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Limit of quantification. According to the methodology on the basis oflinearity the limit of quantification (LOQ) was determined. LOQwas 8 mcg/ml.
Determination of eleutherosides B and E in the dry extract. Chromatogram of the extract obtained in the chromatographic conditions for eleutheroside B and E are shown in Fig. 3 and 4 respectively.
The studies revealed that the content eleutheroside B is 0.08 %, eleutheroside E is 0.06 %, thus the total content eleutherosides B and E is — 0.14 %.
Conclusion
Thus we have developed and confirmed method of quantitative determination eleuterosides B and E in a dry extract of
Eleutherococcus according to parameters: specificity, linearity and LOQ. Based on studies it can be concluded that in the quantitative content eleutheroside B is 0.08 %, the eleutheroside E is 0.06 % and this fraction equals 0.14 %.
Summary
The method of determination eleuterosides B and E in the dry extract of Eleutherococcus by HPLC was developed. Represented validation techniques according to parameters: specificity, linearity, LOQ.
Quantitative content of eleutherosides in dry extract of Eleutherococcus: eleutheroside B is 0.08 %, eleutheroside E is 0.06 % and total content eleutherosides B and E is 0.14 %.
References:
1. Watson D. G. Pharmaceutical Analysis: A Textbook for Pharmacy Students and Pharmaceutical Chemists, 2nd Revised edition. -Churchill Livingstone, 2005. - 398 c.
2. Zhang Q., Liu Y., Li J., Xu Q., Li X., Yang X., Yao D., Sun J., Cui G., Ying H. Simultaneous determination of Eleutheroside B and Eleutheroside E in rat plasma by high performance liquid chromatography-electrospray ionization mass spectrometry and its application in a pharmacokinetic study//J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. - 2013, Feb 15. - 917-918: 84-92.
3. Zhang L., Sun Y. Semipreparative separation and determination of eleutheroside E in Acanthopanax giraldii Harms by high-performance liquid chromatography//J. Chromatogr. Sci. - 2005, May-Jun. - 43(5): 249-252.
Turgunov Erxan, Associate Professor of the Faculty of Chemistry of the National University of Uzbekistan E-mail: [email protected] Suleymanova Gulchehra Gaybullaevna, Tashkent Pediatric Medical Institute, assistant of the Department of Biology, Inorganic and Organic Chemistry, PhD
E-mail: [email protected] Sobirova Diloram Kabulovna, Tashkent Automobile and Road Institute, senior lecturer in Chemistry, PhD E-mail: [email protected]
Hudoyberdieva Zarifa, 4th year student of the Faculty of Chemistry of the National University of Uzbekistan E-mail: [email protected] Kolyadin Vladimir Grigorevich, Associate Professor of the Faculty of Chemistry of the National University of Uzbekistan E-mail: [email protected] Fazullaeva Mariyam, PhD, Department of Chemistry of the National University of Uzbekistan E-mail: [email protected]
Herbicide activity of acetylenic aminoalcohols and their ammonium bases
Abstract: Studied herbicide action of some synthesized acetylenic amino alcohols, hydrochloride, various chlor- and bro-moniy compounds based on them, as well as the selectivity of their actions in relation to such important crops as cotton and corn. It was found that the pretreatment of seeds and weeds studied drugs, depending on their chemical structure and dose exhibit various herbicide activity against annual dicotyledonous (shirica) and annual cereals (hen's proso) weeds.
Keywords: Mannich reaction, Favorskiy reaction, Acetylenic amino alcohols, acetylenic hydrochlorides of amino alcohols, chloroniy salts of acetylenic amino alcohols, Bromoniy salts of acetylenic amino alcohols, herbicide activity, cotton, corn, shirica, hen's proso.
Climatical conditions of cotton — zones of Uzbekistan from May to October mounts are very favorable for sprouting seeds of annual weeds such as shirica, hen's proso and some others. The most quantity ofweeds have appeared in second halfofMay when average daily temperature of air is about 25-30 °C and in some regions — haier 35 °C.
In last time from herbicides supplied by industry to agriculture to using of different compounds obtained on the base of acetylenic alcohols is devoted an important role [1]. One of the peculiarities of these compounds is their low toxicality in relation of warm blooded
organisms [2] what has a main role at their using in medicine and agriculture.
Herbicide activity of some acetylenic aminoalcohols, their hydrochlorides, different chlorine- and bromineoniy compounds and selectivity of their action in relation to such important cultures as cotton and corn has been investigated.
For this aim initial acetylenic alcohols were synthesized from acetylene and phormaldehyde, acetone or methyl ethyl keton by reaction Favorsky according to following scheme [3]:
A1 = -R = -R' = -H; A2 = -R = -R' = -CH3;
A3 = -R =
-CH3, -R' =
"C2H5
Aminoalcohols were obtained by Mannich reaction that is condensation of acetylenic alcohols (A) and secondary amines (dimethylamine,
diethylamine and piperidine) with paraformaldehyde in the presence of Cu2Cl2 or Cu (CH3 COO)2 as catalists in medium of dioxane [4]:
I = -R = -R' = -CH3; -N(R)2= — dimethylamino group;
II = -R = -CH3; -R' = -C2H5; -N(R)2= — dimethylamino group;
III = -R = -R' = -CH3; -N(R)2= — dimethylamino group;
IV=-R = -CH3; -R' = -C2H5; -N(R)2= — dimethylamino group;
V -R = -R' = -H; -N(R)2= — pyperydino group;
VI = -R = -R' = -CH3; -N(R)2= — pyperydino group;
VII =-R = -CH3; -R3 = -C2H5; -N(R)2= — pyperydino group
In following by interaction of compounds I-VII with molecular chlorine and bromine and also hydrochloride in medium of diethyl ether or acetone at temperature 20-25 °C
R
I
R'-C—C=C—CH2-N(R)2 + L—X-OH I - VII
corresponding dihaloidoniy salts (VIII-XX) and hydrochlorides (XXI-XXVII) of acetylenic aminoalcohols have been obtained [5]:
R
[R-Ç-C=C-CH2-N(R)2] .1® OH x
VIII-XX XXI-XXVII
X=-H; L=
L=X = -Cl (VIII-XIV); L=X = -Br(XV-XX); -Cl (XXI-XXVII) — Hydrochlorids
In during of caring out of Mannich reaction simultaneous addition of halogens and hydrogen chloride by -C=C- bond wasn't observed. All obtained compounds VIII-XXVII are soluble in water but their solubility in organic solvents is low; their structures were determined by such methods as IR-, NMR13C spectroscopies.
Herbicide activity of synthesized compounds was investigated in presowing period be course in period of vegetation of plants they have carried out low activity. For testing of the herbicide activity of selected preparates in presowing period seeds of cotton of sort Tashkent-1 and corn of sort VIR-338 and also weed of plants such as shirica and hen's proso by 16 pieces have been used. Seeds were in soil placed which than was treated by choosed compounds in dose 5 kg/h. After 30 day determination of herbicide activity ( % to control) and calculation of number of plants remaining didn't damaged in comparison with control were carried out.
From data presented in table 1 it is shown that compounds V, VI, X, XIV and XXI have shown considerable herbicide activity
again shirica (from 51.6 to 95.0 %); compounds VII, VIII, XI, XII, XV, XXIII and XXIV — an middle activity (from 26.3 to 36.8 %) and remain compounds have possesed by low activity (less than 25 %). Investigated compounds possesed by low herbicid action on gen's proso. Results of measuring damp green ground mass of plants are presented in table 2. Compounds V, VI, VII, X, XIV, XXI correspon-denly have increased the damp green mass of corn on 113.8; 116.3; 122.6; 125.6; 127.1 and 140.3 % and compounds XV, XXI, V, VI, X and XIV correspondenly have increased of damp green mass of cotton on 114.2; 119.9; 120.8; 128.6; 130.6 and 134.4 %. Thus at presowing treatment of seeds by solutions of investigated preparates in dependence on their chemical structure and dose has shown their different herbicide activity relativly to annual dicotyledonous (shirica) and annual cereals (hen's proso) weeds.
Chemical compounds — derivatives of acetylenic aminoalco-hols have shown an high selective and herbicid action against weeds plants and at this they didn't damage an cotton and corn.
Table 1. - Herbicide activity of investigated preparates
№ of compounds Preparates Death of plants, % to control
Shirica Hen's proso
Control 0 0
I. 5- (dimethylamino)-2-methylpent-3-yn-2-ol 4.2 9.0
II. 6- (dimethylamino)-3-methylhex-4-yn-3-ol 20.2 13.3
III. 5- (diethylamino)-2-methylpent-3-yn-2-ol 8.3 10.2
IV. 6- (diethylamino)-3-methylhex-4-yn-3-ol 5.9 2.9
V. 4- (piperidin-1-yl)but-2-yn-1-ol 51.6 26.0
VI. 2-methyl-5- (piperidin-1-yl)pent-3-yn-2-ol 58.3 6.0
VII. 3-methyl-6- (piperidin-1-yl)hex-4-yn-3-ol 34.2 28.3
VIII. dichloronium salts 5- (dimethylamino)-2-methylpent-3-yn-2-ol 36.8 22.2
IX. dichloronium salts 6- (dimethylamino)-3-methylhex-4-yn-3-ol 17.3 19.5
X. dichloronium salts 5- (diethylamino)-2-methylpent-3-yn-2-ol 78.5 30.1
XI. dichloronium salts 6- (diethylamino)-3-methylhex-4-yn-3-ol 27.8 18.6
XII. dichloronium salts 4- (piperidin-1-yl)but-2-yn-1-ol 33.9 20.1
XIII. dichloronium salts 2-methyl-5- (piperidin-1-yl)pent-3-yn-2-ol 22.6 18.0
XIV. dichloronium salts (S)-3-methyl-6- (piperidin-1-yl)hex-4-yn-3-ol. 95.0 7.1
XV. dibromonium salts 5- (dimethylamino)-2-methylpent-3-yn-2-ol 27.8 5.6
XVI. dibromonium salts (S)-6- (dimethylamino)-3-methylhex-4-yn-3-ol 20.5 15.3
XVII. dibromonium salts (S)-6- (diethylamino)-3-methylhex-4-yn-3-ol 11.8 13.1
XVIII. dibromonium salts 5- (diethylamino)-2-methylpent-3-yn-2-ol 14.7 12.8
XIX. dibromonium salts 4- (piperidin-1-yl)but-2-yn-1-ol 16.3 17.9
XX. dibromonium salts 2-methyl-5- (piperidin-1-yl)pent-3-yn-2-ol 9.3 11.6
XXI. hydrochloridum 5- (dimethylamino)-2-methylpent-3-yn-2-ol 54.7 39.1
XXII. hydrochloridum 6- (dimethylamino)-3-methylhex-4-yn-3-ol 23.3 18.8
XXIII. hydrochloridum 5- (diethylamino)-2-methylpent-3-yn-2-ol 26.3 21.6
XXIV hydrochloridum 6- (diethylamino)-3-methylhex-4-yn-3-ol 34.5 18.8
XXV. hydrochloridum 4- (piperidin-1-yl)but-2-yn-1-ol 22.5 29.0
XXVI. hydrochloridum 2-methyl-5- (piperidin-1-yl)pent-3-yn-2-ol 30.4 9.8
XXVII. hydrochloridum (S)-3-methyl-6- (piperidin-1-yl)hex-4-yn-3-ol 14.9 4.0
Table 2. - Influence of investigated preparates on damp green ground mass of plants
Preparates Cotton Corn Shirica Hen's proso Cotton Corn Shirica Hen's proso
grams %
1 2 3 4 5 6 7 8 9
Control 13.0 35.4 26.4 10.5 100 100 100 100
I. 13.3 35.9 23.6 9.5 102.0 101.3 88.9 90.4
II. 13.3 36.5 23.0 8.4 102.5 103.2 87.2 79.8
III. 13.3 36.6 23.8 9.3 101.9 103.4 90.2 89.0
IV. 13.7 36.8 24.4 8.9 105.4 104.0 92.3 84.4
V. 15.7 41.2 11.2 6.3 120.8 116.3 42.5 60.0
VI. 16.7 43.2 16.1 9.4 128.6 122.1 60.9 90.0
VII. 13.7 40.3 22.3 7.6 105.7 113.8 84.4 72.1
Control 19.3 50.6 40.2 23.1 100 100 100 100
VIII. 20.8 52.3 26.7 17.0 107.9 103.4 66.5 73.7
IX. 20.4 51.6 34.0 18.5 105.7 102.0 84.6 80.3
X. 25.2 64.3 9.4 8.1 130.6 127.1 23.4 35.1
XI. 21.0 51.3 26.1 17.4 109.2 101.1 64.9 75.4
XII. 20.5 50.9 31.6 15.0 106.2 100.5 78.6 65.3
XIII. 20.0 54.0 35.1 17.5 104.0 106.7 87.4 75.6
XIV. 25.9 71.0 3.6 19.8 134.4 140.3 9.0 85.9
XV. 22.0 56.1 27.9 21.6 114.2 110.9 69.5 93.4
XVI. 19.9 54.5 34.3 20.1 103.1 107.8 85.3 87.2
XVII. 20.1 51.0 35.2 21.8 104.2 100.9 87.7 94.3
XVIII. 20.4 54.5 32.5 20.7 105.5 107.8 80.8 89.7
XIX. 19.9 54.0 35.5 19.9 103.1 106.7 88.4 86.0
XX. 19.8 54.7 36.4 20.8 102.9 108.0 90.5 89.9
XXI. 23.1 63.6 11.1 9.0 119.9 125.6 27.6 39.0
1 2 3 4 5 6 7 8 9
XXII. 19.5 52.7 30.9 18.9 100.8 104.2 76.9 82.1
XXIII. 20.3 54.4 29.8 19.5 105.2 107.6 74.0 84.6
XXIV. 21.3 55.1 27.8 17.6 110.6 108.9 69.1 76.2
XXV. 20.7 51.5 36.1 19.5 107.4 101.8 89.9 84.6
XXVI. 21.0 53.6 28.5 20.8 109.5 106.0 70.8 90.0
XXVII. 20.6 53.6 31.6 20.8 106.5 106.7 78.7 90.2
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2. Patent, Russian № 2155759. 2000. Aminoalcohols of acetylenic raw having pronounced M-holinolitical properties and weak oppessing action on the central nerve system./Libman N. M., Zacepin E. P., Pashkevich B. P.
3. Bonrat Verner, Sher Peter L., Chumi Johannes, Zenhoyseren Reto. Method of ethynilation. Patent 2005107412/04, 09.08.2003. C07C33/042 (2006.01) C07C33/048 (2006.01). C07C33/14 (2006.01) C07C43/303 (2006.01) C07C41/48 (2006.01)C07C29/42 (2006.01).
4. Libman N. M., Kuznetsov S. G. Aminoalcohols of acetylenic raw. I. Obtain of 1,1-twosubstituted 4-dialkylaminobutin-2-ols-1.//J. Obs. Chem., - 1960, - V. 30, № 4. - P. 1197-1202.
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