Derivatives of 1,4-bis-substituted 2,6,7-dioxabicyclo [2.2.2] octanol

 

(57) Abstract:

Usage: as a pesticide to kill insects. Product: derivatives of 1,4-bis-substituted 2, 6, 7 dioxabicyclo /2.2.2/ octanol, f-ly 1 R-C(CH2O)3C-X (1), where R and X have the respective meanings LD50less than about 400 mg/kg muli Musca domtica. AND LD50in the presence of the synergist, less than about 60 mg/kg Pesticide activity was detected against a wide class of different insects. Pesticidal activity of the composition greatly increases when using certain types of synergist. 4 C. p. F.-ly, 4 PL.

The invention relates to a new class of pesticides, which are 1,4-bis-substituted-2,6,7-dioxabicyclo(2.2.2)octane.

The invention was developed with the support of the government of the United States in accordance with document N S00049 issued by the National Institute of health. The United States government has certain rights in this invention.

Pesticides are chemicals that are used to influence various insects found on valuable agricultural plants, livestock and people and their environment is to destroy weeds), the nematicides, substances for destruction of shells, acaricides and substances for the destruction of parasites.

Currently there are a large number of classes of compounds which possess pesticidal activity, however, known pesticide composition may become less effective due to the fact that there is an increase in the resilience of those organisms for destruction which they are intended. This is due to the fact that you need continuous development and the development of new types of pesticides.

The ideal pesticide must have high efficiency in destroying insects and to be biodegradable.

The purpose of the invention to develop pesticide compounds with desired properties.

In accordance with one aspect of the present invention pesticides containing compound characterized by the formula R-C(CH2O)3C-X, where R and X have the above meanings, and this connection has pesticidal activity, because its 50% lethal dose LD50expressed in micrograms of compound per gram wet weight of flour Musca domestica (fly home), is not more than about 400.

In the SUB>C-X, where R and X have the meanings stated below, in combination with a synergist to provide pesticidal activity and together they provide a 50% lethal dose LD50expressed in micrograms per gram wet weight of not more than about 60.

In accordance with another aspect of the present invention, the composition as described above, contains a compound characterized by the formula R-C(CH2O)3C-X, where R represents propyl, isopropyl, butyl,3-C10-cycloalkyl or phenyl, X6-C10-cycloalkyl,6-C10-cycloalkenyl,2-C6-quinil or phenyl substituted by one or more substituents selected from a halogen atom, cyano, azido - or nitro-group or WITH1-C2-alkyl, possibly substituted by 1-3 halogen atom, provided that when X 4-forfinal, R is not phenyl.

In accordance with another aspect of the present invention, the composition as described above, contains a compound characterized by the formula R-C(CH2O)3C-X, where X represents 4-chlorophenyl, and R represents propyl, isopropyl, butyl, cyclopentyl, cyclohexyl or phenyl, or where X is a cyclohexyl, and R is the, 4-bromophenyl, 4-cyanophenyl, 3,4-dichlorophenyl or cycloheptyl, or where R represents tert-butyl, and X is a 2-forfinal, 3-chlorophenyl, 4-forfinal, 4-bromophenyl, 4-triptoreline, 4-nitrophenyl, 4-cyanophenyl, 4-azidophenyl, 3,4-dichlorophenyl, 2,3,4,5,6-pentafluorophenyl, Nord-pentyl, cyclohexyl, cycloheptyl or ethinyl or where R represents isopropyl and X represents 4-nitrophenyl, cyclohexyl or cycloheptyl; or where R is a standards-propyl, and X is a 2-bicyclo(2.2.1)heptyl or cyclohexyl-3-enyl.

In accordance with other aspects of the present invention pesticidal compounds and compositions mentioned above, are used to destroy certain, pre-selected insect species.

The compounds of formula (I) can be used for combating arthropods, for example, parasitic insects and mites. Therefore, another aspect of the present invention is also a method of combating arthropod parasites of animals, including processing animal an effective amount of the compounds of formula (I).

For these purposes the compounds of formula (I) can be used as themselves, and in the form known diluted preparations, e.g. the fuel, solid vapor sources, such as briquettes, emitting a pair of active substances, wettable powders, granules, sprays, concentrates, emulsions, oil suspensions, oil solutions, soaked items, or drugs for rinsing. Concentrates bath is not used by themselves, and diluted with water, after which the animal is placed in a bath filled with a solution. Treatment sprays done manually or by using a device that creates a strong stream or devices for volume spraying. Animals, plants or the surface can be processed with high volume spray method or subjected to surface treatment of low-volume or ultra-low volume method. Treatment of aqueous suspensions may also be used in the same manner as and using sprays or solutions of water for bathing. Processing bustami can be carried out with the help of special devices for spraying, or (in the case of their use for treatment of animals) they can be placed in perforated bags, suspended on trees or attached to the bars for rubbing animals. Pastes, shampoos and grease can be applied manually or distributed on the surface of inert material. Prepare part of it remained on the animal.

Consumption of compounds of formula (I) in the processing of the animal may vary depending on the nature of the connection, the time between treatments, the type used for processing of the drug and the intended parasite, however, as a rule, the concentration in the preparation is in the range 0.001 to 20.0, preferably 0.01 to 10 wt. The number applied to the animal connection depends on the method of application, size of the animal, the concentration of the compound used in the preparation, dilution of the drug and the type of drug. Usually it ranges from 0.0001 to 0.5% (with the exception of undiluted drugs such as drugs for irrigation, in which the concentration of the compounds of formula (I) is in the range from 0.1 to 20.0, preferably from 0.1 to 10%).

The compounds of formula (I) can be used to process and plant protection. In this case, the active component is used in an effective, from the point of view acaricidal and insecticidal activity quantities. The flow rate of the active ingredient depends on the nature of the connection you use, type of drug, method of its use, nature, plants, alleged pests and other factors. Usually when processing agricultural to the Arata for processing of agricultural crops is in the range of 0.0001-50, preferably 0.1 to 15 wt.

Crops for processing which can be used in the proposed remedies include cotton, wheat, corn, rice, sorghum, soybeans, grapes, tomatoes, potatoes, fruit trees and spruce.

Dusty, greases, pastes, surface and volume sprays and aerosols are used for this purpose as described above. The concentration of the compounds of formula (I) is in the range 0.001-20 wt.

It was found that the compounds of formula (I) have activity against flies bedroom (Musca domestica), and other arthropods parasites, including tetranychus urticae Plutella xylostella, various species of Culex and Blatella germanica. Therefore, they can be used for combating arthropods, such as insects and mites, in any area where they do damage, in particular in agriculture, animal husbandry, medicine, and everyday life.

To insect parasites, against which can be used for the proposed compounds are groups of Coleoptera (e.g., Anobium, tribolium, Sitophilus, Deabrotica, futhonomus or different species of Anthrenus), Lepidoptera (e.g., Ephestia, Plutella, Chilo, Heliothis, Spodoptera, or various kinds fineola), Diptera (e.g., Musca, Aedes, Culex, Glossina, Stomoxys, Haemotobia, Tabanus, Hydrotaea, Lucilia, Chryso is R, Pediculus humanus capitis, Pediculus humanus phythiruspubis Linognathus and Haematopinus), Hemiptera (e.g., Aphis, Bemisia, Aleurodes, Nibopavata, Nephrotetis or different species Cimex), Orthoptera (e.g., Schisticerca or different species Acheta), Dictyoptera (e.g., Blatella, Periplaneta or different kinds Blatta), Hymenoptera (e.g., Solenopis or different species of Monomorium), Isoptera (for example, different species of Reticulitermes), Siphopartera (for example, Clenocphalides or Pulex), Thysanura (for example, different types of Lepisma), Dermaptera (for example, different types of Forficula) and Pscoptera (for example, different types Peripsocus).

To parasites-ticks include, for example, various species of the genus Boophilus, Phipiceplialus, Amblyomma, Hyalomma, Ixodes, Haemaphysalis, Dermocentor and Anocentor, and manges such as Sarcoptes Scabiei and Tetranychus, Psoroptes, Psorergates, Notiedres, Chorioptes and different types Dimodex.

The proposed connection can be used in combination with one or more other active ingredients (e.g., pyrethroids, carbamates and organophosphates) and/or attractants, fungicides, etc., it Was determined that the proposed activity of the compounds can be enhanced by supplements synergists, for example one of the synergists belonging to the class oxidase inhibitors, in particular piperonylbutoxide or N1A 16388; other compounds in accordance with the present invention or a PYRETHROID, have settled between him and the compound of formula (I) in the preparation is between 25:1-1:25, for example about 10:1.

Stabilizers introduced into the product to prevent possible chemical decomposition of compounds may be, for example, antioxidants, such as tocopherol, butylhydroxyanisole and butylacetyl, and acceptors, such as epichlorohydrin.

The proposed types of pesticide compositions have the required high pesticidal activity, in particular in those cases when they are used together with the active substance synergetic, and these compositions are capable of biological decay. These pesticidal compositions have significant pesticidal activity against insect pests, like an ordinary house fly, black and red cockroaches, moths, aphids, larvae of mosquitoes, bugs, etc.

In accordance with the present invention features a compound characterized by the formula R-C(CH2O)3C-X, in which R and X each represent an organic substituents, located, respectively, in the 4th position 1st position in the specified connection. It was found that this class of compounds includes a number of chemicals that have significant pesticide activity. In table. 1 and 2 shows the relative performance is an integral part of the formula, when using these compounds in pure form or together with synergetic-butyl butoxide (PB). In these tables, the following abbreviations are used: PL-phenyl, n-normal, i-out, S-secondary t-tertiary, and with the cyclo, Pr is propyl; Bu is butyl, Pen-pencil; Hex-hexyl; Hept-heptyl.

The proposed pesticides are characterized by pesticidal activity, as defined in 50% lethal dose LD, expressed in micrograms of pesticide per gram wet weight of selected insect, and this value is not more than about 400. For example, this activity was identified in relation to fly home. The proposed alternative pesticides or additionally possess pesticidal activity, expressed through the 50% lethal dose LD50micrograms of pesticide per gram weight of the selected insect, not greater than about 60 and more preferably not exceeding about 20. This activity was shown when using insecticide against flies home.

The use of synergists together with pesticides is a well known fact, a detailed discussion of this problem is given in [2]

Proposed connections become even more effective together with synergists, chocolina pesticide providing a longer period of action of the pesticide, and therefore its higher toxicity.

The proposed composition can be used in combination with an inert carrier, which serves as a diluent or carrier for the active pesticide. So, for example, a toxic substance can be dissolved in hydrocarbons, obtained from petroleum, tetrahydrofuran, acetone, monoalkyl ether of ethylene glycol (cellosolve), as well as other suitable inert carriers before use. Alternative toxic substance can be adsorbed on a solid inert carrier such as talc, clay, melkoizmelchennye silicon dioxide and the like materials.

Toxicity in relation to domestic flies depends on the nature of the R-substituent, and X is a substituent that is presented in the table. 1, the data which are the main evidence of the effectiveness of the proposed compounds. The compound 1,4-bis-substituted-2,6,7-dioxabicyclo(2.2.2)octane were tested in pure form or together with butyl butoxide (PB).

The toxicity of the proposed compounds in relation to black cockroaches for example, topical administration of 1,4-bis-substituted-2,6 with butyl butoxide. The obtained test results are shown in table. 2.

Determination of biological activity.

Was obtained and tested some of the proposed compounds. Tests were conducted on insecticidal activity against Musca domestica as a synergist, and without it.

From the results of these tests, it follows that each of the following compounds has a higher insecticidal activity (lower value LD50) than 1-(n-butyl)-4-(tert.butyl)-2,6,7-dioxabicyclo-[2.2.2] octane (compound 51 in the table. 1 with LD50450 µg/g) without the synergist and higher activity with synergist than 1-phenyl-4-(tert.butyl)-2,6,7-dioxabicyclo[2.2.2] octane (compound 17 in table. 1 with LD5023 µg/g, with a synergist). In the tested compounds 4-m Deputy was tert.butyl, and 1-m Deputy 3-chloro-4-methoxyphenyl, 4-itfeel, 3-cyanophenyl, 4-cyano-2-chlorophenyl, 4-methoxyphenyl, 4-were (tolyl), 2-bicyclo[2.2.1]heptyl, cyclooctyl, 3-cyano-4-were, 3-methoxy-4-chlorophenyl, 3-ethylphenyl, 4-trimethylsilylethynyl, 4-methoxy-3-cyanophenyl and 4-vinylphenol. In addition were tested and showed the same high activity of the following compounds: 1-(3,4-dibromocyclohexane)-4-(n-propyl)-2,6,7-dioxabicyclo[2.2.2] octane is phenyl)-4-cycloheptyl-2,6,7-dioxabicyclo[2.2.2] octane, 1-(4-cyanophenyl)-4-isobutyl-2,6,7-dioxabicyclo[2.2.2] octane, 1-(4-cyanophenyl)-4-(Deut.butyl)-2,6,7-dioxabicyclo[2.2.2]octane, 1-(4-cyanophenyl)-4-(1-methylprop-2-enyl)-2,6,7-dioxabicyclo [2.2.2]octane and 1-(4-trimethylsilylethynyl)-4-(phenyl)-2,6, 7-dioxabicyclo [2.2.2]octane.

P R I m e R 1. the 50% lethal dose LD50for house flies.

The compounds listed in table. 1, were tested to determine their insecticidal activity, and these compounds were dissolved in acetone or tetrahydrofuran in the case, if they were insoluble in acetone. A series of solutions was obtained using the same solvent. Solutions of compounds with a volume of 0.5 μl was applied tapicerki on the ventrum of the abdominal cavity shot adult female house flies (Musca domestica); SCR after 3-5 days after birth, each fly had a weight of 20 mg.

Studies to determine the toxicity was carried out by treatment (topical) house flies, using butyl butoxide in 250 micrograms per gram, 2 or 3 h before use of toxic substances. The treated flies were given sugar and water, and the mortality was determined after 24 h at 25aboutC. Data predamage, needed to kill 50% of flying insects, these data indicated as 50%) lethal dose LD50.

In table. 1 shows the relationship between structure and activity of the compounds of the subject tests on the flies, and flies, pretreated with butyl butoxide. Many of these compounds are active in the same range for this type of testing, as currently produced by the pesticides industry.

Significant insecticidal activity against house flies was detected by respective combinations of the R-substituent and X is a substituent. These combinations are the following:

R represents norms.propyl, isopropyl, norms.butyl, secondary butyl, tertbutyl, cyclopentyl, cyclohexyl or phenyl, and X represents norms. butyl, norms. pentyl, cyclohexyl, cycloheptyl, 4-cyanophenyl, 3,4-dichlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-forfinal, 4-nitrophenyl, 4-azidophenyl, pentafluorophenyl, 2-bicyclo[2.2.1] heptyl, phenyl, 2-forfinal, 4-triptoreline, ethinyl or cyclohex-3-enyl.

Other X or R substituents, which can ensure the activity, are replaced by cyclea the x, when is a substituted phenyl group. It seems preferable that R was not a phenyl in the cases when X is a phenyl or 4-forfinal.

Compounds characterized by pesticidal activity, include such compounds in which R is a normal or branched propyl or butyl, or phenyl or cycloalkyl containing from 3 to 10 carbon atoms, and X represents cycloalkyl or cycloalkenyl containing from 6 to 10 carbon atoms, or substituted phenyl. Another group of compounds with pesticidal activity, are compounds in which R is a normal or branched propyl or butyl, or phenyl or cycloalkyl containing 5 or 6 carbon atoms, and X represents a cyclohexyl, cycloheptyl, cyclohexenyl, ethinyl or phenyl, substituted halo-, cyano-, azido-, nitro - or1-2the alkyl and specified WITH1-2alkyl is substituted by 1-3 halogen atoms. Another group of active compounds is that group of compounds in which R represents norms.propyl, normal or branched butyl, cyclopentyl or cyclohexyl, and X represents a cyclohexyl, cycloheptyl e one group of active compounds are those compounds in which R represents phenyl and X represents phenyl substituted in the 3 position or 4-position by chlorine and/or bromine.

Compounds that were obtained and subjected to tests to determine their insecticidal activity, and which are characterized by very high activity (in the General case their 50% lethal dose LD50is less than or equal to about 5.5 micrograms/g wet weight, when used in conjunction with butyl butoxide) are such compounds in which:

X represents 4-chlorophenyl, and R represents nonproper, Nembutal, secondary butyl, tertbutyl, cyclopentyl, cyclohexyl or phenyl;

R represents tert-butyl and X represents a cyclohexyl, cyclopentyl, 4-forfinal, 4-bromophenyl, 4-nitrophenyl, 4-cyanophenyl or 3,4-dichlorophenyl; and

R represents cyclohexyl, and X represents a cyclohexyl, cycloheptyl, 4-forfinal, 4-bromophenyl, 4-cyanophenyl or 3,4-dichlorophenyl.

Summarizing the above, we can say that R and X can represent almost any organic substituents that provide the desired insecticidal activity. So, insecticidal loukil, substituted cycloalkyl, phenyl or substituted phenyl substituents. At that time, as not all connections with these substituents have activity, however, there are many suitable combinations. Further simple tests at home flies, or similar tests conducted with any other insects, and helps to identify those combinations that are suitable for purposes of destruction, of any particular insect.

P R I m m e R 2. Tests with other insects.

The compounds listed in table. 2, were tested to determine their toxicity against adult males black cockroaches (Periplaneta Americana). The test consisted in applying solutions subjected to the tests as described in example 1, in the region of toraks using one microliter of a solution of the carrier in one insect. In each case, the cockroaches were also tested after pre topical treatment with butyl butoxide in 250 micrograms/g wet weight for 2 h to enter trioxosilicate. 50%) lethal dose LD50was determined after 24 h at 25aboutC. the Compounds under test were very Silicea the which was achieved during testing at home flies treated with butyl butoxide, except for two compounds (13 and 38), which is about 10 times are more toxic to house flies than cockroaches. Other tests showed that compound 6 is also toxic to larvae of mosquitoes, aphids living on the black beans, red cockroaches and bedbugs. Thus a wide range of effectiveness of a new class of pesticides, mentioned above, was confirmed.

P R I m e R 3. Experiments with other synergists.

Other synergists, which, as you know, are inhibitors of oxidative detoxification, can be used instead of butyl butoxide. This effect was confirmed by tests on house flies using compounds in which R is a tertiary butyl and X represents 4-chlorophenyl. A synergistic effect is achieved when using butyl butoxide in 250 micrograms/g, has also been made in cases where this synergist replaced the other: -(2-methylpropyl) -(2-PROPYNYL) phenylphosphate at a concentration equal to 125 micrograms/g wet weight or synergetic: 0,0-diethyl-0-phenyl phosphorothioate when contee fact, to most closely simulate the situation associated with the application. These synergists are relatively low cost and toxicity for mammals. Many compounds are thus useful and give economic effect as synergists provide improved insecticidal activity trioxosilicate used to kill insects.

P R I m e R 3V. In experiments carried out on the house flies using the same compounds as in example 3, but when the content of piperonylbutoxide 1 g/g of the active substance, observed the same activity as when fewer piperonylbutoxide.

Even when the content of piperonylbutoxide 25 g/g of the active substance obtained the drug has the same effect.

P R I m e R 4. Experiments on determination of toxicity to mammals.

The level of mammalian toxicity of the two compounds that are the subject of the present invention was determined as follows. These two compounds were individually dissolved in olive oil, thus obtained solution was administered intraperitoneally to mice to determine the mortality after 24 hours These compounds represented followed by the Oh cyclohexyl (compound 59). The values of the 50% lethal dose LD50when injection for tert-Putilkovo connection and ISO-propyl compounds are respectively more than 200 and more than 500 milligrams/kg of body weight.

Thus the proposed compounds are characterized by low toxicity towards mammals, 50% lethal dose LD50is more than 200 milligrams/kg of body weight. Toxicity towards mammals can vary greatly depending on the media type, the method of introduction into the organism and type of mammal.

The proposed compounds have significant activity when used as a pesticide against a large class of different insect species. These compounds easily undergo biological decomposition.

One of the advantages of the proposed insecticides is that their pesticidal activity is significantly above their toxicity towards mammals. Therefore, those small amounts of pesticides that are used in the fight against parasites, will not have a harmful effect on mammals. Obviously, this is beneficial to the environment. In addition samloem chemical structure differs significantly from the known pesticides. Therefore, they differ from nanologica known pesticides and surpass them.

P R I m e R 5. Konkurentnoe or prior use of the synergist.

The synergist equally or more effective when applied with insecticide, in this example, the connection 6, in the case where it is used two hours earlier.

A. Connection N 6

< / BR>
The synergist AI - Noah

PB 5 µg/fly 1,25 1,0

NIA 16824 2.5 µg/fly 1,0 0,35

R33865 1 µg/fly 0,6 0,6

These data show almost equal to the efficiency of the joint application and pre-treatment with synergist. Street 111A 16824 (-(2-methylpropyl) -(2-PROPYNYL) phenylphosphonate described in the description in example 3; R 33865 --diethyl-phenyl Fosforit also described. All these compounds as butyl butoxide, (PB), are known synergists for insecticides.

P R I m e R 6. The ratio of synergist and insecticide.

The ratio of the insecticide synergist is in the range from 1 part of synergist to 20 parts of insecticide, to 200 parts of synergist to 1 part insecticide. Cm. an example for the connection 6 and the example for the connection 6, and the example for the connection 24.

C. Compound 6 + PB/ mg/g of destruction

5 mcg/g + 0 10

5 is argest insecticide 2001

C. Connection 24 + synergist RV destruction

250 µg/g 0 30

250 µg/g 12.5 ág/g 40

The ratio of the insecticide synergist 1 20

1.9 µg/g 0 0

1.9 µg/g 250 mg/g 50

The ratio of the insecticide synergist 1321

P R I m e R 7. The use of insecticidal compounds in destroying insects plants.

The leaf of a plant with a diameter of approximately 3 inches, sprayed with 3 ml of 1% solution of the compound No. 6 in acetone. Adults and nymphs of insects on watchlike giant, Oneofelus facialus feeding on this plant, were placed on the treated leaf. All insects were killed at 12 o'clock In the control experiment, none of the insects placed on a sheet of the same size, sprayed only with acetone, were killed at 12 o'clock

In the accompanying following table provides additional data showing the effect of compounds and methods of use thereof. Compound is dissolved in acetone and the solution is applied topically to Mature individuals home flies according to methodology described previously in the description. When using the synergist it is applied topically in the amount of 250 micrograms/piperonylbutoxide per gram flies for two to three hours before application of the test compounds. Compounds were characterized ω synergistic compositions, it is shown that their activity below 40 µg/g when using the tested compounds in pure form.

The active ingredient and synergist can be applied together with the same impressive result, but previously presented data do not indicate simultaneous deposition of toxic substances and synergist. Applicants used the technique of preprocessing.

P R I m e R 8. The activity of representative pesticides is higher in comparison with the known pesticides.

In table. 3 shows the values of toxicity (local) home flies at 25aboutC.

The presented data indicate that the compounds characterized by the formula R-C(CH2O)3C-X, are effective pesticides.R or X may be an alkyl, quinil, cycloalkyl or cycloalkenyl, each of which may be normal, branched or substituted, or they may represent an aryl or substituted aryl. In those cases, when R is a normal or branched alkyl, cycloalkyl or aryl, the compounds give a useful effect. It seems preferable that the number of carbon atoms in R was in the range from 3 to 10. Seems more PM, secondary bootrom or phenyl. X preferably should be cycloalkyl or substituted cycloalkyl, or cycloalkenyl containing from 6 to 10 carbon atoms, a normal alkyl, quinil or substituted phenyl. Effective pesticides are those pesticides that X-substituents are cyclohexenyl and cycloheptenyl. Other suitable alternates are standards-Patil, cyclohex-3-enyl and 2-bicyclo[2.2.1] heptyl. Substituents on the phenyl group in cases where the phenyl group is a group X are halogen, cyano-, nitro - or sidegroup.

The procedure of synthesis. Methods for obtaining compounds characterized by the above General formula presented in the following publications:

Relationship between structure and toxicity of 1-substituted-4-alkyl-2,6,7-dioxabicyclo[2.2.2] octanol. D. C. Milbrath, De.L.Engel, J. G.Verkade and j. E. Casida. Toxicology and applied pharmacology, 47, 287-293 (1979); (Structere Toxicity Relation ships of 1-Substituted-4 alkyl-2,6,7-trioxabicyclo(2.2.2)octanes, D. S. Milbrath; I. L. Engel; I. G. Verkade; I. E. Casida Toxicology and Applied Pharmacology; , 287-293 (1979);

Relationship between structure and toxicity 2,6,7-dioxabicyclo(2.2.2)octanol and similar compounds. J.E. Casida, M It, A. D. Moscioni, J. L.Engel, D. C. Mivr the nd Related Compoudns, I. E. Casida; M. Eto; A. D. Moscioni; I. L. Engel; D. S. Milbrath; I. G. Verkade; Toxicology and Applied pharmacology; , 261-279 (1976);

Nuclear magnetic resonance in polycyclic compounds. II. Communication long range H1H1and H1P31in some derivatives of adamantane and bicyclo(2.2.2)octane. E. J. The Boros, K. J. Cochran, R. C. king and J. G.Arcade, IACS 88, 1140-1143 (1966) (Nuclear-Magnetic Resonance in Polycyc lie Compaunds II Song-Range H1-H1and H1-P31Coupling in Sona Ackamantane and Biciclo (2.2.2) octane Derivativer, I. E. Boros; K. I. Coskran, R. W. King; I. G. Werkade; IACS, , 1140-1143 (1966);

Unusual behavior of hexaferrite and benzene in effect displacement of the aromatic nuclear magnetic resonance. R. D. Bertrand, R. D. Compton and J. G.Verkade, IACS, 92, 2702-2709 (1970) (Unusual Behavior of Hexafluorobenzene and Benzene in the Aromatic Nuclean Magnetic Resonance Shift Effect. R. D. Bertrand, R. D. Compton, I. G. Verkade; IACS, , 2702-2709 (1970);

A new General synthetic method to complex orthoepical carboxylic acid with a bridge connection. E. J. Coca and N. Raju. Tetrahedron Letters , 5571-5574 (1983) (A. New General Synthetic Route to Bridged Carboxylic Ortho Esters E. I. Cokey; N. Raju; Tetrahedron Letters, 24, 5571-5574 (1983).

Intermediate products for these reactions are described: Acetals of ketene. XXXIV. Tetra - and pentamethylene of ketene acetals. S. M. Mckelvin and R. E. Starn, IACS 77, 4571-4577 (1955), (Ketene Acetals, XXXIV, tetra-and Pentamethylene Ketene Acetals, S. M. Mc Elvain; R. E. Starn, IACS, , 4571-4577 (1955).

Getting trimet is.The Appel. Oxazines, receiving method oxosynthesis aldehydes alcohols and secondary products based on them. All-Union scientific research Institute of petrochemical processes, 156-163 (1963);

The development of condensation Talanov. O. S. Dermer and P. C. Solomon. IACS 76, 1697-1699 (1954) (Extension of Tollens Condensation; O. C. Dermer; P. W. Solomon. IACS, , 1697-1699 (1954);

Simple cyclic ethers, obtained by pyrolysis of a complex carbonate esters. D. B. Pattison, IACS 79, 3455-3456 (1957) (Cyclic Ethers Made by Pyzolysis of Carbonate Ethers, D. B. Pattison; IACS; , 3455-3456 (1957);

Two typical methods (a and b) were used to obtain dioxabicyclo octanol (PL. 4). In each of the procedures in the quality of the source material used triol, synthesized from the corresponding substituted acetaldehyde by reaction oxymetholone and subsequent cross-reaction of Cannizaro (reaction of formation of alcohols and acids in the oxidation of the recovery of aromatic aldehydes, trans.). (Reaction described by Demerom and Solomon, in 1954 and Ceslava and others 1963). The reaction was carried out according to the following scheme:

RCH2CHO RC(CH2OH)3< / BR>
Each trioxosilicate gave the corresponding characteristic proton nuclear magnetic resonance and the corresponding characteristics of the mass spectrum. doublet, 2 x d two doublet, dd = doublet of doublets, t triplet, 2 x t two triplets, g Quartet and m, multiplet.

Method A. Condensation of Tirol with orthocarboxylic catalyzed by acid. (Boros et. al. 1966; Bertrand et. al. 1970). The reaction equation is as follows:

R R X where RIcan be alkyl or aryl, preferably the stands or ethyl. For example, a mixture of 2-t-butyl-2-hydroxymethyl-1,3-propane diol (R t-Bu) (0.4 g, 2.5 mmol), trimethyl of articlesantabuse (Hos-Neh; RICH3) (0.5 g, 2.5 mmol) and 4-toluenesulfonic acid (10 mg) is heated to 160aboutWith up until no methanol distills over. The residue is dried in vacuum (1 mm Hg) and then passed through a short column filled with alumina, getting trioxosilicate 60 (Hos-Neh; Rt-Bu) (0.6 g, 95%). Similar techniques are used to obtain the compounds 2-9, 13, 14, 17-19, 21, 23-27, 38, 39, 51, 59, 60 and 65.

Intermediate the trimethyl orthocarboxylic commercially available or synthesized by either of the two ways illustrated complicated methyl esters. According to the first method, the corresponding benzotrichloride or benzotrifluoride (from the synthesized corresponding toluene with N-bromosuccinimide (NBS)) is subjected to substitution of halogen by methoxide (McElvain and Venerable, 1950). These SP as halogen or trifluoromethyl.

According to the second method, the corresponding nitrile is treated with methanol and hydrochloric acid, getting hydrochloride aminoether, and, ultimately, the trimethyl orthocarboxylic (McElvain and Starn, 1955). This method looks as follows:

XCN XC XC(OCH3)3< / BR>
The way Century. Rearrangement acylated hydroxytamoxifen (Corey and Raju, 1983). Acylation of 3-substituted-3-hydroxytamoxifen (obtained from the corresponding triol by pyrolysis of ester carbonate) (Pattison, 1957) gives the corresponding oxetane esters, which can be converted in the presence of epirate boron TRIFLUORIDE to form trioxosilicate. The reaction equation is:

R R< / BR>
< / BR>
For example, 4-nitrobenzoyl chloride (2.28 g, 12.3 mmol) in dry dichloromethane (4 ml) are added to 3-isopropyl-3-hydroxyatomoxetine (1.6 g, 12.3 mmol) in dry dichloromethane (15 ml) and dry pyridine (2 ml) at 0aboutC in nitrogen atmosphere. The solution is stirred overnight, then extracted with water, dried (sodium sulfate), filtered and evaporated, receiving 4-nitrobenzyloxy ether (3.4 g, 99%) as a residue, which in the future is not clear.1H NMR (DCl3), 1,0 (6N, D., (CH3)2C) 2,3 (1H, m, CH), 4,55 (2H, s, ω dichloromethane (15 ml) under nitrogen atmosphere, cooled to (-)55aboutWith and add 2 ml of epirate of boron TRIFLUORIDE. Mixture was allowed to warm to room temperature and quenched with triethylamine, is evaporated to dryness and partitioned between water and dichloromethane. The organic layer is separated, dried (potassium carbonate) and evaporated.

The residue is purified by passing through a short column of basic alumina,

obtaining trioxosilicate 28

(X 4 NO3Ph; R1 Pr) (1.7 g, 50%)

Similarly receive connections 28-32, 43, 53, 61, 62, 71, 72 and 74.

1. DERIVATIVES of 1,4-BIS-SUBSTITUTED 2,6,7-DIOXABICYCLO [2 2 2] OCTANOL General formula

R C(CH2O)3C X,

where R is propyl, butyl, C3C10-cycloalkyl or phenyl;

X C6C10-cycloalkyl, C6- C10-cycloalkenyl, C2C6-quinil or phenyl substituted by one or more substituents selected from halogen, cyano, azido - or nitro, or C1C2-alkyl, possibly substituted by 1-3 halogen atoms, provided that when X 4-forfinal, R should not be phenyl.

2. Connection on p. 1, wherein R is cyclohexyl, cycloheptyl, cyclohexenyl, ethinyl or phenyl, substituted by halogen atom, cyano, azido or nikogda X 4-forfinal, R is other than phenyl.

3. Connection under item 1 or 2, characterized in that R N.-propyl, butyl, cyclopentyl or cyclohexyl and X is cyclohexyl, cycloheptyl or phenyl substituted in the 3 and/or 4 - position substituents, independently selected from the group comprising halogen, cyano, azido - or nitro-group.

4. Connection on p. 2 or 3, wherein R is phenyl and X is phenyl, substituted in the 3rd and/or 4th provisions Deputy independently selected from the group comprising chlorine and bromine.

5. Connection on p. 1, characterized in that it has a pesticidal activity.

Priority signs:

30.01.84 if R C6C10-cycloalkyl, propyl or butyl, X is the value specified in paragraph 1 of the claims;

23.01.85 if R C6C10-cycloalkyl, propyl, butyl or phenyl, X has the values specified in paragraph 1 of the claims.

 

Same patents:

The invention relates to a method for production of new chemical compounds having pesticidal activity

The invention relates to 7-examinerlawrence heterocyclic Amida - analogues of prostaglandins, which are receptor antagonists AND thromboxane a2(THA2or combined receptor antagonists AND thromboxane a2(thromboxane synthetase inhibitors, and are used, for example, in the treatment of thrombotic disease and/or vascular spasm: have a long duration of action

The invention relates to new derivatives of benzo(b)naphthiridine General formula

R(I) where R1hydrogen, alkyl or hydroxyl radical;

R2hydrogen, linear or branched C1-C4-alkyl, foralkyl, cycloalkyl, alkyloxyalkyl or alkylamino radical;

R3WITH1-C4-alkyl, and R4and R5different and mean hydrogen or C1-C4-alkyl;

or R3hydrogen or alkyl, or cycloalkyl and R4and R5individually, each means hydrogen;

R6hydrogen or fluorine;

n is 1 or 2, or their salts, possess antibacterial property

The invention relates to the field of pest control, in particular fungicidal means on the basis pyrrol-carbonitrile and methods of combating fungi

The invention relates to the derivatives of uracil and their use in agriculture, namely use as herbicides

FIELD: agriculture.

SUBSTANCE: invention describes a method for feeding potato and tomato with 6-benzylaminopurine an aqueous solution taken in the concentration 10-4 M and growing pants up to preparing harvest according to technology accepted for the culture crop. Invention proposes 3-fold treatment of plants for vegetation: at the lateral branching phase, at onset of forming economically value organs and immediately after the growth termination. Method provides the effective enhancing the productivity of the most important vegetable crops - tomato and potato.

EFFECT: improved enhancing method.

6 tbl, 4 ex

FIELD: organic chemistry, chemical technology, herbicides.

SUBSTANCE: invention describes a method for preparing compounds of the formula (I):

wherein each R1, R2, R3 means independently of one another (C-C6)-alkyl; R can represent also pyridyl; R4 and R5 in common with nitrogen atoms to which they are joined form unsaturated 5-8-membered heterocyclic ring that can be broken by oxygen atom; G means hydrogen atom. Method involves interaction of compound of the formula (II):

wherein R1, R2 and R3 have above given values; R6 is a group RR9N-; R7 is a group R10R11N-; each among R8, R, R10 and R11 means independently of one another hydrogen atom or (C1-C6)-alkyl in inert organic solvent being optionally with the presence of a base with compound of the formula (IV) ,

(IVa)

or (IVb) ,

wherein R4 and R have above given values; H x Hal means hydrogen halide. The prepared compound of the formula (I) wherein G represents ammonium cation is converted to the corresponding compound of the formula (I) by treatment with Brensted's acid wherein G represents hydrogen atom. Also, invention describes compound of the formula (II) wherein R1, R2, R3, R6 and R7 have above indicated values.

EFFECT: improved preparing method.

9 cl, 12 ex

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

FIELD: agriculture, plant science, plant protection.

SUBSTANCE: the suggested herbicidal composition of selective action contains, except generally accepted additional substances for the composition, a mixture as an active substance including a) herbicidally efficient quantity of compound of formula (I) , where R1 and R3 each independently means ethyl, ethynyl, C1- or C2alkoxy; R4 and R5 forms together the group Z2-CR14(R15)-CR16(R17)-O-CR18(R19)-CR20(R21)-(Z2); R14, R15, R16, R17, R18, R19, R20 and R21 means hydrogen; G means hydrogen, -C(X1)-R30, -C(X2)-X3-R31; X1, X2, X3 means oxygen; R30, R31 each independently means C1-C10alkyl, or salts or diastereoisomer of compound of formula (I), and b) efficient quantity of antidote of formula IIa to prevent harmful action of herbicide, where R22 means hydrogen, alkaline-earth metal or ethyl, or of formula IIb , where R23 means hydrogen, alkaline-earth metal or ethyl, and method for selective control for weed plants and grasses in cultivated plants. Thus, the antidote decreases the damage of cultivated plants induced by herbicide of formula (I).

EFFECT: higher efficiency of plant protection.

3 cl, 4 ex, 4 tbl

FIELD: organic chemistry, agriculture, herbicide composition.

SUBSTANCE: invention relates to herbicide composition, containing conventional inert additives and mixture of a) herbicidically effective amount of substance satisfying the formula I [in formula R1 and R3 are the same or different C1-C4-alkyl; R4 and R5 together form groups of formulae: -C-R6(R7)-O-C-R8(R9)-C-R10(R11)-C-R12(R13)-(Z1), -C-R14(R15)-C-R16(R17)-O-C-R18(R19)-C-R20(R21)-(Z2), or -C-R22(R23)-C-R24(R25)-C-R26(R27)-O-C-R28(R29)-(Z3), wherein each R6-R29 is hydrogen; G is hydrogen or -C(X2)-X3-R31; X2 and X3 independently are oxygen; R31 is C1-C10-alkyl]; b) herbicidic synergic amount of at least one herbicide selected from group containing sulfonylureas, phenoxyacetic acids, as well as florsulam, tralcoxidim, klodinafol-propargil, phenoxaprop-P-ethyl, trifluramine, pendimethaline, picolinafen, etc. Composition also may contain safety effective amount of protective agent, such as chloquintocet-mexyl and additive (e.g., mineral oil or C8-C22-fat acid alkyl esters) in amount of 0-2 mass %. Also disclosed is method for selective controlling of weeds and grassy plants in cultural plants by treatment of cultural plants, seeds or seedlings thereof, or vegetation area thereof with claimed composition.

EFFECT: effective composition and method for weed controlling.

5 cl, 11 tbl, 7 ex

FIELD: organic chemistry, veterinary science.

SUBSTANCE: invention relates to a method for control over exto- and endoparasites taken among group including acariform mites, parasitoformous mites and nematodes parasitizing in animals, productive cattle and domestic animals. Method involves applying veterinary preparation comprising 1-[4-chloro-3-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-(2,6-difluoro)urea and compound of the formula (i):

wherein R1 means one of radicals:

or ; R2 means -CH(CH3)-CH3, -CH(CH3)-C2H5, -C(CH3)=CH-CH(CH3)2 or cyclohexyl; R3 means hydrogen atom or hydroxy-group if a bond between atoms 22 and 23 represents a double bond, or it means hydrogen atom or group =N-O-CH3 if an ordinary bond presents between atoms 22 and 23; R4 means HO-, and the preparation can be in free form or in physiologically acceptable form. Invention provides preparing preparations with good tolerance and rapid effect and persistence with respect to different helminth-associated diseases, parasitiformous and acariformous mites being without adverse effect on normal behavior of animals.

EFFECT: valuable properties of compounds.

7 cl, 3 tbl, 8 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to selective herbicidal compositions, containing customary auxiliary substances, as well as: a) herbicidal effective amount of compound of formula I or agriculture acceptable salt thereof wherein R are independently C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alcoxy-C1-C4-alkyl, or C1-C4-alcoxy-C1-C4-alcoxy-C1-C4-alkyl; m = 2; Q is group of formula wherein R23 is hydroxyl and Y is C1-C4-alkylen bridge; and b) synergetically effective amount of one or more herbicides; and methods for controlling of undesired plants in tame cultures using the said composition. Also disclosed is composition containing customary auxiliary substances, as well as herbicidal and synergetically effective amount of 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]octo-3-ene-2-one of formula 2.2 and herbicidal antagonistically effective amount of antidote of formula 3.1. Compositions based on 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]octo-3-ene-2-one and herbicidal antagonistically effective amount of antidote, as well as methods for controlling of weeds and cereal grasses in tame cultures also are described.

EFFECT: compositions useful in effective controlling of many weeds both in pre-spring and post-spring phases.

5 cl, 63 tbl, 12 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to herbicidal composition containing synergetically effective amounts of (A) and (B) components, wherein (A) has formula II (R1 is C1-C6-alkyl, substituted with halogen; R2, R3 and R4 are hydrogen; R5 is rest of formula -B1-Y1, wherein B1 is direct bond and Y1 is acyclic C1-C6-hydrocarbon or cyclic C3-C6-hydrocarbon; F is -CH2-CH2-, -CH2-CH2-CH2- and CH2-O-; X are independently halogen or C1-C4-alkoxy; n = 0-2; and (B) represents one or more herbicides, selected from group containing isoprothuron, flufenacet, anylophos, ethoxysulphuron, mecoprop-(P), ioxinyl, florazulam, pendimethalin, MV 100, etc. Also disclosed is method for weed controlling using abovementioned composition.

EFFECT: composition with improved herbicidal action.

12 cl, 23 ex, 23 tbl

FIELD: agriculture, in particular method for controlling of specific insect pests.

SUBSTANCE: invention relates to method for controlling of lepidopterous, homopterous, hemipterans, coleopterous, and physopods by contacting of said pests or environment thereof with effective amount of compound of formula I SSS1, N-oxide or agriculturally acceptable salt thereof being effective against abovementioned insects, wherein A and B are independently O or S; R1, R2 represent H, C1-C6-alkyl; R3 represents H, optionally substituted C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, or C3-C6-cycloalkyl; R4 represents H, C1-C6-alkyl, C2-C6-alkinyl, C1-C6-haloalkyl, CN, halogen, C1-C4-alkoxy, C1-C4-haloalkoxy, NO2;. R5 represents H, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-hydroxyalkyl, CO2R11R12, halogen or C1-C4-alkoxy; R6 represents H, C1-C6-alkyl, C1-C6-haloalkyl; R7 represents H, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, phenyl ring, benzyl ring, or 5-6-membered heteroaromatic rind, naphthyl ring system, or 8-10-membered condensed heterodicyclic system. Also claimed are compound of formula I and benzoxazine derivative of formula 10 .

EFFECT: compounds effective against agriculture spineless depredators.

22 cl, 13 tbl, 1 dwg, 24 ex

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a composition showing the selective effect and comprising as conventional inert adjuvants and the following mixture as an active component: a) effective amount of compound of the formula (I): as a herbicide wherein each R1 and R3 means independently of one another (C1-C4)-alkyl; R4 and R5 mean the group: -C-R14(R15)-C-R16(R17)-O-R18(R19)-C-R20(R21)-(Z2) wherein R14, R15, R16, R17, R18, R19, R20 and R21 mean hydrogen atom; G means hydrogen atom, -C(X1)-R30, alkaline metal cation, earth-alkaline metal cation, sulfonium or ammonium cation; X1 means oxygen atom; R30 means hydrogen atom, (C1-C10)-alkyl, and salts and diastereomers of compounds of the formula (I) under condition that R1 and R3 don't methyl group simultaneously; b) effective amount of protective agent (antidote) for prevention of hazard effect of herbicide wherein antidote is taken among the group comprising clochintocet, clochintocet with alkaline metal cation, earth-alkaline metal cation, sulfonium or ammonium cation, clochintocet-mexil, mefenpir, mefenpir with alkaline metal cation, earth-alkaline metal cation, sulfonium or ammonium cation and mefenpir-diethyl, and c) additive comprising (C8-C22)-saturated acids alkyl ester or emulsified vegetable oil, or mineral oil taken in the amount 0.01-2% as measured to the spraying mixture mass. Also, invention describes a method for selective control of weed and grassy plants in cultural plant plantings that involves using the abovementioned composition for treatment. Invention provides the selective effect in control of weed and grassy plants, in particular, in cereals crops plantings.

EFFECT: improved control method, valuable agricultural properties of composition.

3 cl, 8 tbl, 2 ex

FIELD: organic chemistry, chemical technology, medicine, oncology, pharmacy.

SUBSTANCE: invention relates to new derivative of taxane of the formula (I):

that elicits strong antitumor effect. Also, invention relates to intermediates substances, a method for preparing compound of the formula (I), a method for preparing 1,14-β-hydroxy-1,14-carbonate-baccatin III-derivatives substituted with isoserine residue at position 3 and to pharmaceutical composition based on compounds of the formula (I). Invention provides preparing new derivative of taxane that elicits higher activity and reduced toxicity as compared with paclitaxel.

EFFECT: improved preparing method, enhanced and valuable medicinal properties of compound.

10 cl, 7 tbl, 6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of taxane, namely 13-(N-Boc-β-isobutylisoserinyl)-14-β-hydroxybaccatin III-1,14-carbonate of the formula (I): from 10-desacetylbaccatin III for nine stages. Invention provides the effective method for preparing valuable biologically active compound from the more available parent raw.

EFFECT: improved preparing method.

11 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: derivatives of 7-aryl-3,9-diazabicyclo(3.3.1)non-6-ene of general formula I , general formula I, where X and W or both represent -CH-, or one of them represents -CH-, and the other -N. V represents -A-(CH2)s-, -(CH2)s-A-, -A-(CH2)v-B- or -CH2-A-(CH2)3-B-; A and B represent-O- U -phenyl, possibly 1-3 substituted with halogen, alkyl, alkoxy, CF3, CF3O - or alkylcarbonyl, or pyridyl, monosubstituted with cyanogroup. T represents -CONR1-, -(CH2)pOCO- or -(CH2)pN(R1)CO- Q-alkylene; M - hydrogen, phenyl, possibly substituted, benzo[1,3]dioxol, possibly substituted, or pyridyl; L represents -R3, -COR3, -COOR3, -CONR2R3 or -SO2R3; R1 - hydrogen, alkyl, C3-7 cycloalkyl, pyrrolidinyl, benzo[b]thienyl, chinoxalinyl, phenylalkyl, thienylalkyl or tetrazolylalkyl, possibly substituted. m=1, n=0 or m=0, n=1, p - integer 1-4, s - integer 2-5, v - integer 2-4, optically pure enantiomers, mixtures of enantiomers, pharmaceutically acceptable salts and complexes with solvents, possessing activity of phenin inhibitors.

EFFECT: efficient application in medicine for treatment of cardio-vascular diseases and renal failure.

8 cl, 743 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to methods for synthesis of bicyclo[3.1.0]hexane derivatives, used as mGIuR agonists having formulae ,

, where R1 and R2 represent hydrogen, X is a halogen, R3 is -O-Ra , Ra is C1-10alkyl, and R4 is (1) hydrogen or (2) Si-(R9)(R10)(R11), where each of R9, R10 and R11 is C1-10alkyl, as well as intermediate compounds obtained when realising the said methods.

EFFECT: design of an efficient method for synthesis of bicyclo[3,1,0]hexane derivatives.

26 cl, 17 ex, 1 tbl

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