Biologically active compounds and preparations for agriculture
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N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry
 of Siberian Branch of Russian Academy of Sciences

Handout

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INTERMEDIATE PRODUCTS FOR THE SYNTHESIS OF MODERN AND PERSPECTIVE PYRETHROID INSECTICIDES

Research conducted in 1989-1994 under the supervision of A.V.Tkachev; State Prize for Young Scientists, 1995 and 1996; Gold Medal of the 44th International Exhibition of Inventions, Research and Industrial Innovations, BRUSSELS EURECA'95 (1995).

inter_1Pyrethroid insecticides are the most effective birth control means of arthropoda which insectoracaricide activity largely depends on the structure of the molecules. Production of (1R)-configuration pyrethroid insecticides in enantiomeric pure form makes it possible to increase significantly their biological activity and decrease environmental damage of their application. One of the most perspective approaches to the production of optically active pyrethroids is based on the use of natural chiral compounds as initial products for their synthesis. Natural monoterpene hydrocarbon (+)-3-carene – a turpentine component obtained in the processing of many conifers (family Pinaceae) – is one of such substances.

 

The conducted research has made it possible to develop a new approach – instead of traditional oxidation systems – to the construction of molecules of intermediate products for the synthesis on the basis of (+)-3-carene pyrethroid insecticides in optically pure form:

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The new approach is based on the reaction of nitrosochlorination of carene for disintegration of a six-membered carbocycle of the initial molecule instead of traditional oxidation reactions. Available synthetic methods of obtaining target compounds have been developed, which opened up new routes for the production of derivatives from (1R)-cyclopropanecarboxylic acids with the use of rearrangements running in mild conditions at nitrogen atom (Beckman, Hofman, Timan).

The main idea of the new synthetic approach is transformation of oxime 3-(N,N-dimethylamine)-carane-4-on to ketonitrile with almost quantitative yield in the action of acetic anhydride, with the target product being easily isolated from the reaction by-products. The given method can be easily scaled and produced at the pilot plant of the Novosibirsk Institute of Organic Chemistry:

 

 +(-)-3-carene  inter_4

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Pyrethroid esters on the basis of (1R)-trans-chrysanthemic acid are characterized by the combination of high biological activity with very low toxicity for mammals, which makes them extremely perspective as indoor domestic insecticides. In general case, pyrethroid esters of (1R)-trans-chrysanthemic acid exceed the esters of (1R)-cis-chrisanthemic acid in insecticide activity; however, (1R)-cis-chrisanthemates appear to be more active in respect of some objects (e.g.: mosquitos). Therefore, the development of convenient synthetic methods of (1R)-cis-chrisanthemic acids is of special interest. (1R)-cis-nor-chrisanthemic acid is a structural  hybrid of (1R)-cis-chrisanthemic and  permetrine acids. The obtained pyrethroids combine the properties of both chresanthemates and esters of permethrine acids; in terms of insecticide activity, they are closer to the correspondent derivatives of permethrine acid, but unlike the latter, they are significantly less toxic for fish, which is sure to be their prime advantage.

Simple and effective schemes of obtaining three pyrethroid acids:

 

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Production of nitrogen-containing analogues of pyrethroids. Hydrolysis of a molecule on the place of ester rearrangement in the action of esterases is one of the most important mechanisms of pyrethroid detoxication in the organisms of insects. There have been developed synthetic methods of (1R)-cis-chrisanthemilamine – an important intermediate compound in obtaining aza-analogues of pyrethroid insecticides, such as (1R)-cis-chrisanthemil-(3-phenoxy benzyl)-cyanamide:

 

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Thus, the conducted research has made it possible to develop a simple, efficient and easily scalable synthetic routes which allowed us to transform natural terpene hydrocarbon (+)-3-carene with high yield to valuable biologically active substances of pyrethroid series. The results of the research work can be applied in various spheres – production of birth control pesticides, synthesis of pharmaceutical products, fine organic synthesis of chiral substrates, etc.

 

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences
9, Acad. Lavrentiev Ave,  630090, Novosibirsk, 90, Russsia
PhD. A.V. Tkachev, Head of the Laboratory
E-mail:This email address is being protected from spambots. You need JavaScript enabled to view it.  Tel.: 8(383) 330-98-55   Fax: 8(383) 330-97-52

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BIOLOGICALLY ACTIVE COMPOUNDS EXTRACTED FROM NATURAL PRODUCTS

 

Application: individual compounds and compositions extracted from vegetable raw materials as well as the products of their chemical modification reveal a wide range of biological activities used in science intensive production (pharmaceutics, protectors of biological objects, etc.) and scientific research.

We have developed extraction methods and technologies for the following complex chemical compounds from renewable vegetable raw materials:

 

Lappaconitin hydrobromide

Antiarhythmic of  cardio activity

Extracted from aconite roots

Ursolic acid

Applied in cardiology

Extracted from sea-buckthorn and cranberries

Glycyrrhizic acid

Applied in the synthesis of anti-HIV agents

Extracted from licorice roots

Peroxidase

Reagent in immune-ferment analyses and diagnostics

Extracted from horseradish roots

Betuline

Applied in the synthesis of anti-virus

preparation

Extracted from birch bark           

Essential oils

Applied inphytotherapy

Extracted from herbs

Novosil

Immune- and growthstimulator of agricultural plants

Extracted from the needles of Siberian fir

D3carene

Applied in the synthesis ofpirehtroid pesticides

Extracted from galipot of conifers

 

Order-driven production of the compounds is organized in the pilot plant of Novosibirsk Institute of Organic Chemistry, Siberian Branch of the RussianAcademy of Sciences. Extraction technologies are patented.

 

 

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences
9, Acad. Lavrentiev Ave,  630090, Novosibirsk, 90, Russsia
Tel.: 8(383) 330-73-93    G.I.  Schukin
Fax: 8(383) 330-97-52      E-mail:This email address is being protected from spambots. You need JavaScript enabled to view it.

Handout

Scientific, technical and technological novelty

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At the N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry special consideration is paid to development of the plant protection products from renewable natural raw materials. Advantages of preparations:

  • complex action to the plants;
  • increase of plant resistance and raising the level of crop yield;
  • high efficiency with low product consumption;
  • human and environment friendly;
  • conduce the production of ecologically pure products;
  • unlimited renewable vegetable raw material resources;
  • possibility of production from lumbering and woodwork waste.
 

 

Products produced from fir-tree and developed at the NIOCH SB RAS
Name, Patent number Known application Active components agr_2
NOVOSIL (fir)
23369539		 Immune- and growth stimulator of agricultural plants Acid fraction of extract from the needles of Siberian fir, triterpene acids composition
VITAPRINOL (fir)
23369539		 Feed additive for poultry (analogue of composition RASTSTIM) Neutral(lipidic) fraction of extract from the needles of Siberian fir
COMPOSITION FOR PRODUCTION OF PREPARATION FOR CROP YIELD INCREASING AND FUNGICIDAL ACTION (FIR)
2469539		 Increasing of the level of crop yield for vegetables and cereal crops, fungicidal activity Bornilacetate, borneol 45-50 weight%, composition of terpenes from waste of Novosil production process (volatile fraction)
CONCENTRATE OF AQUEOUS EXTRACT FROM THE NEEDLES OF SIBERIAN FIR (FIR)
2348168		 Feed additive for cattle Concentrate of sugars, oligosaccharides, flavonoids, aqueous extract - waste of Novosil production process
ABISTIM (FIR)
2355170		 Growth of cereal crops and vegetables with fungicidal and antistress properties Composition of biologically active glycosides of phenol and polyphenol compounds of mono- and polysaccharides, maltole from the needles of Siberian fir
PIHTOROS (FIR)
2432744		 Preparation for agricultural plants protection with growth stimulation and fungicidal action Fir oil in the form of stable emulsion with liquid soap
PIHTOROS+ (FIR)
2443111		 preparation for agricultural plants protection with growth stimulation and fungicidal action fir oil in the form of stable aqueous emulsion
KLIPS (FIR)
2372930		 Growth and immune stimulator with fungicidal activity Composition of biologically active compounds from lipidic fraction
LEOLILA (FIR)
2437286		 Growth stimulation and protection of agricultural plants from diseases Composition of aliphatic and diterpene acids, sterols
BIUS (FIR + LICHEN)
2437285		 Suppression of root rot formation and plant growth stimulation Extract from the needles of Siberian fir, extract from lichen (usnic acid)

Products produced from larch, lichen and developed at the NIOCH SB RAS
Name, Patent number Known application Active components agr_2
LARUS (LARCH + LICHEN)
2464785		 Preparation for wheat protection from diseases and increase level of crop yield Composition of dihydrokvercetine, usnic acid with salts additive
BIOFUNGISTIM (LARCH)
2324352		 Increase of the level of crop yield for cereal crops due to growth stimulation and decrease of morbidity level Composition of phenilpropanoids, sterols, diterpenes. The composition is produced from fresh chopped Siberian larch timber

 

NOVOSIL

novosil

NOVOSIL – high-performance bioactive new generation preparation for growth stimulation and protection of agricultural plants from diseases

NOVOSIL – ecological balanced phytogenous preparation which demonstrates:

  • increase of the level of crop yield by 25-30%;
  • enhancement of seeding, plant viability in extreme climatic conditions by 14-17%;
  • enhancement of fruits and seeds quality – seed mass increase by 4-5%, increase of seed unctuosity by 3-3.5%, as a result raising the level of crop yield of 5-8 centner per hectare);
  • 15-27% increase of productive bushiness;
  • decrease of plants morbidity of fungous, bacterial and viral diseases (phytophthora, root rot, etc.) by a factor of 5;
  • decrease of crop losses during a storage.

NOVOSIL also stimulates growth of plants and decreases ageing time:

  • fruitification enhancement;
  • reduce of harm from plant deseases;
  • enhance a quality of plants – saccharinity and unctuosity , decrease of acidity and nitrates content;
  • suitable for seed wetting for acceleration of germination and growth activity;
  • better ovary preservation especially at low temperatures.

NOVOSIL is a registered preparation in national Russian catalog of pesticides suitable to applicatio in Russia.

Patents №2108803, №2147400 (RU)

 

PIHTOROS

pihtoros

PIHTOROS - low dose preparation produced from renewable natural raw materials.

PIHTOROS is a stable 1-5% water emulsion with liquid soap and containing fit oil extracted from the needles, verdure and cortex of Siberian fir.

Field tests of PIHTOROS on cereal crops (wheat, barley, oat), onion, potato plant showed decrease of plant morbidity of root rot, dust-brand and raising of crop yield level by 32-69% in comparison to infected control plants.

Advantages of PIHTOROS:

  • high efficiency against fungous and bacterial diseases of agricultural plants;
  • low consumption of preparation in preplant and vegetation phase processing;
  • easy application and dosing;
  • full safety for agrocenosis and human;
  • easy producing technology without expensive equipment;
  • solving the problem of rational use of Siberian fir lumbering waste.
Patent№ 2432744 (RU)
 

LIPIDIC FRACTION OF EXTRACT FROM THE NEEDLES OF SIBERIAN FIR (VITAPRINOL)

vitaprinol

New technology of production of biologically active lipid FRACTION OF EXTRACT FROM THE NEEDLES OF SIBERIAN FIR (Abies Sibirica) was developed at NIOCH SB RAS. The technology allows to produce LIPIDIC FRACTION and additional biologically active compounds (used as a fodder additive for fowl) from waste of NOVOSIL production process.

Efficiency of fodder additive (norm consumption 0.7 kg per ton of fodder) was demonstrated on chicken-broilers and quails:

  • increase of average 20-days broiler weight by 9.1%;
  • enhancement of young animals safety by 14%;
  • average daily live weight increase by 11-13%;
  • decrease of forage consumption per 1 kg of addition weight by 6-12%;
  • increase of quails egg production in preproduction period by 7.9-20% ;
  • decrease of forage consumption for quails by 12.3-24.6%.

Fodder additive is registered under the trade mark VITAPRINOL.

Patent № №2336889 (RU)

 

COMPOSITION FOR PRODUCTION OF PREPARATION FOR CROP YIELD INCREASING AND FUNGICIDAL ACTION

composition

New COMPOSITION for production of preparation from needles of Siberian fir extract was developed at NIOCH SB RAS. The composition contains bornilacetatil borneol 45-50 weight%, sum of terpenes and serves to increase the level of crop yield for vegetables and cereal crops, fungicidal action like preparations NOVOSIL and RASTSTIM.

Advantages of the composition:

  • high biological, fungicidal and growth stimulating activity resulting in increase of the crop yield level by 12-46% (wheat, oat, cucumber, potato plant, garlic, onion)/li>
  • easy-to-use preparative form for use and dosing/li>
  • reducing ecological effect to environmental due to decrease of processing ration and total preparation consumption;
  • simple producing technology without expensive equipment thus possibility to large-scale production of the preparation at the fir lumbering manufacture.

Patent № 2469539 (RU)

 

CONCENTRATE OF AQUEOUS EXTRACT FROM THE NEEDLES OF SIBERIAN FIR

concentrate

We developed ecologically clean technology for production biologically active composition - CONCENTRATE of sugars, oligosaccharides from waste of Novosil production process. The CONCENTRATE is used as a fodder additive for cattle.

CONCENTRATE was demonstrated to increase safety, stimulate growth and productivity of chickens.

Patent № 2348168 (RU)

 

ABISTIM

abistim

ABISTIM – low dose ecologic preparation for growth of cereal crops and vegetables with fungicidal and antistress activiry. ABISTIM is a composition of biologically active glycosides of phenol and polyphenol compounds of mono- and polysaccharides, maltole from the needles of Siberian fir.

ABISTIM serves for preplant processing of seeds, tubers, bulbs during vegetation period.

Use of low dose of ABISTIM results:

  • early crop with increasing crop level for vegetables - by a factor of 1.2 for garlic, 1.2 for cucumber, 1.3 for pepper, 1.3 for aubergine, 1.4 for cabbage;
  • increase of crop level for cereals crops - by a factor of 1.2 for wheat, barley, oat;
  • decrease of diseases action - 100% biological efficiency against dust-brand for barley, 69.4% decrease of covered smut effect for wheat, barley, oat;
  • decrease of root rot action 75.8% for wheat, 42.5% for barley, 88.6% for oat.

Norm consumption of ABISTIM for preplant processing the is 100 ml per ton.

Patent №2355170<RU)

 

PIHTOROS+

pihtoros+

PIHTOROS+ - ecologically safe emulsion preparation from natural raw material with growth stimulation and fungicidal action for a large number of agricultural and decorative plants.

The preparation contents fir oil from needles of Siberian fir (1-10%), water-soluble polymer (1-10%) and water (the rest).

PIHTOROS+ demonstrates:

  • high growth and root formation activity;
  • effective protection from 52 to 94 % against root rot, dust-brand, powdery mildew, brown rust, helminthes spore disease;
  • increase the level of crop yield and plants quality – for cereals crops 62-109%, for vegetables 20-80% and 10-100% for decorative plants.

PIHTOROS+ is used for preplant processing, spraying in vegetation period - safe for agrocenosis and human with easy-to-use dosing, low consumption and easy production technology.

Patent №2443111 (RU)

 

KLIPS (ACIDIC LIPID FRACTION)

klips

KLIPS is a composition of biologically active compounds extracted from needles of Siberian fir. KLIPS is produced from the waste of lipid fraction.

The preparation demonstrated high efficiencies as growth and immune- stimulating agent for agricultural plants with additional fungicidal activity.

KLIPS showed:

  • efficiency for wide range of agricultural plants – pea, garlic, wheat, potato plant;
  • increase of seeds germination by 15-50% for agricultural plants;
  • suppression of fungous diseases.

Biological activity of KLIPS is comparable with widely used preparation NOVOSIL.

KLIPS is used as aqueous emulsion with emulsifiers at different concentrations for wetting , preplant processing and spraying at any vegetation period.

Patent №2372930 (RU)

 

LEOLILA

leolila

LEOLILA is a new low dose ecological natural preparation for growth stimulation and protection of cereals crops, leguminous plants and vegetables.

LEOLILA is biologically active composition of aliphatic and diterpene acids, sterols, diterpene alcohols, and polyprenols with additives as mono- and sesquiterpene compounds produced from Siberian fir.

The preparation demonstrated:

  • high efficiency for increase of crop yield level for cereals crops, leguminous plants and vegetables with fungicidal activity;
  • growth stimulation and increase crop yield level by 12-116% to total crop level and by 12-283% to early crop;
  • decrease the agricultural plants morbidity of fungous diseases.

Simple technological process for LEOLILA allow large-scale production of the preparation at the fir lumbering waste manufacture.

Patent №2437286 (RU)

 

LARUS
(PREPARATION FOR WHEAT PROTECTION)

larus

LARUS is a special preparation for effective wheat protection from diseases and for increae the level of crop yield. LARUS was developed in cooperation with Siberian Research Institute of Agriculture and Chemicalization of Siberian Sranch of Russian Agricultural Academy. The preparation is based on extracts of larch (98.5%), lichen (1%) and special additives (0.5%).

Wide action of the composition allows using it at early period of wheat growing.

Preplant wheat seed processing shows:

  • seed grain enhancement – suppress root rot by a factor of 2.6 , crop yield level increase to 1.6 centner per hectare);
  • for spring wheat increase of the ear standing thickness and wheat height in florescence period by 7.4 sm or 12.6%.

Spraying of the wheat:

  • in bushing period results in additional growth of overground mass;
  • in ear formation period results in decrease of wheat leaf blotch formation by 62% and increase of the crop yield level by 6 centner per hectare or 30.4%.

LARUS consumption during spraying in bushing and formation period is 0.2 liters per hectare.

Patent №2464785 (RU)

 

BIOFUNGISTIM

biofungustim

BIOFUNGISTIM is a preparation for protection of cereals crops from diseases.

BIOFUNGISTIM contains a composition of phenilpropanoids, sterols, diterpenes from fresh chopped Siberian larch timber.

Results of BIOFUNGISTIM tests showed the preparation efficiency for cereals crops like wheat, barley, oat against the following diseases - covered smut, dust-brand, root rot, cormophyte infections.

The developed preparation allows one to simplify of plants processing at preplant period, increase the crops yield level of cereal crops due to growth stimulation and additional diseases protection. Consumption norm is 100 ml per ton.

Patent №2324352 (RU)

 

BIUS

bius

Preparation BIUS was developed in the close cooperation with Siberian Research Institute of Agriculture and Chemicalization of Siberian Branch of Russian Agricultural Academy. The preparation is based on natural extracts from the needles of Siberian fir and lichen.

Natural compounds contained in BIUS forwards the stress resistance and resistance of plants to extreme environmental conditions. The preparation was tested on wheat and potato plant. Use of BIUS preparation resulted in the suppression of root rot formation and growth stimulation with the following crop yield level increase by 15 centners per hectare.

BIUS showed the outstanding results during testing on potato plant namely increase of healthy tubers formation level by 85 centners per hectare.

Patent №2437285 (RU)

 

 
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Commercial offer

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Science offers:

  • Partnership aimed to increase of production scale;
  • Partnership aimed to organize the production of developed preparations on industrial scale;
  • License agreement.

CONTACT:

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Science

Applied Products Promotion Department
9, Academician Lavrentjev ave.,
Novosibirsk 630090, Russia
Tel.: +7(383) 330-96-61
Fax.: +7(383) 330-96-61
E-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.
www.nioch.nsc.ru

 

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