PL157468B1 - Pesticide - Google Patents

Abstract

A method for producing new ditiane derivatives defined by the general formula 1, where m and n signify independently 0.1 or 2, R<1> stands for C2-C9-alkinyl which may possibly be substituted by C1-C4-alkoxyl or tri(C1-C4-alkyl)-silyl or 4 halogen atoms; C2-C10-alkenyl possibly substituted by 2, 3 or 4 halogen atoms; C4-C12-alkadienyltio group; C1-C10-alkyl possibly substituted by C2-C7-alkynyl, C1-C4-alkoxyl or C1-C4-alkyl-C3-C5-cycloalkyl, or hydroxyl and/or 2 or 3 halogen atoms; C3-C5-cycloalkyl substituted by 2 C1-C4-alkyls and 2 halogen atoms; C5-C7-cycloalkyl possibly substituted by C2-C8-alkynyl, C1-C5-alkoxycarbonyl or hydroxymethyl; pyridyl substituted by ethinyl or a halogen atom; phenyl substituted in positions 3,4 or 5 by 1-3 substituents selected from the group comprising: a halogen atom, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxyl, C1-C4-halogenoalkyltio group, cyanic group, C2-C5-alkynyl possibly substituted by a substituent selected out of a halogen atom, C1-C4-alkylocarbonyloxyl, C1-C4-alkoxylcarbonyl, C1-C4-alkoxyl, tri(C1-C4-alkyl)-silyl or hydroxyl with a possibility of additional substitution in the positions 2 and/or 6 with a fluorine atom; R<1> does not stand for propyl or butyl and R<2> and R<3> stand independently for a hydrogen atom or methyl. The method is distinctive in that the compound defined by the general formula 2 where X stands for SH group and R<2> and R<3> signify as stated above, in the form of a ditiaborine complex with dimethyl sulphite is reacted with a carboxylic acid defined by the general formula 3.<IMAGE>

Description

The subject of the invention is a process for the preparation of new dithian derivatives which exhibit pesticidal, in particular arthropicidal, e.g. insecticidal and acaricidal activity, as well as vermicidal, e.g. nematocidal activity.

Currently used pesticides are effective against some, but not all, pest species. It is also desirable to develop a new type of pesticide as pests tend to develop resistance to any pesticide, and sometimes to any type of pesticide after they are selected or exposed to such pesticides for extended periods of time.

Certain 2-5 dialkylsubstituted dithians have been tested as liquid crystalline materials (see, e.g., Mol. Cryst. Li, Cryst., 131,101), but there are no reports of pesticidal activity of such compounds.

Certain new 2,5-disubstituted dithians have now been found to be pesticidal. These compounds are represented by the general formula 1, wherein m and n are independently 0, 1 or 2, R 1 is C 2 -C 9 -alkynyl optionally substituted with C 1 -C 4 -alkoxy or tri (C 1 -C 4 -alkyl) silyl or 3 halogen atoms, C2-C10-alkenyl optionally substituted with 2,3 or 4 halogen atoms, C4-C12-alkadienyl, C1-C10-alkyl optionally substituted with C2-C-alkynylthio, C1-C4-alkoxylene or C1-C4-alkyl-C3-C5 -cyoalkyl or hydroxy and / or 2 or 3 halogen atoms, Cs-Cs-cycloalkyl substituted with 2 Ci-C4-alkyls and 2 halogens, C5-C - cycloalkyl optionally substituted with C2-C6-alkynyl, Ci-Cs-a .lkoksykarbonylem or hydroxymethyl, ethynyl or pyridyl substituted with halo, phenyl substituted in the pozy157 468 tions 3, 4 or 5 by one, two or three substituents selected from the group consisting of halogen, _Ci-4 haloalkyl, _Ci-C4 -haloalkoxy, _Ci-C4 -chlorowcoalkilotio, cyano, C ^ Cs-alkynyl optionally substituted with a substituent constituting ato m halogen, C1-C4-alkylcarbonyloxy, C1-C4-alkoxycarbonyI, C1-C4-alkoxyalkoxy, C1-C4-alkoxy, tri-(C) -C4-alkyl) silyl or hydroxy and optionally further substituted in the 2-positions and / or 6 a fluorine atom, wherein R ¹ is not propyl or butyl, and R ² and R ³ independently represent hydrogen or methyl.

The term "halogen" denotes a fluorine, chlorine, bromine or iodine atom.

A feature of the process according to the invention is that the compound of the general formula II, in which X represents the SH group and R2 and R3 are as defined above, is reacted in the form of a dithiaborinate complex with dimethyl sulphide with a carboxylic acid of the general formula III in which R ¹ is as defined above, and optionally one or both of the ring sulfur atoms is oxidized or the resulting compound of formula I is converted to another compound of formula I.

The reaction of the compounds of formulas 2 and 3 is carried out in the presence of a reducing agent such as stannous chloride in an inert solvent such as ether, preferably tetrahydrofuran, at a non-extreme temperature, e.g. from -20 ° C to 100 ° C, preferably at 10- 30 ° C.

The complex of dithiaborinan with dimethyl sulfide is prepared from the corresponding dithiol by methods known to those skilled in the art.

It is often convenient to prepare compounds of formula by converting other compounds of formula 1. Examples of such transformations are given below.

(a) When it is desired to prepare a compound of Formula 1 wherein R 1 is C 1 -C 4 alkoxycarbonylethynylphenyl and the other substituents are as defined above, a compound of Formula 1 wherein R 2 ^b is ethynylphenyl is reacted with a C 1 -C 4 alkoxycarbonyl halide ;

(b) When it is desired to prepare a compound of Formula 1 wherein R1 is optionally substituted C2-C6-alkynylphenyl and the remaining substituents are as defined above, a compound of Formula 1 wherein R1 is halogenphenyl is reacted with an optionally substituted C2- C - alkyne.

(c) When it is desired to prepare a compound of formula 1 in which R1 is C2-C-alkynylphenyl and the remaining substituents have the above meanings, a compound of formula 1 in which R2b is tri (C1-C4-alkyl) sihyl-C2 -C - alkynylphenyl, desilylated.

(d) When it is desired to prepare a compound of Formula 1 wherein R 1 is C 1 -C 4 alkylthiophenyl and the remaining substituents are as defined above, a compound of Formula 1 wherein R 2b is haloophenyl is reacted with a di-C 1 -C 4 disulfide. alkyl.

(e) When it is desired to prepare a compound of Formula 1, wherein R 1 is hydroxymethyl-C5-C7-cycloalkyl and the remaining substituents are as defined above, a compound of Formula 1 wherein R 2b is C 1 -C 5 -alkoxycarbonyl-C5-C7 -cycloalkyl is reduced.

(f) When it is desired to prepare a compound of Formula 1 where R1 is ethynyl-Cs-C7cycloalkyl and the remaining substituents are as defined above, a compound of Formula 1 wherein R2b is (halo) 2-C = CH-C5- C7-cycloalkyl is reacted with n-butyl lithium.

(g) When it is desired to prepare a compound of Formula 1 in which the hydrogen on the carbon attached to R 1 is in the equatorial position, the corresponding compound in which this hydrogen is in the axial position is reacted with a strong base.

The compounds of formula I may exist in numerous stereoisomeric forms, and the process of the present invention comprises the preparation and use of the active ingredient of an agent of the invention, both individual conformic and stereoisomeric forms and mixtures thereof. The process of the invention can also prepare radiolabelled compounds of the formula I, especially those in which one of the carbon atoms is 14c or one or more hydrogen atoms are replaced with tritium atoms.

The preferred compounds of formula I in terms of potency and spectrum of activity are: 2 (e) - (4-bromophenyl) -5 (e) --- butyl-1,3-dithian, 5 (e) -t-butyl- 2 (e) - (4-chlorophenyl) 1,3-dithian, 5 (e) -t-butyl-2 (e) - (4-odophenyl) -1,3-dithioate, 5 (e) -t-butyl- 2 (e) - (- ethynylphenyl) -1,3-dithian, 2 (e) - (4-biOmophenyl) -5 (ej) t-butyl-2 (aj) -methyl-1,3 -dithian, 2 (a) - (4-bromophenyl) -5 (e} -t-butyl-2 (e> -methyl-1,3-dithian, 5 (e) -t-butyl-2 (e) - [4- (2-Trimethylsilylethynyl) phenyoyl-1,3-dithian, 5 (e) -t-butyl-2 (e) - (3,4-doublet

157 468 chlorophenyl) -1, 3-1 itthian, 5 (e) -t-butyl-2 (a) - (3., 4-dichlorophenyl) 1,3-dithian, 5 (e) -t- (butyl-) 2 (e) - (4-cyanophenyl) 1,3-dilian, 5 (e) -t-butyl-2 (e) - [4-propyn-1-yl) -phenyl] -1,3-dithian, 5 ( e) -t-butyl-2 (e) (3-trifluoromethylol'enyl) -1,3-dithian, 5 (e) -t-butyl-2 (e) -3,3-dimethylOutin-1-yl) -1,3-dithioate, 5 (e) -t-butyl-2 (e) - (trimethyl] yliioethyn-yo]) 1,3-dithioate, cis-5 (e) -t-butyl-2 (e) - (4-broinophenyl) 1,3-dithian, trans-2 (e) - ('4-bromo-2-fluorophenyl) -5 (e) -t-butyl-1,3-dithian, trans-5 (e ) -t-butyl-2 (e) - (4-trifluoromethylphenyl} -1,3-dithian, trans-2 (e) - [3,5-bis (trifluoromethyl) phenyl-5 (e) -t-butyl -1,3-dithian, trans-5 (e) -t-biityl-2 (e) - (3,4,5-trichlorophenyl) 1,3-dithian, trans-2 (e) 4-bromo-3- chlorophenyl- ^ ej-t-butyyl-1S-dithian, trans-5 (e) -t-butyl-2 (e) - (2,4 - ivuchlorophenyl} - 1,3-dithian, 5 (e) -t -butyio-2 (e) - (3,5-dichk) rophene ^^ Ii ^ oI, 3-dithian, 5 (e) -t-butyl-2 (e) - (2,3,4,5, ó -pentafluorophenyl) -1,3-dithian, 5 (e) -t-butyl-2 (e) - [2-fluoro-4- (trimethylsilylethynyl) phenyl] -1,3-dithioate, 5 (e) -t- bu tylo-2 (e) (4-ethynyl-2-fluorophenyl) -1,3-dithian, 2 (4-bromo-3,5-di ^^^^ rophenyl) -5 (^) - ^ t- ^ l ^ i ^ l: y] i ^^. 1,3-dithian, trans-5 (e) -t-buty'o-2 (e - (4-ethynyl-3-fluo] 0ferlyl] -1,3 -dlthian, trans - 5 (e - t-butyio-2 (e) -Ωuoro-4-trifluoromethylphenyl) -1,3-dithian, Il ^^^ 1,3-dithianyl2 (e) -phenyl-tpropynt2tol, 3- [4- / 5 (e) -t-butyl-1,3-dithianyl-2 (e) -trophenyl-trropin-2-yl, 3- 4- / 5 (e) -tb acetate-1 ^ acetate -dithyanyl2 (methyl e - phenyl propargylate, trans-5 (e) -ttbutyk] t2 (e) -4- {3-2 - netoxyytoxy ypropin-1-yl-phenyl --1,3-dithian, 5 (e) -t-butyl-2 (e - [4- (methoxypropyl 1-yl) phenyl] -1,3-dithioate, 2 (e) - (4-bromophenite-1-t-butyl-egg-methyl) 1,3-dithian, 2 (a) t (4-bromophenyl-5 (e) -t-butyl-5 (a) -methyl-1,3-dithian, 2 (a) t (4-bromophenyl) - 5 (e) ttt-butyl-2 (e), 5 (a) -dimethyl-1,3-dithian, 2 (e) - (4-bromophenyl) t 5 (e) -t-butyl-2 (a), 5 (a --dimethyl-1,3-dithian, trans-5 (e) -t-butylth2 (et (ρentyη-1-yl) -1,3-dithio, cis-5 (e) --- outyl-2 (a ) - propan-1-yl} -1,3-dithioate, transt5 (e) -t-butylth2 (e) - (propyn-1-yl) 1,3-dithioate, cis-5 (e) -t- butyl o-2 (a) - (hexen-1-yn4-yl) -1,3-dithioate, trans-5 (e) -t-butylth2 (e) - (hexene-1-yn4-yl) 1,3-dithian, cis-5 (e) -t-butyl-2 (e) - (pentyn-4-yl) -1,3tdithian, trans-5 (e) tt-butyl-2 (e) t ( hexyn-1-yl) t

1,3-dithian, trans-5 (e) -t-butylth2 (e) - [(E) -3,3,3, -trichloropropen-1-yl] -1,3-dithiane, trans-5 (e ) -t-butyl-2 (e) - (3.3,3-trichloropropyl) -1,3tditian, tran.s ^ eHkbromo-SJ.S-trichloropropen-l-yl-5 (e) -t-butyl-l, 3-dithian, trans-5 (e - t-butyl-2 (e) -methoxy-3-methylobulin-1-yl) -1,3-dithioate, 5 (e) -tbutyl-cyclohexylethenium-1 -dithian, trans-5 (e-tt-butyl-2 (e - (trans-4 (e-tethynylcyclohexyl) 1.3-dithian, cis-5 (e) -t-butyl-2 (a) - (irans-) 4 (e) -ethynylcyclohexyl) -1,3-dithioate, cis-5 (e) -t-butyl-2 (a) (8-chloropyridyl-3) -1,3-dithian, trans-5 (e-tt -buly] o-2 (e) - (2,2-dichloro-3,3-dimethylcyclopropytyl) -1,3-dithioate, 5 (e) -t-butyl-2 (e) t (3.3- dimethylbutyl) -1,3tdithian, ΐrant-5 (e ---- buly] o-2 (e) -3,3tbutyl) -1,3-dithian, cis-Sie ^ t-butyl ^ a ^^ - dimethylbutyl ) 1, ^^ «dithian, 5 (e) -t-butylth2 (e) (3,3-d \ vummtyk) bulen-1-y4o) -k3tditian, trans-5 (e) tt-butyl] -2 ( e) -ln-ethylhexenththin ~ 5-yl) -1,3-dithiothian, 5 (e) -t-butylth2 (e) t (3,3-dimethylbutyl) -5 (a) -methyl o- 1,3-dithian, 5 (e) -t-butyl-2 (a) - | 2- (1-methylcyclorro ryl) ethyl-1,3-dithioate, 5 (e) -t-butyl-2 (e) - [2- (1-methylcyclorororyl) tetyl] -1,3-dithioate, N-5 (ε) - ^ Υίγ1ο-2 (8) - (3,3-dimethylpentyl) -1,3-dithian, transt5 (e) -t-butyl-2 (e) t (3,3tdvumethylpentyl) -1,3-dithian, cis -5 (e) -t-butyl-2 (a) - (3,3-dimethylbulyl]) 1,3tdithian, 5 (e) -t-butyl-2 (e) t (3,3-dimethylbutene-1- yl) -1,3-tdithian, 5 (e) -t-butyl-2 (e) - (2,2-dimethylpropyl) -2 (a) -methyl-1,3t dithian, trans-5 (e) -ttbutyl- 2 (e) -1-methylhexen-2-yn-5-yl) -1,3-dithioate, 5 (e) -t-butylth2 (et (3,3-dimethylbuty'l) -5 (a) -methyl-1 3-dithiane 5 (e} -t-butyl-2 (a) - '[2 - l-methylcyclopropyl) -ethyl] -l, 3tdit tian 5ie _l-yl-2 (e) t2 - l -tnety yocykiopropyl-ethyl-], 3-dithian, cis-5 (e) -t-butyl-2 (aX3,3-dimethylpentyl) -1,3-dithian, trans-5 (e) tt-butyl-2 (e) - (3,3-dimethylpentyl) -1,3-dithioate, 1 (e) -oxide 5 (e) t-butyl-2 (e) - (4-ethynylphenyl) -1,3-dithian, 1 -cis-5 (e) -t-butyl-2 (a) - (2,2-diethylpropyl) 1,3-dithian oxide, 1 (e) -oxide 2 (e) - (4-bromophenyl) -5 (e) -ttbuty'Ίo-1,3-dithian.

The compounds of formula I are capable of controlling pests such as arthropods, e.g. insects and mites, and worms, e.g. nematodes.

The compounds of formula I are used in human and veterinary medicine, public health surveillance and agriculture.

The compounds of formula I are especially valuable for the protection of fields, pastures, plantations, greenhouses, orchards and vineyards, ornamental crops and plantations of trees and forests, e.g. cereals (such as corn, wheat, rice, millet, oats, barley, sorghum) cotton, tobacco, vegetables and salads (such as beans, canola, pumpkin, lettuce, onions, tomatoes and pepper), field crops (such as potatoes, sugar beet, peanuts, soybeans, oilseed rape), sugar cane, grassland and forage crops (such as alfalfa), plantations (such as tea, coffee, cocoa, bananas, oil palms, coconut palms, rubber trees, spices), orchards and groves (such as stone fruit orchards, pome fruit orchards, citrus, kiwi, avocado, mango, olive and hazel groves),

157,468 vineyards, ornamental plants, flowers and shrubs under glass and in gardens and parks, forest trees (both with fleeting leaves and evergreen plants in forests, on plantations, schools, as well as plants grown for medicinal and industrial purposes (such as Compounds of formula I are also valuable as tree preservatives (biomass, felled wood, sawn timber, storage and construction wood) against attack by pilates (e.g. Urocerus) or beetles (e.g. scolytids, platypodids, lyctids, bostrychids, cerambycids, anobiids), termites (e.g. Isoptera) or other pests.

The compounds of formula I also find use in the protection of storage products such as cereals, fruits, nuts, spices and tobacco, whether whole or ground or blended into various products, from attack by butterflies, beetles, mites and spider mites. They are also used to protect animal products such as skin, hair, wool and feathers, both in natural and processed form (e.g. in the form of carpets or fabrics) against moth and beetle attack, and to protect stored meat and fish. against beetles, mites, spider mites and flies.

Compounds of formula I are valuable in controlling public health pests, e.g., cockroaches and ants.

The compounds of formula I are also used to control arthropods or worms harmful to humans and animals, or carriers of human and animal diseases or that spread such diseases, e.g. the aforementioned, in particular for the control of ticks, spider mites, lice, fleas, biting bloodworms, midges and flies, mosquitoes and bugs from the order Hemiptera.

The compounds of formula I are used for the abovementioned pest control purposes, by applying them as such or in dilution form in known manner, i.e. as dipping preparations, spray liquids, mists, varnishes, foams, dusts, powders, aqueous suspensions, pastes, gels, creams, shampoos, lubricants, flammable solids, mats releasing vapors of the active substance, flammable spirals, baits, food additives, powders for suspensions, granules, aerosols, emulsifiable concentrates, suspensions in oil, solutions in oil, pressure-impregnated products , microcapsules, pourable formulations and other standard formulations well known to those skilled in the art.

The biological activity of the compounds of formula I was confirmed by the results of the following tests, in which the numbers of the compounds correspond to the numbering in Tables Ia, Ib and Ib.

Trials with the spray liquid. The activity of compounds of formula I was tested by dissolving the compound in acetone (5%) and then diluting five times with a water / Symperonic mixture (94.5%: 0.5%) to give an aqueous emulsion. The following insects were treated with the prepared solution.

1. Musca domestica. 20 female flies were placed in a cardboard cylinder covered on both sides with gauze. The flies placed in the cylinder were sprayed with a solution of the test compound and after keeping them for 48 hours at 25 ° C. The compounds with the following numbers show activity at concentrations below iOOOppm: 5, 7, i2, 13, i4, i7, 20, 23, 25, 26, 32, 33, 35, 42, 56, 57, 58, 62, 64, 65 66, 78, 88.

Compounds with the following numbers showed activity below 200 ppm: i, 3,4, 6,8,9, ii, i4, i5, i6, 2i, 38, 4i, 50.5i, 75.76, 77, 80, 82, 83, 87-, 89.

2. Sitophilue granarius and Tribolium castanenum. To 10 g of wheat, pre-treated with ml of a solution containing the test compound, 20 adult Sitophilus and Tribolium were added. Mortality was assessed after 6 days of storage at 25 ° C.

In this test, the compounds with the following numbers showed activity against Sitophilus granarius at a concentration below i000 ppm: i, 6.7.8, ii, i6.20.22.34, 35.42.54.57.58.64.65, 66.88, 89.

The compounds of the following numbers showed activity against Sitophilus granarius below 200 ppm in this test: 4, 9, 27, 32, 33, 37, 38, 56, 80, 82, 83, 84, 87.

The compounds with the following numbers showed in this test activity against Tribolium castaneum in a concentration below 200 ppm: 9, 32, 33, 34, 37, 38, 4i, 50.5i, 56, 57, 58, 82.

3. Myzus persicae. 10 adult Myzus were placed on the Chinese cabbage leaf discs. After 24 hours, the discs were sprayed with a solution containing the test compound. Mortality was determined after storage for 2 days at 25 ° C. In this test, the compounds with the following numbers showed activity at a concentration below 1000 ppm: 23,26,27,62,76,77,82, and the compounds with the following numbers showed activity at a concentration below 200 ppm: 4.9, ^2, 54 , 80. '

4. Plutella xylostella. Plutella larvae (7 individuals) were sprayed with a solution containing the test compound and placed on Chinese cabbage leaves, similarly sprayed and allowed to dry. Alternatively, 8-10 Plutella larvae were placed on leaf discs and sprayed with a solution containing ^y m ^b a ^d any harvester. ^L Smiert no ^SC OCEM the ^p rzechow ^y wc ^{Dig its} waniu of ² days at 25 ° C. In this test, the compounds with the following numbers showed activity at a concentration below 100 ppm: 4, 14, 16, 20, 23, 29, 30, 35, 41, 55, 57, 58, 65, 84, 87, and the compounds with the following numbers showed activity at concentrations below 200 ppm: 9, 22, 28, 32, 33, 38, 50, 51, 56, 82, 83.

5. Tetranyus urticae. Leaf discs containing mixed population ^of Tetranychus urticae p ^{r k} ys cyano solution ane ^{b d g} o ^ conjunction compound. Mortality was assessed ^{KDR Sc p} O ^{p k} rzechowywaniu rązków for 2 days at 25 ° C. In this test, the compounds with the following numbers showed activity at a concentration below 1000 ppm: 3, 4, 7, 9, 14, 16, 26, 29, 32, 33, 37, 50, 51, 55, 60.

Additional spray tests.

Further studies were carried out on the biological activity of compounds of formula 1. The compounds were dissolved in acetone (75%) and water (25%) was added. Then the insects mentioned below were sprayed with the solution.

6. Aphis fabae. A mixed population of Aphis fabae was tested on a nasturtium leaf. In this test, the compounds with the following numbers showed activity at a concentration below 1000 ppm: 9.11, 14, 15, 16, 19, 20, 35, 76, 77, 84, 89.

7. Macrosteles fascifrons. Adult Macrosteles fascifrons were tested on wheat germ. In this test, the compounds with the following numbers showed activity at a concentration below 1000 ppm: 9, 19, 20, 35.77.

8. Diabrotica undesimpunctata. Diabrotica undecimpunctata individuals in the post-third instar stage were examined on filter paper. In this test, the compounds with the following numbers showed activity at a concentration below 1000 ppm: 9, 11, 20, 27, 84, 89.

The activity of the compounds of formula I against non-anesthetized female Musca domestica (strain WRL) was demonstrated by topically applying a solution of the test compound in ^b utanone to test insects. ^KDR Miert ^{l p} evaluated POWER to about ^{48 g} odzmac ^{h. The p} rot> ing the compounds of the following seq ^{ę a} c ^s c ^h were active at less than lpg: 1, 3, 4, 5. 6, 8, 9.

The activity of the compounds of formula I against non-anesthetized female Musca domestica (strain WRL) was demonstrated by topically applying a solution of the test compound in ^b ut: anone with piperone butoxide to test insects. Mortality was assessed after ^{48 g} odzmac ^{h. In} addition, the compounds with the following numbers had an activity below 1 pg: 9, 11, 38, 76, 77, 80, 82, 83.

Topical application.

The activity of the compounds of formula I against anesthetized male Periplaneta americana was demonstrated by applying a solution of the test compound in butanone topically to the test insects. ^KDR Miert ^{l th} not evaluated ⁶ dmach ^{p. The p} rot> ing the related ^± zlri of seq ^ę following numbers ^and Cyc ^h with a ^kebab wa ^{s BRIEFINGS} activity of less than 50 pg: 1, 4, 7, 8, 9, 19, 23, 27, 81.

The activity of the compounds of formula 1 against anesthetized male Blattella germanica in subjects ^yk azano ^applying topically to the t> ^y stacked insect roztwfo ^b and ^d ane ^{g ±} about connection Relationship in utanonie ^{b. KDR} miertelność evaluated after 6 days. In this test, the compounds with the following numbers show activity below 5 / g: 4, 5, 9, 26, 27, 33, 37, 38, 41, 50, 51, 56, 57, 58, 78, 82, 83, 87, 88.

The activity of compounds of formula I against immature second stage Meloidogyne was demonstrated by placing a batch of nematodes in a 100 ppm acetone solution of the test compound. Triton Y100 (Supplier-BDH) was used as the wetting agent. The reduction in wrinkling within one minute was assessed after 1 day. In this test, the compounds with the following numbers showed activity in the range of 41-61% at the concentrations of 100, 10 and 1 ppm: 9, 72.

The relationship is illustrated by the following examples.

A ^{visual 1H} - ^nmr mano will wipe ^{y p} y ^y utyciu Bruker AM-2 ⁵⁰ u ^{l b WM} - ³ ° ⁰

157,468 7 deuterochloroform solutions, using tetramethylsilane (TMS) as internal standard and expressed in ppm relative to the TMS signal.

Mass spectra were obtained on a Finnigan 4500 or Hewlett Packard 5985B instrument. Gas chromatography was performed using a Pyc Unicam CCD chromatograph equipped with a 3% OV210 column on a Gas-Chrom Q carrier and a flame ionization detector.

Moreover, the progress of the reaction could conveniently be followed on plastic sheets (40 × 80 mm) previously coated with 0.25 mm thick layers of silica gel with a fluorescent indicator. The chromatogram was run in benzene.

Example i. E-5 (e} -t-butyko2 (e)) (3,3-dimieiycloutene --- yio) -1.3-dian.

A solution of 0.74 g of stannous chloride and 0.5 g of E (3, -3 (dimethibut, enot2-carboxylic acid) in 10 ml of dry THF was stirred under nitrogen while adding 33.2 ml of a 0.2 molar solution of the 5-t complex ( bueylO (1,3,4-dithiaborinate - dimethyl sulfide in THF (J. Org. Chem. 1987, 52 (10), 2114). The solution was stirred at room temperature for 20 hours, then 10 ml of 10% potassium hydroxide was added. and ethyl ether. The ether solution was separated, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to yield an oil. Chromatography on silica and elution with hexane gave 30 mg of Et5 (e) -t-butylth2 (e) - (3,3-dimethyl). ) ylobuten-1-yl) -1,3-diiate.

Other compounds of formula 1, i.e. compounds of formula Ia (Table 1A) and 1b (Table IB) were prepared analogously. The symbols (a) and (e) in the column giving the meaning of R ¹ denote the axial and equatorial position, respectively, of the hydrogen atom bonded to the carbon atom substituted with the R 1 substituent.

Table I A

Relationship number R1 Isomer ratio (0 (H) AND 2 3 AND (c) -4- weapon.funny _and l, (a) -H Ί (e) -4-chlorophenyl, (a) -H 3 (e) -4-iodophenyl, (a) -H 4 (e) -4-ethynylphenyl, (e) -H 5 (e) -4- (2-trimethylsilylethyl) phenyl, (a) -H 6 i) (e) -3,4-dichlorophenyl, (a) -H n) (a) -3,4-dichlorophenyl, (e) -H 7 (E4-cyanophenyl, (a) -H 8 (e) -trifluoromethylphenyl, (a) -H 9 (e) -3,3-dimethylbutin-1-yl, (a) -H 10 (e) -trimethylshlethynyl, (a) -H II (e) -4-bromo-2-fluorophenyl, (a) -H 12 (e) -4-trifluoromethylphenyl, (a) -H 13 (e) -3.5-bis (trifluoromethyl) phenyl, (a) -H 14 (e) -3 ₎ 4,5-Trio-chloro-phenyl, (a) -H 15 (e) -4-bnomo-3-chlorophenyl, (a) -H I6 (e) -2,4-dichlorophenyl, (a) -H 17 (e) -3,5-dichlorphenyl, (a) -H 18 (e) -4-methoxyphenyl, (a) -H 19 (e) -2,3,4,5,6-pentafluorophenyl, (a) -H twenty i) (e) -4-bromo-3,5-dichlorophenyl, (a) -Hu) (a) -4-bromo-3,5-dichlorophenyl, (e) -H 2 1 21 (e) H 2 -fluono-4-trifluoromethylphenyl, (a) -H 22 (ep4- (3-hydroxypropin-1-yl) phenyl, (a) -H 23 (e} -4- (3-acetoxypropγn-1-yl), (a) -H 24 (e? 5-chloro-2-fluorophenyl, (a) -H 25 (a ^^ - biocoyfluoromethylphenyl, (a) -H 26 (e) -4- 3- (2-ιηεΚ.Α5γε ^ 5γ) ρΓορρ · | [| - 1-yl phenyl, (a) -H 27 (e) -4- (3-methoxypropin-1-> 1) phenyl, _r (a) -H 28 i) (e) -pentin-1-yl, (a) -H u) (a) -pentin-1-yl, (e) -H 2.1 29 (α-propyn-1-yl, (e) -H thirty (e) -propyn-1-yl, (a) -H 31 (a) -pentyn-1-yl, (e) -H 32 (a) -E-hexen-1-yn-5-yl, (e) -H 33 (e) -E-hexene-1-yn-5-vl (e) -H

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1 2 3 34 i) (e> pentyn-4-yl, (a) -H ii) (a) o * ntyn-4-yl, (e> H 1: 1 35 (e> heluyn-S-yl, (?> H. 36 i) (e) -butyn-1-yl, (?> H ii) (a) -butyn-1-yl, (c> H 37 (e ^^^ - trichloroproipm-1-yl, (a) -H 38 (e) -3,3,3-triehloropropyl, (a), H. 39 (e> 1-bromo-3,3,3-trichloropropene 1 -yl, (?> H. 40 (e ^^. ^ triiCiloropropin-I-yl, (a) -H 41 (e> methoxy-3-methylbutin-1-yl, (a) -H 42 i) (e> cyclohexylethynyl, (?> H. ii) (a) -cyclohexylethynyl, (e> H 43 i) (e) -3-methylbutyl, (?> H. ii) (a) -3 * methylbutyl, (e) -H 5: 4 44 i) v:) - 2-methylpropyl, (a) -H ii) (a) -2-methylpropyl, (e> H. 10: 7 45 i) (e) -heptyl, (?> H. ii) (α> -heptyl, (e) -H 1: 1 46 i) (e) -pentyl, (?> H. ii) (α> pentyl, (e> H. 1: 1 47 i) (e> 2,6-dimethylheptadien-1,5-yl, (a) -H ii) (a) -2,6-dimethylheptadien-1, S-yl, (e) -H 1: 1 48 i) (e) &lt; nt &gt; nt (&lt; n-1-yl, (a) -H ii) (a) -C ^ and ^ TH ^ n-1-yl, (e) -H 1: 1 49 i) (e) -pcntadi &lt; 1 &gt; and * 1,3-yl. (a> H. ii) (a) -pentaden-1,3-yl, (e) -H 1: 1 50 (e> trans-4 (e) -ethynylcyclohexyl, (?> H Si (a) -traiu-4 (e) ethynylGcyclohexyl, (e) -H 52 (e > &gt; -yklohelayl, (a) -H 53 (e) -346chloropyridyl, (a) -H 54 (α> 3- (6-chloropyridyl), (e) -H 55 i) (e) -2,2-dichloro-3,3-dimethylcyclopropyl, (a) -H ii) (a) -2,2-dichloro-3,3-dimethylcyclopropyl, (e) -H 1: 2 56 (e> 3,3-dimethylbutyl, (?> H. 57 i) (e> 3,3-dimethylbutyl, (a) -H ii) (a) -3,3-dimethylbutyl, (e) -H 1: 1 58 (e) -3,3-dimethylbusein-yl, (?> H. 59 i) (α> 2,2-dimethylpropyl, (e> H ii) (α> 2'-dimethylpropyl, (e) -H 7: 3 60 i) (e) -2,2-dimethylpropyl, (?> H. ii) (α> 2,2-dimethylpropyl 3: 2 61 i) (e) -butyn-3-ylthiomethyl, (e) -H ii) (a) -butyn-3-ylthiomethyl, (e) -H 3: 2 62 i) (e) -E-1-methylhekMml-yn-5-yl, (a) -H 63 i) (e) -3,3-dimethyl-4-methoxybutyl, (a) -H ii) (? JF-dimethyl? -methoxybutyl, (e? H 3: 5 64 i) (¢) -2- (1-methylcyclopropyl yethyl, (a) -H ii) (α> 2- (1-nMrhyl-cyclopropyl) ethyl, (e> H 1: 1 65 i) (e> 3,3-dimethylpentyl, (o> H. ii) (a) -3,3-dimethylpentyl, (e) -H 4: 3 66 (e > 3,3-Dimethylpentyl, (o) -H 67 (e) -2chloro-4-fluorophenyl, (o) -H 68 i) (eMA-dimethylpentene-yl, (a) -H ii) (a) ι4,4ιd dimethylpentene-2-yl, (e> H 20: 1 69 i) E-3,3 ^ wi ^^ t] ^ llDlbi ^ laml-yl, (a) -H ii) E-3,3-diipyrite <O> uteml-yl, (e) -H 2: 1 70 i) (e) -2,3,3-trimethylbutyl, (a) -H ii) (a) -2,3,3-trimethylbutyl, (e) -H 3: 2 71 (e) -4-methoxycarbonylphenyl, (o) -H 72 i) (e) -transι4- (e) -ctynyto ¢ yklohexyn, (o) -H ii) (αJ-irans-ecetinylcyclohexyl, (e) -H 1: 1 73 (eH-trinornomethoxyphenyl, (e) -H 74 (e) -4-trifluoromethylthiefenyl, (o) -H 75 (e) -bromophenyl, (o> -H (a) -Me 76 (e) -4-bromophenyl, (a) -H H. 77 (α 2 bromophenyl, (e> H. H. 78 (e) -3,3-dimethylbutyl, (?> H. H. 79 4-bromophenyl, H. Me

157 468 9

The following Examples 11 - illustrate the preparation of compounds of Formula 1 from other compounds of Formula 1.

Example II. Methyl 2- [4- (5 (e) -t-butyl-1,3-dithianyl-2- (a) -phenyl] butyne-1-carboxylate.

To 113 µl of N-isopropylcyclohexylamine in 8 ml of dry THP under nitrogen at 0 ° C was added 431 1.6 ml of n-butyllithium over 5 minutes. The mixture was stirred for 20 minutes at 0 ° C and then cooled to -70 ° C. A solution of 200 mg of 5 (e) -t-butyl-2 (e)) ethynyl-4) phenyl-1,3-dithian in 6 ml of THF was added over 5 minutes. The mixture was stirred for a further 10 minutes at -70 ° C. Then 70 µl of pure methyl chloroformate was added to the reaction mixture and the reaction mixture was stirred overnight at 20 ° C. The reaction mixture was poured into water and extracted with two 25 ml portions of ether. The ether extracts were dried over anhydrous magnesium sulfate. Evaporation of the ether extracts gave a solid which was purified by chromatography on silica eluting with ether: hexane 1: 4.

Example III. 5 ^^ - Butyl-2 (e) - (4- ^ r <^ I ^ j ^^ - 1-ylph ^; ^ 1 ^ o) ^ 1 ^ 3-dit ^ an.

0.19 g of 5-t-butyl-2 (e) - (4-iodophenyl) -1,3-dithian was mixed in 20 ml of dry diethylamine with about 20 mg of bis (triphenylphosphine) palladium dichloride and about 8 mg of cuprous iodide until complete dissolution, and then bubbled through the propyne mixture for 1 hour. The flask was then capped and the contents stirred for another 3 hours. After concentration, the residue was dissolved in dichloromethane and washed with 2 portions of 10 mt of water. The wash solution was extracted with dichloromethane and the combined organic layers were dried over anhydrous magnesium sulfate and concentrated. The product was purified by chromatography on silica, eluting with 1: 1 hexane: dichloromethane and recrystallizing from hexane-benzene. 0.117 g of product was obtained.

5 (e) -t-butyl-2 (e) -2-fuoro-4-trimethylsilylethynylphenyl) -1,3-dithian and 5 (e)) -butyl-2-e) -3- fluoro-4-trimethylsilyloyo) ynylphenyl) -1,3-dithiate from trimethylsilylacetylene and 5 (e) --- butyl-2 (e) -2-fuoro-4-iodophenyl) -1.3 - <^, respectively itian and 5 (e) -t-butyl-2 ()} - 3-Ωuoro-4-odophenyl) -1,3-dithian.

Example IV. 5 (e) -t-Butyl - (eH2-Fluoro <4e) ynyl)) 1,3-dithian.

0.146 g of 5 (e) -1-butyl-2 (e) -2-fluuro-4-hylosillioe) ynylphen-yo)) 1,3-dithian was dissolved in 20 ml of dry tetrahydrofuran under a nitrogen atmosphere. 0.7 ml of a 1M solution of n-tetrabutylammonium fluoride in 0.7m THF was added and stirred for 1.5 hours. Dissolve & Dodge was removed under vacuum. After crystallization from hexane, 0.12 g of the above compound was obtained as a white solid.

5 (e) -t-Butyl - (e) - 3-fuor (o-4 e) ynylphenyl)) 1,3-dithio was also obtained by the above method.

Example 5 5 (e)) 1-Butyl- (e)) - (4-) yynlphenyl) -1,3-dithian 1-oxide.

A solution of 280 mg of 5 (e) -t-butyl-2 ()) - (4-e) ynylphenyl) -1,3-dithian and 440 mg of n-tetrabutylammonium periodic acid in 10 ml of dry chloroform was heated to reflux under nitrogen atmosphere within 12 hours. Water was added and the solutions were separated. The organic solution was washed with brine, dried over anhydrous magnesium sulfate and evaporated in vacuo to give a solid. After crystallization from ethanol, 190 mg of 5 (e) -t-butyl-2 (e) (4-) ι [; ^ ι ^: ^ 1 <^ ιΓ) ι ^; ^ 1ο) -1-oxide were obtained -dithian.

5 (e) -t-butyl-2 (e)) - (4-bromophenyl)) 1,3-dithian-1-oxide was obtained analogously.

Example VI. 5 (e) -t-Butyl- ()) - 3,3-dimethylbutyn-1-ylo) -1,3-dithian.

A solution of 200 µl of diisopropylamine in 10 ml of dry THP was cooled to 0 ° C and stirred under nitrogen atmosphere by adding 1 ml of a 1.6M solution of n-butyllithium in hexane. After 10 minutes, a solution of 300 mg of 5 (e) -t-butyl-2 (e) - (3,3-iwume) ylbutin-1-yl) -1,3-dithian in 10 ml of dry THF was added. After 30 minutes, water, dilute hydrochloric acid and ether were added, the solutions were separated and the organic phase was washed with brine, dried over anhydrous magnesium sulfate and evaporated. Chromatography on silica, eluting with hexane: ether 19: 1, gave 162 mg of the title compound. The following compound was prepared by working in an analogous manner: 5 (e) --- butyl - (a) - 4-bromophenyl)) 1,3-dithioate.

Example VII. 5-t-Butyl- (3,3-dimethyl) ylbutyyl-1-yl} -1-oxide.

0.46 g of 5-t-butyl-2- (3,3-dim) butyn-1-yl) -1,3-dithian, 10 ml of acetic acid and 200 µl of 30% hydrogen peroxide was stirred overnight at room temperature. The solution was evaporated to

157,468 dry and the product was crystallized from hexane to give 70 mg of the title compound. 5-t-Butyl-2- (3,3-dimethylbutyn-1-yl) 1,3-dithian trioxide and tetroxide were prepared in a similar manner.

Example VIII. 5 (e) -t-Butyl-2 (e) - (4th lotion and o) -1,3-dithian.

2.26 ml of a 1.6M solution of n-butyllithium in hexane was added to a solution of 1.0g of 5 (e) -t-butyl-2 (c) (4-bromophenyl) -1,3-dithian in 50 ml of dry THF. stirred under nitrogen at -20 ° C. After 1 hour, 0.51 g of methyl disulfide in 5 ml of dry THF was added and the mixture was allowed to warm to 20 ° C. Saturated sodium chloride solution and chloroform were added and the solutions were separated. The aqueous phase was extracted with chloroform and the combined organic extracts were dried over anhydrous magnesium sulfate and evaporated in vacuo to yield an oil. Chromatography on silicones, eluting with ether: hexane 1:10, gave 38 mg of 5 (e) -t-butyl-2 (e) - (4-methylthiophenyl) -1,3-dithian.

Example IX. A mixture of 5-t-butyl-2 [((4-propyn-1-yl) cyclohexyl] -1,3-dithiate with 5-t-butyl-2-methyl-2 - [(4-propyn-1-yl) - cyclohexyl] -1,3-dithian.

0.94 ml of a 1.6 M solution of n-butyl'lithium in hexane was added at 0 ° C under nitrogen to a solution of 105 mg of 5-t-butyl-2- (4-ethynylcyclohexyl) 1,3-dithian in 10 ml of dry THF. After stirring for 10 minutes, 117 µl of methyl iodide was added. The reaction mixture was stirred for 3 hours. Water was added and the organic layer was washed with brine. After drying over anhydrous magnesium sulfate, the solvent was removed to yield a crude product. Chromatography on silica, eluting with 10% ether in hexane, gave a mixture of 5-t-butyl-2- [4- (propyn-1-yl) cyclohexyl] -1,3-dithian with 5-t-butyl-2-methyl- 2- [4-propyn-1-yl) cyclohexyl] -1,3-dithian.

The structures of compounds of formula 1c and methods for their synthesis from dithian precursors are given in Table 1C.

Table 1C

Number relationship R1 in n Isomer ratio (> (H) Methods of synthesis from the pics 80 (a) -4-bromophen; l, (e) -H 0 0 VI 81 (e) -2-fluoro-4 (trifluoromethylsilylethyl) phenyl! (a) -H 0 0 III 82 (a) -2-fluoro-4-ethynylphenyl, (a) -H 0 0 IV 83 (e) -3-fluoro-4-ethynylphenyl, (a) -H 0 0 IV 84 (e) -4- (2-methoxycarbonylethynyl) phenyl, (a) -H 0 0 II 85 (e) -4-methylthiophenyl, (a) -H 0 0 VIII 86 (a) -3.3-dimethylbutyn-1-yl. (e) -H 0 0 VI 87 (e) -4-ethynylphenyl, (a) -H l 0 V 88 i) (e) -3,3-dimethylqbutyn-1-yl, (a) -Hu) (a) -3,3-dimethylbutyn-1-yl, (e) -H AND 0 l 9 VII 89 (e) -4-bFomophenyl, (a) -H l 0 V 90 i) (e) -3,3-dimethylbutyn-1ryl, (a) -H 2 2 I and VII u) (a) -3,3-dimethylbutyn-1-yl, (e) -H 2 2 91 (e) -4-propyn-1-yl) tenyl, (a) -H 0 0 III

The analysis of NMR spectra and the properties of the compounds of formula 1 are given in Tables 2 and 3.

Table 2

Relationship number 'HNMR spectra made in CDC1 ₃ 1 expressed as ppm relative to the TMS signal / number of protons, signal fold, J value in Hz 10 of the proton from which the signal comes l 2 and 0.99 (9H.s, -CMe ₃ ), 1.73 (1H, mp, J 11.5 and 2.5 Hz, 5-H), 2.86, (2H, dd, J 14 and 11.5 Hz, 43 6-Ha), 2.99 (2H, dd, J 14: 2.5 Hz, 4 and 6-Η "), 5.08 (1H, s, 2-Ha), 7.38 ( 2H, d, J 7Hz, ArH). 7.49 (2H, d, J 7Hz, ArH) 2 0.97 (9H, s, -CMe3), 1.74 (1H, mp, J 11.5 1 2.5 Hz, 5-Ha), 2.83 (2H, dd, J Mt 11.5 Hz, 4 1 6-Ha), 2.98 (2H dd, J 14 1 2.5 Hz, 4 1 6-H _e ), 5.1 (1H, s, 2-Ha), 7.30 (2H, d , J 7Hz, ArH), 7.41 (2H, d J 7Hz) 3 0.93 (9H, s, -CMe3). 1.76 (1H, mp, J 11.5, 12.5 Hz. 5-Ha), 2.84 (? H, dd, J 14 1 11.5 Hz, 4 1 6-Ha), 2.95 (2H, dd, J 14 1 2.5 Hz, 4 1 6-Η »), 5.08 (1H, s, 2-Ha), 7.14 (2H, d, J 7Hz, ArH), 7.68 (2H, d, J 7Hz, ArH)

157 468

1 2 4 0.98 (9H, s, -CMe3), 1.78 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha), 2.84 (2H, dd, J 14 and 11.5 Hz , 4 and 6-Ha), 2.98 (2H, dd, J 14 and 2.5 Hz, 4 and 6-He), 3.07 (1H, s, -CCH), 5.10 (1H, s, 2-Ha), 7.45 (4H, m, ArH) 5 0.23 (9H, s, -SiMe ₃ ), 0.96 (9H, s, -CMe ₃ ), 1.77 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha). 2.83 (2H, dd, J 14 and 11.5 Hz, 4 and 6-Ha), 2.98 (2H, dd, J 14 and 2.5 Hz, 4 and 6-Ha), 5.10 ( 1H, s, 2-Ha), 7.40 (4H, s, ArH) 6 i) 0.94 (9H, s, -CMe3), 1.79 (1H, mp. J 11.5 and 2.5 Hz, 5-Ha), 2.82 (2H, dd, J 14 and 11, 5 Hz, 41 6-Ha), 2.94 (2H, dd, J 14 and 2.5 Hz, 4 and 6-He), 5.04 (1H, s, 2-Ha), 7.27 (1H , dd, J 7 & 1.5Hz, ArH), 7.40 (1H, d, J 7Hz, ArH), 7.58 (1H, d, J 1.5Hz, ArH) ii) 0.86 (9H, s, -CMea), 1.79 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha), 2.55 (2H, dd, J 14 and 11, 5 Hz, 4 and 6-Ha), 2.70 (2H, dd, J 14 and 2.5 Hz, 4 and 6-Ha), 4.77 (1H, s, 2-Ha), 7.34 ( 1H, d, J 7Hz, ArH), 7.61 (1H, dd, J 7 and 1.5 Hz, ArH), 7.89 (1H, d, J 1.5 Hz, ArH) 7 0.98 (9H, s, -CMe3), 1.76 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha), 2.83 (2H dd, J 14 and 11.5 Hz, 4 and 6-Ha), 3.00 (2H, dd, J 14 and 2.5 Hz, 4 and 6-Ha), 5.15 (1H, s, 2-Ha), 7.55 (2H, d, J 7Hz, ArH), 7.65 (2H, d, J 7Hz, ArH) 8 0.95 (9H, s, -CMe3), 1.80 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha), 2.85 (2H, dd, J 14 and 11.5 Hz , 4 and 6-Ha), 3.00 (2H, dd, J 14 and 2.5 Hz, 4 and 6-H ') 5.20 (1H, s, 2-Ha), 7.45 (1H, t, J 7Hz, ArH), 7.56 (1H, d, J 7Hz, ArH), 7.56 (1H, d, J 7Hz, ArH), 7.72 (1H, s, ArH) 9 0.99 (9H, s, -CHMe3), 1.2 (9H, s, CCMe3), 1.79 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha); 2.7 (2H, dd, J 14 and 11.5 Hz, 4 and 6-Ha) 2.28 (2H, dd, J 14 and 11.5 Hz, 4 and 6-Ha), 4.80 (1H, s, 2-Ha) 10 0.20 (9H, s, SiMe3), 0.95 (9H, s, -CMe3), 170 (1H, mp, J 10 and 3.5 Hz, 5-Ha), 2.70 (2H, dd, J 10 and 14 Hz, 4 and 6-Ha), 2.90 (2H, dd, J 3.5 and 14 Hz, 4 and 6-He), 4.85 (1H, s, 2-Ha) 11 0.9 (9H, s, -CMe3), 1.8 (1H, mp, 5-Ha), 2.8 (4H, m, 4/6-Ha * e), 5.4 (1H s. 2 -Ha). 7.2 (2H, m, Ar-H), 7.5 (1H, t, Ar-H) 12 0.9 (9H, s, CMe 3), 1.8 (1H, mp, 5-Ha). 2.8 (4H, m, 4/6-Ha-a), 5.2 (1H, s, 2-H.), 7.6 (4H, s, Ar-H) 13 0.9 (9H, s, -CMe 3), 1.8 (1H, mp, 5-H.), 2.8-3.1 (4H, m, 4/6-Ha * e), 5.2 (1H, s, 2-Ha), 7.8 (1H, s, Ar-H), 8.0 (2H, s Ar-H) 14 0.9 (9H, s, -CMe ₃ ), 1.6 (3H, s, 2-Me), 1.7 (1H, mp, 5-Ha), 2.3 (2H, dd, 4 / 6-Ha), 2.7 (2H, dd, 4/6-H.), 7.6 (1H, d, Ar-H), 8.0 (1H, d, Ar-H), 8.3 (1H, d, Ar-H) 15 0.9 (9H, s, -CMe3), 1.7 (1H, mp, 5-Ha), 2.7-3.1 (4H, m, 4/6-H. *.), 5.5 (1H, s, 2-Ha), 7.2 (1H, m, Ar-H), 7.4 (1H, s, Ar-H), 7.6 (1H, d Ar-H) 16 0.9 (9H, s, -CMe ₃ ), 1.8 (1H, mp, 5-Ha), 2.7-3.1 (4H, m, 4/6-H. *.), 5. 1 (1H, s, 2-Ha), 7.2 (1H, dd, Ar-H), 7.6 (2H, dd, Ar-H) 17 1.0 (9H, s, -CMe3), 1.75 (1H, tt, 5-Ha), 2.82 (2H, dd, 4/6-Ha), 2.98 (2H, dd, 4 / 6-He), 5.04 (1H, s, 2-Ha), 7.3 (3H, m, Ar-H) 18 0.98 (9H, s, -CMe3), 1.75 (1H, mp, 5-Ha), 2.84 (2H, dd, 4/6-Ha), 2.97 (2H, dd, 4 / 6-He), 3.8 (3H, s, OMe), 5.11 (1H, s, 2-H.), 6.87 (2H, m, Ar-H), 7.41 (2H, m, Ar-H) 19 10 (9H, s, -CMe3), 1.85 (! H, tt, 5-Ha), 2.89 (2H, dd, 4/6-Ha), 3.02 (2H, dd, 4/6-Ha), 5.5 (1H, m, 2-Ha) twenty 0.9 and 0.99 (9H, s, -CMe3), 1.74 and 1.86 (1H, mp, 5-H), 2.5-3.1 (4H, m, 4/6-Ha *.), 7.89 (2H, s, Ar-H) 21 0.9 (9H, s, -CMe3), 1.7 (1H, mp, 5-Ha), 2.8-3.0 (4H, m, 4/6-H. *.) 5.5 (1H, s, 2-Ha), 7.3 (1H, d, Ar-H), 7.4 (1H, d, Ar-H), 7.7 (1H, t, Ar-H) 22 0.9 (9H, s, CMe3), 1.8 (1H, mp, 5-Ha), 2.8-3.0 (4H, m, 4/6 -H _o "), 4.5 ( 2H, d, CH2O), 5.2 (1H, s, -OH), 7.4 (4H, s, Ar-H

157 468

AND 2 23 0.9 (911, s -CMea), 1.8 (1H. U, 5-Ha), 2.2- (3H, s, COMe), 2.8-3.0 (4H. M, 4 (6-Haly), 4.8 (2H, s, CH ₂ O), 5.2 (1H, s, 2-Hah), 7.5 (4H, s, Ar-H) 24 0.9 (9H, s, -CMe ₃ ), 1.7 (1H, mp 5-Ha). 2.8-3.0 (4H, m. 4/6-Ha.e), 5.5 (IH. S. 2-Ha). 7.0 (1H.dd. Ar-H) 7.1 (1H.dd, 4r-H). 7.7 (1H. Dd Ar-H) 25 0.9 (9H, s -CMes), 1.8 (1H, mp, 5-Ha), 2.8-3.1 (4H, m, 4/6-Ha-a). 5.4 (1H, s, 2-Ha), 7.8-8.2 (3H, m, Ar-H) 26 0.9 (9H, s, -CMe ₃ ), 1.7 (1H; mp, 5-Ha), 2.8-3.0 (4H, m, 4/6-Ha ",), 3.4 (3H , s, OMe), 3.6 (2H, m, OH2O), 3.7 (2H, m, OCH2), 4.4 (2H, s -C-CH2O), 5.1 (1H, s, 2-Ha), 7.4 (4H, s, Ar-H) 27 0.98 (9H, s, -CMeo), 1.80 (1H, mp, 5-Ha), 2.8-3.9 (4H, m, 4/6-H), 3.45 (3H, s, OMe), 4.30 (2H, s, CH2O), 5.12 (1H, s, 2-Ha), 7.40 (4H, s, Ar-H) 28 0.9 (12H, m, -CMea and -Me), 1.4-1.6 (2H, m, -CH2), 1.7 (1H, m, 5-Ha), 2.2-3, m, 2-7-9 (4H, m, 4/6-Ha ",), 4.3 and 4.8 (1H, s, 2H) 29 0.9 (9H, s, -CMe3), 1.75 (1H, mp, 5-Ha), 1.95 (3H, s, 2E-Mea), 2.7 (2H, dd, 4 / 6- He), 3.15 (2H, dd, 4/6-Ha), 4.3 (1H, d, 2-H ") thirty 0.9 (9H), s, -CMe ₃ ), 1.7 (1H, mp, 5-Ha), 1.85 (3H, s, 2 - = - Me3), 2.75 (4H, m, 4 / 6-Ha + e), 4.8 (1H, d, 2-Ha) 31 0.9 (9H, s, -CMea), 1.0 (3H, t, Me), 1.5 (2H, m, -CH2), 1.6 (1H, mp, 5-Ha), 2.3 (2H, dt, 2 - = - CH2a). 2.7 (2H, dd, 4/6-He), 3.2 (2H, dd, 4 / 6Ha), 4.4 (lH, s, 2-Ha) 32 0.9 (9H, s, -CMe3), 1.7 (1H, tt, 5-Ha), 2.0 (1H, t, = CH), 2.3 (4H, m, CH2X2), 2. 6 (2H, dd. 4/6-He), 2.8 (2H, dd, 4/6-Ha). 4.1 (1H, d 2-Ha), 5.9 (2H, m, -CH = CH-) 33 0.9 (9H, s, -CMe3), 1.6 (1H, tt, 5-Ha), 2.0 (1H, t, = -CH), 2.3 (4H, m, CH2X2), 2 , 75 (4H, m, 4/6-Ha), 4.6 (1H, d, 2-Ha), 5.7 (1H, dd, -C-H). 5.95 (1H, dt, = C-H) 34 0.95 (9H, s, -CMe3), 1.7 (5H, m, 5-H / 2 xCH _2), 1.9 (1H, s, = CH), 2.3 (2H, m, CH2), 2 , 7 (4H, m, 4 / 6-11 ",) 3.5 and 4.1 (1H, m, 2-H) 35 0.9 (9H, s, -CMea), 1.7 (7H, m, 5-H "and 3 X CH 2), 1.9 (1H, m, = CH). 2.2 (2H, m, CH2), 2.7 (4H, m, 4/6-CH2), 4.0 (1H, m, 2-Ha) 36 0.9 and 1.0 (9H, s, -CMea), 1.1 and 1.25 (3H, t, -Me), 1.7 (1H, mp, 5-Ha), 2.3 (2H. m = C-CH2), 2.6-3.4 (4H, m, 4/6-Ha + e), 4.4 and 4.8 (1H, t, 2-H) 37 0.95 (9H, s, -CMea), 1.6 (1H, m, 5-Ha), 2.8 (2H, m, 4/6-Ha), 2.95 (2H, m, 4 / 6-Ha), 4.75, (1H, m, 2-Ha), 6.4 (2H, m, -CH = CH-) 38 0.95 (9H, s, -CMe3). 1.65 (1H, mp, J 11.5 and 2.5 Hz, 5-Ha), 2.2 (2H, m, 2-OH2), 2.7 (2H, dd, J 14.5 11 Hz, 4/6-Ha), 2.9 (4H, m, 4/6-Ha and CH2CC13), 4.1 (1H, t, J 6.5 Hz, 2-Ha) 39 0.95 (9H, s, -CMea), 1.7 (1H, tt, J 11.0 and 2.5 Hz, 5-Ha), 2.8 (2H, dd, J 14.5 and 11 Hz, 4/6-Ha), 3.05 (2H, dd, J 14.5 and 2.5 Hz, 4/6-H ,,), 4.9 (1H, s, 2-Ha), 7.2 (1H, s, = CH-) 40 0.95 (9H, s, -CMea), 1.75 (1H, mp, J 11 and 2.5 Hz, 5-Ha), 2.75 (2H, dd, J 14 and 11 Hz, 4/6-Ha), 2.95 (2H, dd, J 14 and 2.5 Hz, 4/6-He), 4.9 (1H.s, 2-Ha) 41 0.92 (9H, s, -CMea), 1.45 (6H, s, -CMea), 1.70 (1H, tt, 5-Ha), 2.652.90 (4H, m, 4/6-H ), 3.35 (3H, s, OMe), 4.48 (1H, s, 2-Ha) 42 i) 0.9 (9H, s, -CMea), 1.2 -1.8 (11H, m, 5-Ha + cyclohexyl), 2.5-29 (4H) m, 4/6-H) , 2.5-2.9 and 3.2 (1H, dt, cyclohexyl-1H), 4.80 (1H, d, 2-H.) ii) 0.95 (9H, s, -CM3), 1.2-1.8 (UH, m, 5-Ha + cyclohexyl, 2.4-2.9 (4H, m, 4/6-H), 2 , 5-2.9 and 3.2 (1H, m, cyclohexyl-1H), 4.37 (1H, d, 2-He) 43 0.9 (15H, m), 1.4 (2H, m), 1.7 (4H, m), 2.0-2.9 (4H, m), 3.4 and 4.0 (1H, m) 44 0.9 (15H, m), 1.6 (4H, m), 2.0-3.0 (4H, m), 3.5 and 4.1 (1H, m) 45 0.9 (12H, m), 1.2-1.8 (13H, m), 2.0-2.9 (4H, m), 3.4 and 4.0 (1H, m) 46 0.9 (12H, m), 1.4 (5H, m), 1.5 (2H, m), 1.7 (2H, m), 2.0-2.9 (4H, m), 3.44 and 4.0 (lH, m)

157 468

1 2 47 0.9 (9H, m), 1.6 (1H, m), 1.6. 1.65 and 1.7 (9H, s), 2.1 (4H, m), 2.8 (4H, m), 4.8 (1H, d). 5.1 12H, m) LS 0.9 (I2H1 m). 1.4 (2H, m, 1.6 (1H, m), 2.0 (2H, m), 2.8 (4H, m). 4.6 (1H, d, 5.5 and 5.9 (2H, mj 49 0.9 and 1.0 (9H, s), 1.6 (1H, m). 1.8 (3H, m), 2.9 (4H, m), 4.7 (1H, d), 5.5-6.2 (4H, m) 50 0.9 (9H, s, -CMea), 1.3-2.2 (10H, m), 1.65 (1H, u, J 11 and 2.5 Hz, 5-Ha), 2.04 (1H, d, J 2 Hz-CH), 2.65 (2H, dd, J 13.8 and 11 Hz, 4/6 -H ₂ ), 2.91 (2H, dd, J 13 and 7.5 Hz, 4 / 6-Ha), 3.98 (1H, d, J 6Hz, 2-Ha) 51 0.9 (9H, s, -CMea), 1.0-2.28 (10H, m), 1.8 (1H, mp, J 10 and 4 Hz, 5-Ha), 2.05 (1H, d, J 2 Hz, -CH), 2.6 (2H, dd, J 14 and 4 Hz, 4/6-H _e ), 2.8 (2H, dd, J 14 and 10 Hz, 4 / 6- Ha), 3.25 (1H, d, J 9.1 Hz, 2-Ha) 52 0.92 (9H, s, -CMe3), 1.23 (6H, m, cyclohexyl), 1.68 (2H, m, 5-Ha + cyclohexyTl-H), 1.8 (4H, m, cyclohexyl- 2-ClHX2), 2.69 (2H, dd, 4/6-Ha, 2.93 (2H, dd, 4/6-He), 4.0 (1H, d, 2-Ha) 53 0.99 (9H, s, -CMea), 1.75 (1H, tt, 5-H _a), 2.81 (2H, dd, 4/6-Ha), 2.99 (2H, dd, 4/6 -He), 5.16 (1H, s, 2-Ha), 7.35 (1H, d, Ar-H), 8.1 (1H, dd, 4/6-Ha) 8.81 (1H , d, Ar-H) 54 0.99 (9H, s, -CMea), 1.87 (1H, d, 5-Ha), 2.57 (2H, dd, 4/6-Ha), 2.72 (2H, dd, 4 / 6-He), 4.84 (1H, s, 2-He), 7.36 (1H, d, Ar-H), 8.1 (1H, dd, Ar-H) 8.82 (lH, d, Ar-H) 55 0.95 (9H, s, -CMea), 1.25, 1.3, 1.35, 14 (6H, s, 2 X Me), 1.7 (2H, m, 5-Ha and cyclopropyl H), 2 , 8 (4H, m, 4/6-Ha + a), 3.4 and 3.8 (1H, m, 2-H) 56 0.9 (9H, s, -CMea), 0.95 (9H, s, -CMes), 1.45-1.8 (4H, m, 2XCH2), 2.572.95 (4H, m, 4/6 -Ha + a), 3.95 (1H, t, 2-Ha) 57 0.9 (9H, s, -CMea), 0.95 (9H, s, C \ le _3), 1.3-1.8 (4H, m, 2XCH2), 1,952,05 (1H, m, 5 -Ha), 2.7-3.0 (4H, m, 4/6 -H _ar "), 3.3 and 4.0 (1H, t, 2-H) 58 0.9 (9H, s, -CMea), 1.0 (9H, s, CMea), 1.6-1.7 (IH, m, 5-Ha), 2.6-2.9 (4H, m, 4 / 6-Ha + a), 4.6-6.0 (2H, m, 2x = CH) 59 0.8 and 1.0 (18H, s, -CMeaX2), 1.6 (3H, m, 5-H _a + CHa,), 2.1 (2H, d, CHa), 2.6-2, 9 (4H, m, 4/6-Ha + a), 3.65 (1H, t, 2-H- _e ), 4.0 (1H, t, H-2a) 60 0.9 (9H, s, -CMea), 1.1 (9H, s, -CMea), 1.7 (1H, m, 5-H "), 1.85 (2H, s CHa), 1.95 (2H, s, CH2a), 2.3-3.0 (4H, m, 4/6-Ha + a) 61 0.9 (9H, s, -CMea), 1.7 (1H, mp, 5-Ha), 2.1 (1H, t, = C-H), 2.5-3.0 (10H, m, SCH - CH- + 4/6-Ha + β), 3.7 (1H, t, 2-Ha), 4.2 (1H, t, 2-Ha) 62 0.9 (9H, s, -CMea), 1.6 (1H, tt, 5-Ha), 1.8 (3H, d, -C-Me), 2.0 (1H, t, = C-H), 2.4 (4H, m, 2X2), 2.6-2.9 (4H, m, 4/6-Ha + a), 4.6 (1H, s, 2-Ha) 5.8 (1H, t, = C-H) 63 0.88 and 0.94 (15H, s, -CMe ₃ + CMep, 1, -45-1.75 (5H, m, 5-Ha + CH2x2), 2.75 (4H, m, 4 / 6- H), 3.02 and 3.12 (2H, s, CH ₂ O), 3.32 and 3.35 (3H, s, OMe), 3.38 and 3.9) (1H, t, 2-H 64 0.25 (4H, m, cyclopropyl), 0.92 and 1.04 (3H, s, C-Me), 1.0 (9H, s, -CMea), 1.35-2.2 (5H, m, 5-Ha, CH2X2), 2.58-9 (4H, m, 4/6-H), 3.45 and 4.01 (1H, t, 2- H. 65 0.8 (3H, t, Me), 0.80, 0.82 and 0.9 (15H, -CMe ₃ + CMe2), 1.2 (2H, q, CH 2), 1.35 (2H, m, CHp, 1.58-2.0 (3H, m, 5-Ha + CH3, 2.75 (4H, m, 4/6-Ha + a), 3.35 and 3.97 (1H, t, 2- H) 66 0.78 (3H, t, Me), 0.81 (6H, s, -Cme4, 0.9 (9H, s, -CMea), 1.35 (2H, m, CH2), 1.65 (3H, m, 5-Ha + CH), 2.64 (2H, dd, 4/6-Ha), 2.85 (2H, dd, 4/6-He), 3.95 (1H, t, 2-H) 67 1.0 (9H, s, -CMea), 1.8 (1H, t, 5-Ha), 2.9 (4H, m, 4/6-Ha + e), 5.55 (1H, s, 2-Ha), 7.1 (2H, m, Ar-H), 7.6 (1H, m, Ar-H) 68 1.0 (21H, m), 1.1 (3H, m), 1.6 (1H, m), 2.8 (4H, m), 4.0 (1H, m) 69 1.0 (18H, m, -CMeX2), 1.5 (1H, m, 5-Ha), 2.8 (4H, m, 4/6-Ha + a), 4.1 and 4.6 ( 1H, d, 2-H), 5.5 (2H, m, -CH = CH-) 70 0.9 (21H, m), 1.5 (5H, m), 2.7 (4H, m), 3.5 and 4.0 (1H, m)

157 468

1 2 71 1.0 (9Η, s, -CMea), 1.8 (1H, t, 5-Ha), 2.9 (4H, m, 4/6-Ha + e), 4.0 (3H, s, OMe), 5.2 (1H, s, 2-Ha), 7.8 (4H, m, Ar-H) 7? 0.9 (9H, s, -CMea), 1.0-2.3 (12H, m), 2.6-2.7 (2H, m, 4/6-Ha), 2.8-2. 9 (2H, m, 4/6-Ha), 3.25 and 3.98, (UH, d, 2-Ha) 75 1.0 (9H, s, -CMea), 1.8 (1H, t, 5-Ha), 2.9 (4H, m, 4/6-Ha + a), 5.1 (1H, s, 2-Ha), 7.4 (4H, m, Ar-H) 74 0.9 (9H, s, -CMea), 1.8 (1H, t, 5-Ha), 2.9 (4H, m, 4/6-Ha, »), 5.1 (1H, s, 2-Ha), 7.6 (4H, m, Ar-H) 75 0.97 (9H, s, -CMea), 1.40 (1H, m, 5-Ha), 1.70 (3H, d, J 7Hz, 4-Me.), 2.67 (1H, dd , J 10.5 and 4.5 Hz, 6-H- _e ), 2.95 (1H, dq, J 7 and 2.7 Hz, 4-He), 3.25 (1H, dd, J 14 and 10.5 Hz, 6-Ha), 5.70 (1H, s, 2-Ha), 7.45 (2H, d, J 7Hz, ArH), 7.48 (2H, d, J 7Hz, ArH) 76 0.9 (9H, s, -CMea), 1.3 (3H, s, 5-Mea), 2.6 (2H, d, 4/6-Ha), 3.2 (2H, d, 4 / 6-Ηβ), 5.0 (1H, s, 2-Ha), 7.4-7.6 (4H, m, Ar-H) 77 0.8 (9H, s, -CMea), 1.3 (3H, s, 5-Mea), 2.3 (2H, d, 4/6 -H ») 3 and (2H, d, 4/6 -Ha), 5.0 (1H, s, 2-H "), 7.4-7.6 (4H, q, Ar-H) 78 0.9 and 0.95 (18H, s, -CMe ₃ X 2), 1.25 (3H, s, Me), 1.4 (2H, m, CH ₂ ), 1.7 (2H, m, CH ₂ ), 2.45 (2H, d, 4/6-H "), 3.1 (2H, d, 4/6-He), 3.7 (ΙΗ-t, 2-Ha) 79 1.0 and 1.1 (9H, s, -CMea), 1.4 (1H, m, 5-Ha), 1.5 and 1.7 (3H, d, 4-Me), 2.4-3.5 (3H, m, 4/6-H), 5.2 and 5.3 (1H, s, 2-H), 7.4 (4H, m, Ar-H) 80 0.9 (9H, 2, -CMea), 1.8 (1H, mp, 5-Ha), 2.5-9 (4H, m, 4/6-Ha, »), 4.8 (1H, s, 2-He), 7.4 (2H, d, Ar-H), 7.7 (2H, d, Ar-H) 81 0.27 (9H, s, -SiMea), 0.98 (9H, s, CMea), 1.76 (1H, tt, 5-Ha), 2.88 (2H, dd, 4/6-Ha) , 2.99 (2H, dd, 4/6-Ha), 5.48 (1H, s, 2-Ha), 7.2 (2H, tn, Ar-H), 7.56 (1H, m, Ar-H) 82 0.98 (9H, s, -CMea), 1.45 (1H, s, = CH), 1.78 (1H, mp, 5-Hf), 2.89 (2H, dd, 4 / 6- Ha), 2.99 (2H, dd, 4/6-H.), 5.48 (1H, s, 2-He), 7.23 (2H, m, Ar-H), 7.59 (1H, m, Ar-H) 83 1.0 (9H, s, -CMea), 1.45 (1H, m, = CH), 1.79 (1H, tt, 5-Ha), 2.88 (2H, dd, 4/6-Ha ), 2.99 (2H, dd, 4/6-Ha), 5.04 (1H, s, 2-Ha), 7.16 (3H, m, Ar-H) 84 0.9 (9H, s, -CMea), 1.8 (1H, mp, 5-Ha), 2.8-3.0 (4H, m, 4/6-Ha + a), 3.8 ( 3H, s, Me), 5.2 (1H, s, 2-Ha), 7.4-7.6 (4H, dd, Ar-H) 85 0.95 (9H, s, -CMea), 1.75 (1H, mp, 5-Ha), 2.50 (H, s, SMe), 2.75-3.0 (4H, tn, 4 / 6-H), 5.08 (1H, s, 2-Ha), 7.20 (2H, d, Ar-H), 7.50 (2H, dd, Ar-H) 86 0.95 (9H, s, -CMea), 1.3 (9H, s, = C.CM _{; j} ). 1.7 (1H, m, 5-Ha), 2.8 (2H, tn, 4/6-Ha), 4.3 (1H, s, 2-H.) 87 1.0 (9H, s, -CMea), 2.2 (1H, mp, 5-Ha), 2.75 (4H, tn, 4/6-Ha + a), 3.1 (1H, s = CH), 4.5 (1H, s, 2-Ha), 7.45 (4H, m, Ar-H) 88 0.9 (9H, s, -CMea), 1.1 (9H, s, -CMea), 2.1 (1H, m, 5-Ha), 2.5 (4H, m, 4/6-H), 4.2 and 4.6 (1H, s, 2-H) 89 1.0 (9H, s, -CMea), 2.1 (1H, mp, 5-Ha), 2.7 (4H, m, 4/6-Ha + a), 4.4 (1H, s, 2-Ha), 7.3 (4H, tn, Ar-H) '90 0.9 (9H, s, -CMea), 1.2 (9H, s, -CMea), 1.5 (1H, m, 5-Ha), 2.2-3.6 (4H, m, 4 / 6-Ha + a), 4.6 and 5.1 (1H, s, 2-H) 91 1.0 (9H, s, -CMea), 1.7 (1H, m, 5-Ha), 2.0 (3H, s, = CMe), 2.8 (4H, m, 4/6-Ha + a), 5.1 (1H, s, 2-Ha), 7.4 (4H, m, Ar-H)

157 468

Table 3

Relationship number Mass spectrum Chemical ionization Μ -t- 1 M-electron impact t.t.rc) Vol. Sep. (° C) or no Description 1 2 3 4 1 331 150-5 a crystalline body constantly 2 287 162 crystalline solid 3 180 a crystalline body constantly 4 277 149 crystalline solid 5 349 189 the crystalline body becomes 6 321 100-123 crystalline solid 7 146 crystalline body state 8 321 121-123 crystal biate of the state 9 257 143 light yellow crystalline body state 10 273 112 pale yellow crystalline body state 11 349 163 beat your body constantly 12 321 152 biate ciato state 13 389 68 biate ciato state 14 111 biate ciato state 15 144 biate ciato state 16 322 138 biate body state 17 150 light brown ciato state 18 135-6 light brown ciato state 19 140 biate crystals twenty 107-118 light brown ciato state 21 339 155 biate ciato state 22 307 149 biate ciato state 23 349 117 red ciato state 24 150 buff ciato state 25 389 138 white ciato state 26 365 66 biate ciato state 27 321 yellow state 28 243 yellow oil 29 215 84 biate crystals thirty 215 70 yellow crystals 31 203 - yellow oil 32 1.5420 yellow oil 33 1.5467 yellow oil 34 243 15430 yellow oil 35 1.5424 yellow oil 36 225 colorless oil 37 283 143-5 biate ciato state 38 321 128-30 biate ciato state 39 397 108-12 brown ciato state 40 317 145-50 biate ciato state 41 273 94 yellow body constantly 42 283 yellow oil 43 247 115 ° -26.5 Pa 44 233 130 = -106 Pa 45 275 144 ° -26.5 Pa 46 247 122 ° -40 Pa 47 299 48 245 49 243 42-6 ° C colorless body permanently 50 283 134 biate ciato state 51 283 100-2 biate ciato state 52 95-6 biate ciato state 53 165-6 biate ciato state 54 106-7 biate ciato state 55 313 111-23 yellow state 56 261 115 biate ciato state 57 261 101-3 beat your body constantly 58 259 59 247 63 biate ciato state 60 261 51 beat your body constantly 61 275 yellow oil 62 269 yellow oil 63 291 15160 colorless oil 64 259 ciato pótstate

157 468

1 2 3 4 65 275 semi-solid body 66 275 73 white solid 67 - 151 white solid 68 275 42-5 white solid 69 - 100-3 white solid 70 275 71-3 white solid 71 311 166 white solid 72 283 98.7 white solid 73 337 114.2 white solid 74 353 133.7 white solid 75 345 95 light yellow crystalline solid 76 345 155 white solid 77 345 orange oil 78 275 96 white solid 79 331 92 yellow solid 80 174 white crystals 81 116-8 beige solid 82 133-5 white crystals 83 335 169 yellow solid 84 299 167 white solid 85 257 87 buff solid 86 293 221 white solid 87 273 184-8 white solid 88 345 - orange semi-solid body 89 347 176 white solid 90 321 190-3 white solid 91 291 160-1 white solid

Formula 1c

Department of Publishing of the UP RP. Circulation of 90 copies

Price PLN 5,000.

Claims (2)

Patent claims 1. A process for preparing a dithiane having the general formula 1, wherein m and n are independently 0, 1 or 2, ^R1 is C2-alkmyl optionally substituted C 1 -C 4 alkoxy or tri (Ci-C4-alkyl) siliiem or 3 halogen atoms, C2-Cio-alkenyl optionally substituted by 2, 3 or 4 halogen atoms, C'4-Ci2-alkadienyl, Ci-Cw-alkyl, optionally substituted _C2-C7 -alkinylotio, Ci-C4-alkoxy or Ci-C4 -alkyl-C3-C5-cycloalkyl or hydroxy and / or 2 or 3 halogen atoms, C3-Cs-cycloalkyl substituted with 2 C1-C4-alkyls and 2 halogen atoms, C8-C-cycloalkyl optionally substituted with C2-C6-alkynyl, C1-C8-alkoxycarbonyl or hydroxymethyl, pyridyl substituted with ethynyl or halogen, phenyl substituted in the 3, 4 or 5 positions with 1-3 substituents selected from the group consisting of halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1- C4-haloalkylthio, cyano, C ^ ^ Cs-alkynyl optionally substituted with a halogen substituent a, C 1 -C 4 -alkylcarbonyloxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxyalkoxy, C 1 -C 4 -alkoxy, tri (C 1 -C 4 -alkyl) silyl or hydroxy and optionally further substituted at the 2 and / or 6 positions fluorine atom, wherein R1 is other than propyl or butyl, and R ² and R 3 are independently hydrogen or methyl, characterized in that a compound of the general formula 2, wherein X represents SH and R 2 and R 3 are as defined above meaning, in the form of a dithiaborinate complex with dimethyl sulphide, it is reacted with a carboxylic acid of the general formula 3, in which R 1 is as defined above, and optionally one or both of the ring sulfur atoms is oxidized or the resulting compound of the formula 1 is converted into another compound of formula 1. 2. The method according to p. 3. The process of claim 1, wherein R1 is C2-C6-alkynyl optionally substituted with C1-C4-alkoxy, tri (C1-C4-alkyl) silyl or 3 halogen atoms, C2-C6- alkenyl optionally substituted with 2-4 halogen atoms or C2-C6alkyl optionally substituted with C1-C4-alkoxy or hydroxy and / or 2 or 3 halogen atoms.