether can be used. 1359737 8 Continuation of table.1. Isopropyl or ethyl alcohol Assessment of the correctness of the method of group separation of neutral substances Squalane squalane squalane Methyl oleate methyl oleate Epimanoxide Cetyl Alcohol Cetyl alcohol Cetyl alcohol - Sitosterol Table 3 Evaluation of the reproducibility of the separation of neutral substances Resin is neutral larch Hydrocarbons Oxides, ketones, aldehydes ethers Alcohols Polyfunctional oxygen-containing compounds 1359737 10 Table 2 7,2 tO, 8. 10.0 ± 0.8 . 14, 8 22.7 ± 1.5 23, 5 24.8i: l, 5 69,3tl, 3 70.7tl, 3 74.5j: I, 3 69., 7tl, 3 4.3 0 -4.1 -5.8 -5.8 0 -1.0 -1.0 +0.5 0 20 0.20 0.060 20 0.32 0.068 Results of group separation of neutral terpenoids Resin is neutral larch, sample 1 Resin is neutral larch, sample 2 Resin is neutral larch, sample 3 Resin is neutral elova Oil is neutral fir tree Neutral larch oil Neutral substances of fir balsam Neutral substances of gum rosin13,0 Table A 20.5 69.9 3.5 20.2 69.1 3.8 21.1 68,6 4.7 42.4 34,8 6.4