HUT76814A - Arthropodicidal tetrahydropyrimidines, compositions containing these compounds as active ingredients and use thereof - Google Patents

Description

The present invention relates to tetrahydropyrimidine derivatives and compositions containing such compounds which are useful for the control of arthropods, and to a process for the control of arthropods using such compounds.

U.S. Pat. No. 4,831,036 discloses tetrahydropyrimidines having insecticidal activity, but these compounds are different from those of the present invention.

The present invention thus relates to compounds of formula (I), to all their geometric and stereoisomers, to their agriculturally acceptable salts, and to agricultural compositions containing them and to their use, which are suitable for killing arthropods in both agricultural and non-agricultural environments.

The compounds of the invention are represented by formula (I) wherein X is Si or Ge,

84073-7340 OE / Hoj

A is C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 3 -C 8 cycloalkylene, C 7 -C 10 aralkylene or phenylene, each of which is optionally

It may be substituted 1 to 3 times by a group W, or A may also be a bond,

R ¹ and R ³ are independently H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, or C 2 -C 10 alkynyl, each of which is optionally

Substituted 1-2 times with halogen, CN, C (O) R ⁷ , C (S) R ⁷ , NO ₂ , OH, SC (O) R ⁷ , SC (S) R ⁷ , OC ( O) R ⁷ , OC (S) R ⁷ , NR ⁸ C (O) R ⁷ , NR ⁸ C (S) R ⁷ , SH, Si (R ⁸ ) (R ⁹ ) (R ¹⁰ ), C 1-4 alkoxy,

C 1-4 haloalkoxy, C 1-4 alkylthio,

C 1-4 alkylamino, C 2-8 dialkylamino, C 3-8 cycloalkyl, or

Phenyl substituted with ^{1 to} 3 times W ¹ ; it may further be C3-C8 cycloalkyl, which may be optionally substituted with 1 to 3 times halogen, C1-C2 alkyl or C1-C2 haloalkyl; C (O) R ⁿ ; C (S) R ⁿ ; phenyl optionally substituted 1 to 3 times with W ¹ ; C 1-3 alkyl substituted with a 5- or 6-membered aromatic ring attached through its carbon or nitrogen atom and containing 1-4 heteroatoms selected from 0-4 nitrogen, 0-1 oxygen and 0-1. sulfur and the ring optionally substituted ^{1 to 3 times} with W ¹

- there are 3; and may also be a 5- or 6-membered aromatic ring linked through its carbon or nitrogen atom containing from 1 to 4 heteroatoms selected from the group consisting of 0-4 nitrogen atoms, 0-1 oxygen atoms and 0-1 sulfur atoms and optionally 1 It may be -3 times substituted with W ¹ ;

R ² is H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 2-6 halo alkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl, or C4-C7 cycloalkylalkyl, each of which is optionally

It may be 1 to 3 times substituted with W; obsession

R ² and R ³ together are CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ , each of which may be optionally substituted with 1 to 2 CH ₃ ;

R ⁴ is H or C 3 -C 6 trialkylsilyl or C 1 -C 10 alkyl, C 2 -C 10 alkenyl,

C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, phenyl, phenoxy, phenylthio or naphthyl, each optionally having

It may be substituted 1 to 3 times with W ¹ ;

R ⁵ and R ⁶ are independently C 1-10 alkyl,

C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, phenyl, phenoxy, phenylthio or naphthyl, each of which is optionally 1- 3 times with any W ¹ group

- 4 may be substituted; or OH or C 3-6 trialkylsilyl;

R ⁷ is H, NH ₂ , OH, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-6 alkylthio C 1-4 alkylamino, C 2-8 dialkylamino or phenyl optionally substituted with 1 to 3 times W ¹ ;

R ⁸ is H or may be C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, phenoxy, phenyl or naphthyl, each of which is optionally 1-3 carbon atoms. -substituted with W ¹ ;

R ⁹ and R ¹⁰ are C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, phenoxy, phenyl or naphthyl, each of which is optionally 1-3 carbon atoms. -substituted with W ¹ ; they may also represent OH;

R ¹¹ is H, NH ₂ , OH, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-2 alkylthio- C 1-4 alkylamino, C 2-8 dialkylamino, or phenyl optionally substituted with 1 to 3 times W ¹ ;

W is halogen, CN, NO ₂ , OH, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy or C 1-6 haloalkoxy, and

W ¹ is halogen, CN, NO ₂ , C 1-2 alkyl,

C 1-2 haloalkyl, C 1-2 alkoxy, C 1-2 haloalkoxy, C 1-2 alkylthio, C 1-2 haloalkylthio, C 1-2 alkyl -Sulfonyl, C 1 -C 2 haloalkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, or C 3 -C 6 trialkylsilyl.

Preferred are compounds A of the above formula I wherein A is C 1-6 alkylene,

R ¹ is C 1 -C 3 alkyl which is 5 or

Substituted by a 6-membered aromatic ring attached through a carbon or nitrogen atom containing from 1 to 4 heteroatoms selected from the group consisting of 0-4 nitrogen atoms, 0-1 oxygen atoms and 0-1 sulfur atoms, optionally 1-3 times with W ¹ is substituted;

R ⁴ is C 1 -C 10 alkyl or phenyl, each of which is optionally substituted with ^{1 to} 3 times W ¹ ;

^R5 and ^R6 are independently C1-10 alkyl or phenyl, each of which is optionally substituted by 1-3 of a W ¹ group; and

W ¹ is halogen or C 1 -C 2 haloalkyl.

Further preferred are compounds B of the above preferred compounds A, wherein X is Si,

- ^6, R ¹ is CH ₂ groups, substituted pyridyl, thiazole or isoxazole group and the ring is optionally substituted with 1 to 2 halogen atoms or even 1 to 2 methyl groups;

R ² and R ³ together are CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ , each of which is optionally substituted with 1 to 2 CH ₃ groups, and

R ⁴ , R ⁵ and R ⁶ are each independently C 1-3 alkyl, C 1-3 alkoxy or phenyl.

Further preferred are compounds C of the above preferred Compounds A wherein X is Si;

R ¹ is CH ₂ substituted with pyridyl, thiazole or isoxazole and optionally substituted with 1 to 2 halogens;

R is H or (1-3C) alkyl; and R ⁴ , R ⁵ and R ⁶ are each independently C 1-3 alkyl, C 1-3 alkoxy, or phenyl. Particularly preferred for biological activity is the following preferred group B compound D:

l - [(6-chloro-3-pyridinyl) methyl] -l, 2,3,5,6,7-hexahydro-2-methyl-8-nitro-6 - [(trimethylsilyl) methyl] - imidazo [1,2-c] -pyrimidine.

Also particularly preferred for biological activity is the following compound E, which is one of the above preferred compounds B:

l - [(6-chloro-3-pyridinyl) methyl] -l, 2,3,5,6,7-hexahydro-8-8-nitro-6 - [(trimethylsilyl) methyl] imidazo [ l, 2-c] pyrimidine.

The compounds of the invention may also exist in the form of one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, and geometric isomers. One of ordinary skill in the art will recognize that one stereoisomer may be more active and / or advantageous when present in the majority relative to the other stereoisomer or when separated from the other stereoisomers or stereoisomers. Further, one skilled in the art will recognize how to separate the stereoisomers. Accordingly, the present invention relates to racemic mixtures, individual stereoisomers and optically active mixtures of compounds of formula (I) as well as their agriculturally acceptable salts.

The term 5- or 6-membered aromatic ring refers to rings that satisfy the Hückel rule; such as 5-6 membered monocyclic aromatic rings containing 0-4 heteroatoms such as phenyl, furyl, furazinyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, and the like. , thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl groups which at any one of their carbon or nitrogen atoms are

can connect. For example, when the aromatic ring is a furyl group, it may be 2-furyl or 3-furyl, and in the case of pyrrolyl, it may be 1-pyrrolyl, 2-pyrrolyl or

In the case of a 3-pyrrolyl group, a pyridyl group may be an aromatic ring

2-pyridyl, 3-pyridyl or 4-pyridyl and the like are also applicable to other monocyclic aromatic rings.

The above-mentioned alkyl group, which may be alone or for example as an alkylthio or haloalkyl group, is a linear or branched alkyl group such as methyl, ethyl, η-propyl, i-propyl or various max. C 10 groups. The alkylene group may be CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ or any other max. C 20 group. The alkenyl group may be a straight or branched chain group such as ethenyl, 1-propenyl, 2-propenyl or other max. C 10 groups. The alkenyl group may be a polyene such as 1,3-hexadiene. The alkenylene group may be CH = CH, CH ₂ CH = CH, CH = CHCH _2, or the like, with max. C 20 group. The alkynyl group may be a straight or branched alkyne group such as ethynyl, 1-propynyl,

3-propynyl or similar, max. C 10 groups. The alkynylene group may be C = C, CH _2, C 1 -C 4, OCCH _2, or the like with max. C 20 group. The alkoxy group may be, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy or the like, max. C 10 groups. The alkylthio group may be a straight or branched alkyl thio group such as methylthio, ethylthio, various propylthio, butylthio, pentylthio or hexylthio. isomers. The alkylsulfonyl group may be CH ₃ S (O) ₂ or CH ₃ CH ₂ S (O) ₂ . The alkylamino group may be methylamino, ethylamino, η-propylamino, isopropylamino, or various butylamino isomers. The dialkylamino group is a nitrogen atom substituted with two alkyl groups, which may be different. Examples include N, N-dimethylamino and N-ethyl-N-methylamino. Cycloalkyl may be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cycloalkylalkyl may be, for example, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl or other various C 6 and C 7 isomers which are bonded to straight or branched alkyl. Halogen, alone or in association with the haloalkyl group, represents fluorine, chlorine, bromine or iodine. Furthermore, the haloalkyl is a partially or milk prowl substituted with an alkyl group with halogen atoms which may be the same or different, for example, may be as follows: F ₃ C C1CH _2, CF ₁₃ CH ₂ and CF ₃ CC1 _second The haloalkenyl group may be, for example, (C 1) ₂ C = CHCH ₂ or CF ₃ CH ₂ CH = CHCH ₂ . A haloalkynyl group can be for example HC ^ CCHCl, CF ₃ C-C, CC1 ₃ C ^ C and FCH ₂ C = CCH _2. The haloalkoxy group may be, for example, CF ₃ O, CCl ₃ CH ₂ O, CF ₂ HCH ₂ CH ₂ O and CF ₃ CH ₂ O. The haloalkylthio group may be, for example, CCl ₃ S, CF ₃ S and CC1 ₃ CH ₂ S.

Examples of haloalkylsulfonyl include CF ₃ SO ₂ , CC _{1 3} SO ₂ , CF ₃ CH ₂ SO ₂ and CF ₃ CF ₂ SO ₂ . The number of carbon atoms in the substituent groups may be C 1 -C 3 where i and j are

1-20. For example, a C 1 -C 20 alkylene group may be methylene, ethylene or propylene, up to the dodecylene isomers. C 2 alkoxy is CH ₃ CH ₂ O and C 3 alkoxy is CH ₃ CH ₂ CH ₂ O or (CH ₃ ) ₂ CHO.

The compounds of formula (I) of the present invention may be prepared, for example, from Scheme A and the compound of formula (II) and one or two equivalents of formula (III)

By reacting a 10-formula amine in a solvent in the presence of at least two molar equivalents of formaldehyde. The reaction is usually carried out at a temperature between 0 ° C and the reflux temperature of the solvent, preferably 0-25 °. Reaction Scheme A generally takes 1 day to complete, but certain reactions in Scheme A may require longer reaction times (up to 5 days). Suitable solvents are, for example, alcohols such as methanol or ethanol, water or polar aprotic solvents such as tetrahydrofuran or dimethylformamide. The amount of formaldehyde is generally 2 to 10 molar equivalents. Paraformaldehyde or an aqueous solution of formaldehyde may be used. In some cases it may be necessary to use small amounts of a strong, non-oxidizing acid such as hydrochloric acid as a catalyst. Alternatively, the hydrogen halide or bisulfonic acid salt of the amine compound of formula (III) may be used.

Compounds of formula (II) are prepared by reacting a compound of formula (IV) with a compound of formula (V) as shown in Scheme B. In general, the compounds of formula (IV) are reacted with from 1 to 20 molar equivalents of an amine of formula (V) in a suitable solvent at a temperature of 0 to 100 ° C. Reaction Scheme B generally takes from 6 to 48 hours, but in some cases longer reaction times may be required. Suitable solvents include, but are not limited to, alcohols such as methanol, ethanol or isopropanol, water, acetonitrile, dimethylformamide or dimethylacetamide. The amines of formula (V) may also be formulated in the form of their hydrochloride salts, in which case an equivalent amount of a base (e.g., sodium hydroxide) is added to the reaction mixture. In Scheme B, X ¹ is a suitable leaving group such as halogen, SCH ₃ or OC ₆ H ₅ .

The compound of formula (II) may also be prepared by reacting a compound of formula (VI) with an amine of formula (VII), which is illustrated in Scheme C. This reaction is carried out in an analogous manner to the reaction shown in Scheme B.

The compound of formula (VII) may be prepared in a known manner, for example by reaction of nitroethane compounds of formula VIII with amines of formula VII (Scheme D). The compound of formula (VI) is obtained in an analogous manner to the preparation of compound of formula (IV). In this reaction, the compounds of formula (VII) and (VIII) are reacted in equimolar amounts in a suitable solvent or mixture of solvents at a temperature of 0 to 100 °. The reaction shown in Scheme D generally takes about 6 to 48 hours to complete. Suitable solvents are those of sufficient polarity to form the compounds of formulas VII and VIII, alcohols such as methanol, ethanol and isopropanol, ethers such as diethyl ether, tetrahydrofuran or dioxane, esters such as ethyl acetate, polar aprotic solvents such as dimethylformamide or dimethylacetamide, and water and mixtures of these solvents.

The compounds of formula (I) may also be prepared from tetrahydropyrimidines of formula (IX) and (VII).

Reaction of the amines of Formula 12, as shown in Scheme E, with the same conditions as in Scheme B. The reaction of Scheme E is particularly preferred for the preparation of compounds of formula I wherein R and / or R is H.

Compounds of formula (IX) are prepared by reacting amines of formula (III) with compounds of formula (VI) in the presence of formaldehyde, which is illustrated in Scheme F, analogous to Scheme A.

The compounds of formula (I) may also ellőállíthatjuk according to Scheme G, there is provided a Compound (I) of formula wherein ^R1 is hydrogen, and the reaction is carried out by reacting a compound of formula (I), wherein R ¹ is hydrogen, and is reacted with an alkylating agent of formula X in the presence of a proton acceptor and a suitable solvent. Examples of proton acceptors include NaH, KH, K ₂ CO ₃ , NaHCO ₃ and Cs ₂ CO ₃ , and solvents such as DMF, THF, acetonitrile and water. In some cases, Scheme G is carried out under phase transfer conditions using a solvent such as toluene, dichloromethane, dichloroethane, ether, hexane, benzene, etc., an aqueous base such as NaOH, KOH, NaHCO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , etc. presence. As phase transfer catalysts, for example, tetrasubstituted ammonium halide salts such as tetrabutylammonium iodide, benzyltriethylammonium bromide, and the like. It can be used. The reaction is usually carried out at a temperature of from 20 to 150 ° C for a period of from 1 hour to 3 days, preferably from 6 to 24 hours. In Scheme G, X ² is a suitable leaving group such as halogen, tosylate, methanesulfonate or trifluoromethanesulfonate. Compounds of formula (I) (wherein R is other than hydrogen) may also be prepared according to Scheme H under similar conditions as Scheme G. In Scheme H, X ² is a suitable leaving group.

Compounds of formula II (R ² and R ³ taken together are a 5- or 6-membered ring and R ¹ is other than hydrogen) are prepared as shown in Scheme I. The reaction conditions for Scheme I are the same as those for Scheme G. In Scheme I, X ² is a suitable leaving group, R H, B = R and R, which together form a 5- or 6-membered ring.

Compounds of formula II (wherein R and R taken together are a 5- or 6-membered ring) may also be prepared as shown in Scheme J. In this reaction, compounds of formula (XII) and (VIII) are reacted in equimolar amounts in a suitable solvent or solvent mixture at a temperature of 0 to 100 ° C for 2 to 48 hours. Suitable solvents are those which have sufficient polarity to dissolve the compounds of formulas XII and VIII, such as alcohols such as methanol, ethanol and isopropanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, esters such as ethyl. acetate, polar aprotic solvents such as dimethylformamide and dimethylacetamide, and water;

- 14 2 3 1 mixtures thereof. In Scheme J, B = R and R together, X is a suitable leaving group.

The diamines of formula (XII) may be prepared, for example, by reacting compounds of formula (X) with amines of formula (XIII) in stoichiometrically excess form, which is illustrated in Scheme K. The reaction is generally carried out in an amount of 1.5 to 10 equivalents of the compound of formula XIII and is carried out in a solvent such as methanol, ethanol, isopropanol, THF, water or acetonitrile or the like. In some cases, the reaction of Scheme K may be carried out without solvent. The reaction time is usually from 30 minutes to several days, preferably from 6 to 24 hours. In Scheme K, X is a suitable leaving group and B is R ² and R ³ together.

The diamines of formula XII wherein B is an optionally substituted CH ₂ CH ₂ group can be prepared by a two step reaction, which is illustrated in Scheme L. In step i, the amine of formula (XIV) is treated with potassium cyanide and a compound of formula (XV) in the presence of 0-3 equivalents of acid to give the aminonitrile of formula (XVI). One skilled in the art will recognize that the compound of Formula XV is formaldehyde, acetaldehyde, or acetone. Other cyanide salts may also be used, as well as HCN and the hydrogen halide or other acid salt of the compound of formula XIV. Suitable solvents are, for example, methanol, ethanol, isopropanol or water, or combinations thereof. The reaction usually takes about 24 hours. Another method is described in

- aminonitriles, for example, for the preparation of compounds of formula XVI, for example, Synth. Commun., 15, 157 (1985); Synthesis, (1979), 127.

In Scheme L, step ii, the aminonitrile XVI is converted to the diamine XII by reduction. This reduction is generally carried out with lithium aluminum hydride or borane in an amount of 0.75 to 3 molar equivalents using, for example, diethyl ether or THF. The reaction temperature is -20 ° C to the reflux temperature of the solvent and the reaction time is usually from 0.5 hours to 2 days. The reduction of compound (XVI) to compound (XIII) can also be accomplished by catalytic hydrogenation using, for example, palladium on carbon or Raney nickel as catalyst. In the hydrogenation reaction, addition of ammonia may occasionally increase the yield of the diamines of formula XII. In Scheme L, R and R are each independently H or CH ₃ .

The preparation of the diamines of formula XII, wherein B is an optionally substituted CH ₂ CH ₂ group, can also be carried out according to Scheme M. Here, in step i, the aminoamides of formula XVII are treated with 1-2 molar equivalents of the acid chloride of formula XVIII with 1-3 molar equivalents of a base such as NaOH, KOH, K ₂ CO ₃ , NaHCO ₃ , pyridine or triethyl. in the presence of amine. Suitable solvents are, for example, THF, CH ₂ Cl ₂ , water or pyridine. The compound of formula (XIX) is obtained by extraction or, more preferably, by removal of solvent, and is generally suitable for use in step (ii) in this crude form. When the amides of formula (XVII) can be used in the neutral form as obtained or in the form of a salt (usually in the form of the HCl or CF ₃ CO ₂ H salt). The salt form of the compound of formula (XVII) is used, and in step i, an equivalent amount of base is added.

In Scheme M, step ii), the amide of formula XIX is converted to the diamine of formula XII by treatment with a reducing agent such as one of LiAlH ₄ , BH ₃ .THF or BH ₃ .SMe ₂ as a solvent, for example THF. or Et ₂ O, the temperature is between 0 ° C and the reflux temperature of the solvent. The reaction time is usually 0.5 hours to 2 days. An analogous procedure to this is also described in the literature (e.g., Synthesis, (1981), 441).

When R is CH ₃ and R is H, the compound of Formula XVII is an alanine amide. When the D or L form or salt of this compound is used, the corresponding enantiomerically rich form is obtained. When the compound (II) is prepared according to Scheme G using the enantiomerically rich compound (XII), the compound (II) is obtained in the enantiomerically rich form. When the compound of formula (I) is prepared according to Scheme A using the enantiomerically rich compound of formula (II), the compound of formula (I) is obtained in an enantiomerically rich form. In Scheme M, R ¹⁴ is CH ₃ SCH ₂ ,

17 3-pyridyl, 5-thiazolyl, 6-chloro-3-pyridyl, 3-chloro-5-thiazolyl or 5,6-dichloro-3-pyridyl.

The diamines of formula (XII) may also be prepared in pure enantiomeric form by resolution with enantiomeric acids such as boric acid. This resolution method is known to those skilled in the art (see, for example, Synthesis (1991), 789).

The amines of formula (III) may be prepared by reacting the silyl halide of compound of formula (XX) with excess ammonia, which is illustrated in Scheme N. In this transformation reaction, compound (XX) is added to anhydrous liquid ammonia (2-100 equivalents) at -78 to + 100 ° C. In the case where the temperature is above -33 ° C, the reaction is carried out in a closed, high-pressure apparatus. In general, no solvent is used, but in some cases the reaction may be carried out in the presence of, for example, THF or diethyl ether. The reaction time is usually 0.5 to 72 hours. The work-up is generally carried out by evaporation of excess ammonia, precipitation of the ammonium halide with ether and removal of the solvent. One skilled in the art will recognize that several other methods may be used to convert the halides of formula (XX) to the primary amines of formula (III). Such a procedure is described, for example, in March, Adv. Org. Chem., 4th ed., 1276-7. In Scheme N, tone X is a leaving group.

Silanes or germans of the compound of formula XX may be prepared, for example, from the compound of formula XXI

Reaction of Grignard's reagent or lithium organic compound 18 with a chlorosilane or chloro-germanium compound of the formula (XXII) is illustrated in Scheme O. The reaction comprises reacting an equimolar amount of a compound of formula (XXI) and (XXII) in an organic solvent such as pentane, hexane, THF, ether, or the like at -78 to 25 ° C, sometimes for 2 hours to 4 days. . In Scheme O, M = Li, MgCl, MgBr or Mgl and X is a suitable leaving group.

For example, the chlorosilane and chloro-germanium of compound (XXII) can be prepared by reacting dichloride (XXII) with 1 molar equivalent of compound (XXIV), an organic metal compound, as shown in Scheme R in. The reaction conditions are analogous to those described in Scheme O. Preparation of a compound of Formula XX wherein R ^{4 is the} same as R ⁵ using 2 equivalents of a compound of Formula XXIV in Reaction Scheme R.

Compounds of formula (XX) wherein R ⁴ , R ⁵ and R ⁶ are the same are prepared by reacting the trichloride of compound (XV) with 3 equivalents of the organometallic compound (XXIV) according to Scheme S . The reaction conditions are the same as described in Scheme O. In Scheme S, X is a suitable leaving group and M is Li, MgCl, MgBr or Mgl.

- 19Action of compound of formula XX wherein R ⁴ is alkoxy or phenoxy by reacting an alcohol or phenol of formula XXVI with a chlorosilane or chloro-germanium derivative of a compound of formula XXII in the presence of a base such as triethylamine, pyridine or NaOH, the reaction is illustrated in Scheme T. In the scheme, R ⁴ is alkoxy or phenoxy.

The preparation of compounds of formula XX (R ⁴ = alkoxy or phenoxy) is known to those skilled in the art (Org. Synth., 69, 96; J. Chem. Soc. Chem. Commun., 1988, 802; J. Organomet. Chem. (1970), 22, 599).

The silanes and germans of the compound of Formula XX, wherein R ⁴ and R ⁵ are alkoxy or phenoxy, can be prepared by reacting the dichlorides of the compound of Formula XXIII with 2 equivalents of the alcohol of Formula XXVI in the presence of a base. according to. Similarly, compounds of formula (XX) wherein R ⁴ and R ⁵ are alkoxy or phenoxy are obtained by reacting trichlorosilane or trichloro-germanium of compounds of formula (XXV) with 3 equivalents of alcohol (XXVI) in the presence of a base. , the reaction is analogous to that described in Scheme T.

It will be apparent to those skilled in the art that other alternative methods of preparation of compounds of formulas XX, XXII, XXIII and XXV are known. Examples of silanes include the following references: Fleming, I., Organosilicon Chemistry, Comprehensive Organic

-20 Chemistry (1979), 3, 541; Colvin, E., Silicon, Organic Synthesis, Butterworths, Boston, (1981); and Pawlenko, S., Organosilicon Chemistry, Walter de Gruyter, New York (1986); with regard to the Germans, Riviere, P., et al., Germanium, In Comprehensive Organometallic Chemistry (1982), 2, 399; Lesbre, M., et. al, The Organic Compounds of Germanium, Wiley, London, (1971).

It will be appreciated that the reagents and reaction conditions described above may sometimes be incompatible with certain functional groups present in the starting materials. In such cases, the process is carried out by introducing protecting groups and then removing the protecting groups. The use and selection of protecting groups is known to those skilled in the art of chemical synthesis.

Example 1

The step:

Methyl-N - [(6-chloro-3-pyridinyl) carbonyl] -alanine

6-Chloronicotinyl chloride (50.5 g, 0.29 mol) was dissolved in CH ₂ Cl ₂ (290 mL) and DL-alanine methyl ester (60 g, 0.43 mol) in saturated aqueous sodium bicarbonate (290 mL). hydrochloride, 5 ml aliquat 366 (Aldrich) was added and the resulting biphasic mixture was stirred vigorously at 25 ° for 24 hours. The resulting mixture was partitioned between CH ₂ Cl ₂ and saturated NaHCO ₃ , the aqueous phase was extracted three times with CH ₂ Cl ₂ , the organic phases were combined, washed twice with saturated NaHCO ₃ solution, dried over MgSO ₄ and concentrated. 56.1 g of the title compound are obtained in the form of a viscous yellow oil.

1 H NMR (300 MHz, CDCl 3) δ 8.82 (d, J = 2.4Hz, 1H), 8.10 (dd, 1H), 7.41 (d, 1H), 7.10 (br d, 1H) ), 4.78 (quintet, 1H), 3.80 (s, 3H), 1.53 (d, 3H).

Step B:

6-Chloro-N- [l- (aminocarbonyl) ethyl] -3-pyridinecarboxamide

50.5 g (0.21 mol) of the product of Step A are dissolved in 150 ml of anhydrous MeOH and 575 ml of 15% ammonia / anhydrous methanol are added. The resulting solution was stirred at room temperature for 48 hours, then the solid product was collected by filtration, washed with ethanol and dried in vacuo to give 43.5 g of the title compound as a white solid, m.p.> 200 ° C.

NMR (400 MHz, _{(CH3) 2} SO-d₆ δ 8.87 (apparent s, lH);

8.79 (d, 1H), 8.29 (d, 1H), 7.65 (d, 1H), 7.45 (br s, 1H), 7.03 (br s, 1H), 4.41 (quintet, 1H), 1.33 (d, 3H).

Step C:

N - [(6-Chloro-3-pyridinyl) methyl] -1,2-propanediamine

18.7 ml (0.19 mol) of borane methyl sulfide complex was added dropwise to a mixture of 119 ml of THF and 8.5 g (0.04 mol) of the product of Step B at 50-60 ° C with stirring. The resulting orange-yellow slurry was heated at reflux for 2 hours, cooled to room temperature, carefully added dropwise with 62 ml of 6N HCl and the resulting pale yellow mixture was stirred at room temperature for 24 hours. The material is then washed three times with ether and the aqueous phase is made basic with 25 ml of 50%

(22 portions under cooling) and extracted with 3 x 150 ml of methylene chloride / chloroform = 2/1. The organic phases are combined, dried over K ₂ CO ₃ and concentrated to give 3.5 g of the title compound as a yellow oil.

1 H NMR (400 MHz, CDCl 3) δ 8.33 (apparent s, 1H), 7.69 (d, 1H), 7.30 (d, 1H), 3.78 (ABq, 2H), 2.75 ( d, 1H), 2.63 (dd, 1H), 2.53 (dd, 1H), about 1.50 (br s, 3H), 1.07 (d, 3H).

Step D:

2-Chloro-5- [I5-methyl-2- (nitro-methylene) -l-imidazolidinyl] methyl] pyridine

2.5 g (0.013 mol) of the product from Step C, 1.6 g (0.009 mol) of 1,1-bis (methylthio) -2-nitroethylene are suspended in 63 ml of anhydrous EtOH and heated at reflux for 3 hours, and allowed to stand at 24 ° for 72 hours. The resulting mixture was concentrated, chromatographed on silica gel (15/1 / 0.1 = CH ₂ Cl ₂ / EtOH / 30% NH ₄ O) to give 0.7 g of the title compound as a yellow solid, m.p. 127-131 ° C. C.

^! 1 H NMR (400 MHz, CDCl 3) δ 8.70 (br s, 1H), 8.27 (s, 1H),

7.56 (d, 1H), 7.35 (d, 1H), 6.56 (s, 1H), 4.33 (ABq, 2H), 3.95-3.85 (m, 2H), 3 , 45-3.35 (m, 1H), 1.33 (d, 3H).

Step E:

l - [(6-Chloro-3-pyridinyl) methyl] -l, 2,3,5,6,7-hexahydro-2-methyl-8-nitro-6 - [(trimethylsilyl) methyl-imidazo [1,2-c] Pyrimidine (Compound 1)

0.5 g (1.9 mmol) of the compound of Step D, 0.31 mL (4.1 mmol) of 37% aqueous formaldehyde, 0.21 g (2.1 mmol) of trimethylsilylmethylamine and 4 ml of ethanol at room temperature

After stirring for 23 hours, the product was concentrated and the yellow residue was stirred with diethyl ether and filtered to give 0.32 g of the title compound as a yellow solid, m.p. 112-115 ° C.

^! NMR (300 MHz, CDCl3) δ 8.30 (s, 1H), 7.81 (d, 1H), 7.30 (d, 1H), 5.04 (l / 2ABq, 1H), 3.98-. 3.68 (m, 6H), 3.23 (dd, 1H), 1.94 (s, 2H), 1.26 (d, 3H), 0.08 (s, 9H).

Example 2

The step:

2-nitromethylene-imidazolidine

1,1-bis (methylthio) -2-nitroethylene (125 g, 0.76 mol) and ethylenediamine (50.6 ml, 0.76 mol) were suspended in ethanol (757 ml) and heated at reflux for 4 hours. The reaction mixture was cooled to 0 ° C and filtered. The solid was washed with cold ethanol and dried in vacuo to give 102.5 g of a beige solid.

1 H NMR (200 MHz, Me ₂ SO-d ₆ ) δ 8.27 (br s, 2H), 6.33 (s, 1H),

3.58 (s, 4H).

Step B:

l, 2,3,5,6,7-hexahydro-8-nitro-6 - [(trimethylsilyl) methyl] imidazo [l, 2-c] pyrimidine

0.98 g (7.6 mmol) of the product of Step A, 1.26 mL (16.7 mmol) of 37% aqueous formaldehyde are suspended in 15 mL of ethanol and 1.11 mL (8.3 mmol) of trimethylsilyl at room temperature. -methylamine. After 18 hours, the resulting solution was concentrated to give 1.85 g of a yellow solid.

1 H NMR (400 MHz, CDCl ₃ ) δ 8.33 (br s, 1H), 4.00 (s, 2H),

3.80 (overlapping t, 2H and s, 2H), 3.66 (t, 2H), 2.14 (s, 2H),

0.10 (s, 9H).

- Step C:

l - [(6-Chloro-3-pyridinyl) methyl] -l, 2,3,5,6,7-hexahydro-8-nitro-6 - [(trimethylsilyl) methyl] imidazo [l, 2-c] -piriinidin

0.5 g (2 mmol) of the product of Step B, 0.8 g (3.9 mmol) of 6-chloro-3-chloromethylpyridine hydrochloride, 0.004 g (0.1 mmol) of tetran-n-butyl ammonium iodide, 6.4 mL of 50% aqueous KOH and

8.4 mL of methylene chloride was stirred vigorously for 24 hours. The resulting material was poured into water, extracted 3 times with methylene chloride, the organic phases were combined, washed with saturated aqueous sodium bicarbonate solution, dried over K ₂ CO ₃ and concentrated. The crude product was stirred with diethyl ether and filtered to give 0.34 g of the title compound as a yellow solid, mp 145.5-147 ° C.

1 H NMR (400 MHz, CDCl ₃ ) δ 8.35 (d, 1H), 7.90 (dd, 1H), 7.33 (d, 1H), 4.86 (s, 2H), 3.90 (s, 2H), 3.77 (s, 2H), 3.68-3.55 (m, 4H),

2.02 (s, 2H), 0.10 (s, 9H).

Proceeding as described above, the obvious modifications are made to the compounds of Examples 1-16. and Tables A-D. Row 1 of Table 1 is referred to as 1-1, 1-2, 1-3, and 1-4. The other compounds listed in these tables are designated similarly. 1-6. and Tables A-D use the following abbreviations:

ο-Ρ m-Ph p-Ph

Me = CH ₃

Et = CH ₂ CH ₃ n-Pr = (CH ₂ ) ₂ CH ₃ i-Pr = CH (CH ₃ ) ₂ n-Bu = (CH ₂ ) ₃ CH ₃ i-Bu = CH ₂ CH (CH ₃ > ₂ s). Bu = CH (CH ₃ ) CH ₂ CH ₃ 1 -Bu = C (CH ₃ ) ₃ Ac = C (O) CH ₃ n-pentyl = (CH ₂ ) 4 CH ₃ n -hexyl = (CH ₂ ) 5 CH ₃ cP. , = _ <3 c-Bu c-pentyl

0>

c-hexyl =

CH2 (2-O-Ph)

CH ^ SOPh) + -

4 PJR

2-CH ^ pir =

3-CH ^ pir =

4-CH2-pyr =

2-CH ₂ -6Opir

3-CH2-6-Q-PJR

6-F 3-pyr

CH

CH

2-CH2-3-Me · pyrazil

Me

CH

2-CH2-5-Me-pyrazyl ^x

Me

CH

Me

2-CH 2 -pyrazyl =

2-CH 2 -O-Me-pyrazil

2-CH2-5O · pyrazil

CH

3-CH 2 -pyridazin 1 = cu

3-pyridazyl CH2-6O- = CH ₂ 2-pyrimidyl CH 2 =: o:

N - N

Όλ- °

N - N "2— <)>

4-CH 2 pyrimidyl = CH

5-CH2-thiazolyl

- 27 5-0 ^ -2-0- Thiazolyl

2-CH 2 -thienyl =

2 <H2-5-Br-Thienyl ·

2-CH2-2-CH2-2 pyrrolyl

S-CH3-Methiazolyl =

5-C-2-2-Br-thiazolyl =

Me

5-CH2-3-Me-isoxazolyl =

CH ₂ '

α

2-thiadiazolyl

N-N

S-Me-2-thiadiazolyl =

2-CH2-thiadiazolyl =

- Table 1 Compounds of general formula (1)

R =

1 2 3 4 1 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 2 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 3 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 4 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 5 i-Pr 4-Cl-Ph CHjNMejI 2-CH ₂ -5-Cl-pyr 5 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 7 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 3 i-Bu 3-CH, pyrrole CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 3 Pr-c 4-CH, pyrrole CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 10 hccch ₂ 5-CH, isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 11 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 12 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 13 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 14 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ S-CH ₂ -2-Cl-thiazolyl 15 AcSCH, 5-CH _; 2-Me-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 16 Et ₂ NCH ₂ 5-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 17 c-Bu 2-CH, 5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 18 c-pentyl 3-CH ₂ -pyrazolyl 2-CH _; pyrrolyl ch ₃ chchch ₂ ch ₂ 19 c-hexyl 4-CH _; pyrazolyl 3-CH ₂ -pyrrolyl Et, NCH ₂ CH ₂ 20 6-F-2-pyr 5-CH _; pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me, CH ₂ CH ₂ 21 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 22 6-Br 3-pyr 2-CH, 5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 23 6-F 3-pyr 3-CH _; -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 24 6-OMe 3-pyr 3-CH _; 6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 25 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 26 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 27 5-Cl-2-pyr 3-CH, 6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 28 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 29 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 30 5-F-2-pyr 2-CH, 6-Me-pyr 4-CH ₂ -pyrimidyl 5-C 1-2-thiadiazyl 31 6-OMe-2-pyr 2-CH, 6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil

32 2-Thiadiazole 1 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 33 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 34 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 35 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 36 6-Cl-4-pyr

Table 2 Compounds of Formula 2 r '=

1 2 3 4 37 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 38 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 39 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 40 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 41 i-Pr 4-Cl-Ph CHjNMejI 2-CH ₂ -5-Cl-pyr 42 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 43 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 44 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5.6-di-Cl-pyr 45 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 46 hccch ₂ 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 47 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 48 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 49 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 50 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 51 AcSCH _; 5-CH ₂ -2-Me-thiazolyl 2-CH _; furyl CH ₂ CHCH ₂ CH ₂ 52 Et ₂ NCH ₂ 5-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH, 53 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 54 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl ch ₃ chchch ₂ ch ₂ 55 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH, CH ₂ 56 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 57 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH2-l-Me-pirazolyt 2-CH ₂ -1 -Me-pyrrolyl 58 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 59 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazyl 5-CH ₂ -thiazolyl 60 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazil _{2-thienyl-CH2} 61 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 62 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 63 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr

64 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH, 6-Me-pyridazyl 2-CH ₂ -thiadiazil 65 5-Br-2-pyr _3-CH2-pyr -6-OCFj 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 66 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 67 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 68 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 69 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 70 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 71 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 72 6-Cl-4-pyr

Table 3 Compounds of general formula (3)

R ^{1 =}

1 2 3 4 73 H Ph 2-CH-5-CF ₃ -thienyl CH _: (3,4-di-Cl-Ph) 74 Me -Ph ncch _; ch ₂ 2-CH ₂ -6-Cl-pyr 75 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Ct-pyr 76 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 77 i-Pr 4-Cl-Ph CH ₂ NMe ₃ L 2-CH ₂ -5-Cl-pyr 78 n-Bu CH- (c-Pr) CH ₂ CH _; NMe ₃ L 2-CH ₂ -4-Cl-pyr 79 s-Bu 2-CH, pyrrole CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 80 i-Bu 3-CH _; -blush CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 81 Pr-c 4-CH, pyrrole CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 82 hccch ₂ 5-CH, isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 83 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 84 2-pyr CH- (c-Bu) ch _: chch ₂ 3-CH _; 5,6-di-Cl-pyr 85 3-pyr CH _; (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 86 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 87 AcSCH ₂ 5-Me-2-CH thiazolyl 2-CH _; furyl CH ₂ CHCH ₂ CH ₂ 88 Et-NCH ₂ 5-CH ₂ -2-Br- thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 89 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 90 c-pentyl 3-CH, pyrazolyl 2-CH _; pyrrolyl ch ₃ chchch ₂ ch ₂

91 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 92 6-F-2-blush 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 93 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 94 6-Br 3-pyr 2-CH ₂ -5-Me 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -t-Me-pyrrolyl 95 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazyl 5-CH ₂ -thiazolyl 96 6-OMe-3- -blush 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 97 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 98 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 99 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 100 S-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 101 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 102 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 103 6-OMe-2- -blush 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 104 2- -thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ - -thiadiazil 2-CH ₂ -5-Me-thiadiazil 105 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 106 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Me-isoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 107 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 108 6-Cl-4-pyr

Table 4 Compounds of formula (4)

R ^{, =}

1 2 3 4 109 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 110 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 111 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 112 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 113 i-Pr 4-Cl-Ph CH ₂ NMeI 2-CH _: -5-Cl-pyr

»· ₍ · *« · * * ♦ · · · <*

1 14 n-Bu CH _; (C-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 115 s-Bu 2-CH _; -blush CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 116 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 117 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 118 hccch ₂ 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH 2 3-CH ₂ -4-Cl-pyr 119 NCCHj Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 120 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr • 121 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 122 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl * 123 AcSCH ₂ 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl ch ₂ chch ₂ ch ₂ 124 ₂ Et2NCH 5-CH ₂ -2-Br- thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 125 c-Bu 2-CH _: -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 126 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl ch ₃ chchch ₂ ch ₂ 127 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 128 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 129 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 130 6-Br 3-pyr 2-CH _: -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 131 6-F 3-pyr 3-CH _; -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 132 6-OMe 3-pyr 3-CH _; 6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 133 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 134 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 135 5-Cl-2-pyr 3-CH, 6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 136 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 137 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 138 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 139 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 140 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 141 MeS CH2 2-CH, 6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 142 6-Cl-2-pyr 5-CH _: -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 143 6-C 1-3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 144 6-Cl-4-pyr

Table 5 Compounds of general formula (5)

- 33 R =

1 2 3 4 145 Η Ph 2-CH ₂ -5-CF ₃ -thienyl CH2 (3,4-di-Cl-Ph) 146 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH2-6-Cl-pyr 147 et 2-Cl-Ph AcNHCH ₂ 3-CH2-6-Cl-pyr 148 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH2-6-Cl-pyr 149 i-Pr 4-Cl-Ph CH ₂ NMe ₃ L 2-CH2-5-Cl-pyr 150 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH2-4-Cl-pyr 151 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH2-3-Cl-pyr 152 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH2-5,6-di-Cl-pyr 153 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH2-5-Cl-pyr 154 hccch ₂ 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH2-4-C) pyrrole 155 NCCH; Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH2-2-Cl-pyr 156 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH2-5,6-di-Cl-pyr 157 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH2-2,6-di-Cl-pyr 158 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH2-2-Cl-thiazolyl 159 AcSCH ₂ 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl CH2CHCH2CH2 160 Et ₂ NCH ₂ 5-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH2C (Me) CH2CH2 161 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH3CHCHCH2 162 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl CH3CHCHCH2CH2 163 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et2NCH2CH2 164 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me2NCH2CH2 165 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH2-1-Me-pyrrolyl 166 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH2-l-Me-pyrrolyl 167 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH2-thiazolyl 168 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl 2-CH2-thienyl 169 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -S-Me-pyrazil 5-CH2-2-Cl-pirinvdyl 170 6-Br-2-pyr 2-CH ₂ -6-CF 3 -pyr 2-CH ₂ -6-Me-pyrazil 2-CH2-5-Cl-pyrazyl 171 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazole 2-CH2-6-OCF3-pyr 172 5- \ le-2-pyr 3-CH ₂ -6-CF 3 -pyr 3-CH ₂ -6-Me-pyridazil 2-CH2-tiadiazil 173 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 174 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 175 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF2-2-tiadiazíl 176 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH2-5-Me-tiadiazil 177 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH2-5-Cl-tiadiazil 178 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH2-3-Cl-isoxazolyl 179 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH2-3-Br-isoxazolyl

180 6-Cl-4-pyr

r '=

Table 6 Compounds of general formula (6)

1 2 3 4 181 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH2 (3,4-di-Cl-Ph) 182 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH2-6-Cl-pyr 183 et 2-Cl-Ph AcNHCH ₂ 3-CH2-6-Cl-pyr 184 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH2-6-Cl-pyr 185 i-Pr 4-Cl-Ph CH, NMe, I 2-CH2-5-Cl-pyr 18-6 n-Bu CH ₂ (c-Pr) CH2CH2NMe31 2-CH2-4-Cl-pyr 187 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH2-3-Cl-pyr 188 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH2-5,6-di-Cl-pyr 189 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH2-5-Cl-pyr 190 HCCCHj 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH2-4-Cl-pyr 191 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH2-2-C1-pyrid 192 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH2-5,6-di-Cl-pyr 193 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH2-2,6-di-Cl-pyr 194 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH2-2-Cl-thiazolyl 195 AcSCH. 5-CH ₂ -2-Me-thiazolyl 2-CH-furyl CH2CHCH2CH2 196 ₂ Et2NCH 5-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH2C (Me) CH2CHü 197 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH3CHCHCH2 198 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl CH3CHCHCH2CH2 199 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et2NCH2CH2 200 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me2NCH2CH2 201 6-Me-3-pyr 2-CH _; 5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH2-1-Me-pyrrolyl 202 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH2-1-Me-pyrrolyl 203 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH2-thiazolyl 204 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl 2-CH2-thienyl 205 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH2-2-Cl-Pyrimidine D1 206 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH2-5-Cl-pyrazyl 207 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH2-6-OCF3-pyr 208 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-Cl-i2-tiadiazil

209 5-Br-2-pyr 3-CH, 6-OCF, pyrrole 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 210 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-thiothiazil 211 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF2-2-tiadiazil 212 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ - -thiadiazil 2-CH2-5-Me-tiadiazil 213 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH2-5-Cl-tiadiazil 214 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH2-3-Cl-isoxazolyl 215 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH2-3-Br-isoxazolyl 216 6-Cl-4-pyr

Table 7 Compounds of general formula (7)

R ^{1 =}

217 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 218 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 219 et 2-Cl-Ph Ac \ HCH ₂ 3-CH ₂ -6-Cl-pyr 220 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 221 i-Pr 4-Cl-Ph CH _; NMe ₃ L 2-CH ₂ -5-Cl-pyr 222 n-Bu CH ₂ (c-Pr) CH, CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 223 s-Bu 2-CH ₂ -pyr CH _; (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 224 i-Bu 3-CH ₂ -pyr CH _; (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 225 Pr-c 4-CH ₂ -pyr CH _: (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 226 hccch ₂ 5-CH ₂ -isoxazolyl CH _: C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 227 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 228 2-pyr CH ₂ (c-Bu) ch _; chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 229 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 230 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 231 AcSCH ₂ 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 232 Et ₂ NCH ₂ 5-CH ₂ -2-Br- thiazolyl 5,6-di-Cl-3-blush CH ₂ C (Me) CH ₂ CH ₂ 233 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 234 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl CH ₃ CHCHCH ₂ CH ₂ 235 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 236 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂

237 6-Me-3-pyr 2-CH, 5-Cl-thienyl 4-CH ₂ - 1-MeIpirazole 2-CH ₂ -1-Me-pyrrolyl 238 6-Br 3-pyr 2-CH _: -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 239 6-F 3-pyr 3-CH _r 6 -Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 240 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 241 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 242 6-Br-2-pyr 2-CH-CFj-6-pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 243 5-Cl-2-pyr 3-CH-b-D-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 244 5-Me-2-pyr 3-CH ₂ -6-CF 3 -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 245 5-Br-2-pyr 3-CH ₂ -b-OCF ₃ -pyr 3-CH ₂ -b-Cl-pyridazyl 5-Me-2-tiadiazil 246 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 247 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 248 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 249 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 250 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 251 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 252 6-Cl-4-pyr

Table 8 Compounds of formula (8) r. =

1 2 3 4 253 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 254 Me CH ₂ Ph NCCHjCH, 2-CH ₂ -6-Cl-pyr 255 et 2-Cl-Ph AcNHCH. 3-CH ₂ -6-Cl-pyr 256 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 257 i-Pr 4-Cl-Ph CH ₂ NMe, I 2-CH ₂ -5-Cl-pyr 258 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ XMe ₃ I 2-CH ₂ -4-Cl-pyr 259 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 260 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 261 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 262 HCCCH, 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 263 NCCH. Me ₂ NCH ₂ HCCCH-CH; 3-CH ₂ -2-Cl-pyr 264 2-pyr CH ₂ (c-Bu) CH ₂ CHCH ₂ 3-CH ₂ -5,6-di-Cl-pyr 265 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 266 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 267 AcSCH. 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl ch ₂ chch ₂ ch ₂ 268 Et _: \ CH ₂ S-CH ₂ -2-Br-thiazolyl 5,6-di-Ci-3-pyr CH ₂ C (Me) CH ₂ CH ₂ 269 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂

270 c-pentyl 3-CH _; pyrazolyl 2-CH ₂ -pyrrolyl ch ₃ chchch ₂ ch ₂ 271 c-hexyl 4-CH _; pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 272 6-F-2-pyr 5-yl-CH 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 273 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl L-2-CH-Me-pyrrolyl 274 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 275 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 276 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 277 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 278 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 279 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 280 S-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 281 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-Thiadiazil · 282 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 283 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 284 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 285 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 286 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 287 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 288 6-Cl-4-pyr

Table 9 Compounds of formula (9)

R ^{1 =}

1 2 3 4 289 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 290 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 291 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 292 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 293 i-Pr 4-Cl-Ph CH ₂ NMe, I 2-CH ₂ -5-Cl-pyr 294 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 295 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 296 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 297 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 298 HCCCH ₂ 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 299 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 300 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 301 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 302 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 303 AcSCHj 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 304 Et ₂ NCH ₂ S-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 305 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 306 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl ch ₃ chchch ₂ ch ₂ 307 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 308 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 309 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 310 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 311 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazole 312 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 313 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 314 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 315 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 316 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 317 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 318 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 319 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 320 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 321 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 322 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-C 1 -isoxazolyl 323 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl

324 6-Cl-4-pyr

Table 10 Compounds of general formula (10)

R ³ =

1 2 3 4 325 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 326 Me CHjPh NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 327 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 328 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 329 i-Pr 4-Cl-Ph CH ₂ NMe ₃ L 2-CH ₂ -5-Cl-pyr 330 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 331 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 332 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 333 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 334 HCCCHj 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 335 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 336 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 337 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 338 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 339 AcSCH ₂ 5-CH _; 2-Me-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 340 EtjNCHj 5-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 341 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₂ CHCHCH ₂ 342 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl ch ₂ chchch ₂ ch ₂ 343 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 344 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1 -Me-pyrazolyl Me, NCH ₂ CH ₂ 345 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 346 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1 -Me-pyrrolyl 347 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl S-CH ₂ -thiazolyl 348 6-OMe 3-pyr 3-CH _; 6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 349 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 350 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 351 5-Cl-2-pyr 3-CH _: -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 352 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 353 5-Br-2-pyr 3-CH ₂ -6-OCF, -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 354 5-F-2-pyr 2-CH _; -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 355 6-OMe-2-pyr 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 356 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -S-CF _; -tiadiazil 2-CH ₂ -5-Me-thiadiazil 357 MeSCHj --CH2 - 6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil

358 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 359 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 360 6-Cl-4-pyr

Table 11 Compounds of Formula 11. R ³ =

1 2 3 4 361 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 362 Me CH 2 Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 363 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 364 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 365 i-Pr 4-Cl-Ph CH ₂ NMe ₃ L 2-CH ₂ -5-Cl-pyr 366 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 367 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 368 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 369 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 370 hccch ₂ 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 371 NCCH ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 372 2-pyr CH (c-Bu); ch ₂ chch ₂ 3-CH-5,6-di-Cl-pyr 373 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 374 4-pyr CH ₂ (e-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 375 AcSCH ₂ 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 376 ₂ Et2NCH 5-CH ₂ -2-Br-thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 377 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 378 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl ch ₃ chchch ₂ ch ₂ 379 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 380 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 381 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 382 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 383 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 384 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 385 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 386 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazil 387 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 388 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 389 5-Br-2-pyr _3-CH2-pyr -6-OCFj 3-CH2-6-Cl-pyridazyl 5-Me-2-tiadiazil 390 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil

391 6-OMe-2-pyr 2-CH _; 6-OMe-pyr 5-CH ₂ -2-Me-pyrimidine S-2-tiadiazil CF. 392 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH _; 5-Me-tiadiazil 393 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 394 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 395 6-Cl 3-pyr 2-CH ₂ -pyrimidyl S-CH ₂ -3-F-isoxazolyl S-CH ₂ -3-Br-isoxazolyl 396 6-Cl-4-pyr

Table 12 Compounds of general formula (12)

R ³ =

1 2 3 4 397 H Ph 2-CH2-5-CF3-thienyl CH ₂ (3,4-di-Cl-Ph) 398 Me CH ₂ Ph NCCH2CH2 2-CH ₂ -6-Cl-pyr 399 et 2-Cl-Ph ICH2-AcNl 3-CH ₂ -6-Cl-pyr 400 n-Pr 3-Cl-Ph AcNHCH2CH2 4-CH ₂ -6-Cl-pyr 401 i-Pr 4-Cl-Ph CH2NMe3I 2-CH ₂ -5-Cl-pyr 402 n-Bu CH ₂ (c-Pr) CH2CH2NMe31 2-CH ₂ -4-Cl-pyr 403 s-Bu 2-CH ₂ -pyr CH2 (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 404 i-Bu 3-CH ₂ -pyr CH2 (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 405 Pr-c 4-CH ₂ -pyr CH2 (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 406 hccch ₂ S-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 407 ncch ₂ Me ₂ NCH, HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 408 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 409 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 410 4-pyr CH ₂ (c-hexyl) AcSCH _: CH ₂ 5-CH ₂ -2-Cl-thiazolyl 411 AcSCH ₂ 5-CH ₂ -2-Me-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 412 ₂ Et2NCH 5-CH ₂ -2-Br- thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 413 c-Bu 2-CH ₂ -S-Me thienyl 5-OMe-2-pyr CH ₃ CHCHCH ₂ 414 c-pentyl 3-CH ₂ -pyrazolyl 2-CH _; pyrrolyl ch ₃ chchch ₂ ch ₂ 415 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 416 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 417 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 418 6-Br 3-pyr 2-CH ₂ -5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 419 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl

··· ·

-42 • · · · · · · · · · ······ · · ·

420 6-OMe 3-pyr 3-CH ₂ -6-OMe-pyr 2-CH _; -3-Me-pyrazolyl _{2-thienyl-CH2} 421 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 422 6-Br-2-pyr 2-CH ₂ -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 423 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 424 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 425 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 426 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 427 6-OMe-2-pyr 2-CH2-6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 428 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ - -thiadiazil 2-CH ₂ -5-Me-thiadiazil 429 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br thienyl 2-CH ₂ -5-Cl-thiadiazil 430 6-el-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Q-isoxazolyl 431 6-Cl 3-pyr 2-CH ₂ -pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 432 6-Cl-4-pyr

Table 13 Compounds of general formula (13)

R ³ =

1 2 3 4 433 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 434 Me CH ₂ Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 435 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 436 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 437 i-Pr 4-Cl-Ph CH ₂ NMe ₃ L 2-CH ₂ -5-Cl-pyr 438 n-Bu CH ₂ (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 439 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 440 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 441 Pr-c 4-CH ₂ -pyr CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr 442 hccch ₂ 5-CH ₂ -isoxazolyl CH ₂ C (Me) CH ₂ 3-CH ₂ -4-Cl-pyr 443 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH ₂ -2-Cl-pyr 444 2-pyr CH ₂ (c-Bu) ch ₂ chch ₂ 3-CH ₂ -5,6-di-Cl-pyr 445 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH ₂ 4-CH ₂ -2,6-di-Cl-pyr 446 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 447 AcSCH ₂ 5-CH ₂ -2-Me- 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂

thiazolyl 448 Et; NCH _; 5-CH 2-Br thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 449 c-Bu 2-CH ₂ -5-Me-thienyl 5-OMe-2-pyr ₂ CHjCHCHCH 450 c-pentyl 3-CH ₂ -pyrazolyl 2-CH ₂ -pyrrolyl CH ₃ CHCHCH ₂ CH ₂ 451 c-hexyl 4-CH ₂ -pyrazolyl 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 452 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 453 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 454 6-Br 3-pyr 2-CH2-5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 455 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 456 b-OMe 3-pyr 3-CH ₂ -6-OMe-Pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 457 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil 5-CH ₂ -2-Cl-pyrimidyl 458 6-Br-2-pyr 2-CH, -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 459 5-Cl-2-pyr 3-CH, 6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 460 5-Me-2-pyr 3-CH ₂ -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 461 5-Br-2-pyr 3-CH ₂ -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 462 5-F-2-pyr 2-CH ₂ -6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-tiadiazil 463 6-OMe-2-blush 2-CH ₂ -6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 464 2-thiadiazolyl 2-CH _: -6-Br-pyr 2-CH ₂ -5-CF 3 - thiadiazil 2-CH ₂ -5-Me-thiadiazil 465 Mesch, 2-CH _; -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 466 6-Cl-2-pyr 5-CH ₂ -pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH2-3-Cl-isoxazolyl 467 6-Cl 3-pyr 2-CH _; pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazolyl 468 6-Cl-4-pyr

Table 14 Compounds of formula (14)

R ³ =

1 2 3 4 469 H Ph 2-CH ₂ -5-CF ₃ -thienyl CH ₂ (3,4-di-Cl-Ph) 470 Me CH _; Ph NCCH ₂ CH ₂ 2-CH ₂ -6-Cl-pyr 471 et 2-Cl-Ph AcNHCH ₂ 3-CH ₂ -6-Cl-pyr 472 n-Pr 3-Cl-Ph AcNHCH ₂ CH ₂ 4-CH ₂ -6-Cl-pyr 473 i-Pr 4-Cl-Ph CH ₂ NMe ₃ L 2-CH ₂ -5-Cl-pyr 474 n-Bu CH- (c-Pr) CH ₂ CH ₂ NMe ₃ I 2-CH ₂ -4-Cl-pyr 475 s-Bu 2-CH ₂ -pyr CH ₂ (2-Cl-Ph) 2-CH ₂ -3-Cl-pyr 476 i-Bu 3-CH ₂ -pyr CH ₂ (3-Cl-Ph) 2-CH ₂ -5,6-di-Cl-pyr 477 Pr-c 4-CH _; -blush CH ₂ (4-Cl-Ph) 3-CH ₂ -5-Cl-pyr

478 HCCCH, 5-CH _; isoxazolyl CH ₂ C (Me) CH ₂ 3-CH, 4-Cl-pyr 479 ncch ₂ Me ₂ NCH ₂ HCCCH ₂ CH ₂ 3-CH, 2-Cl-pyr 480 2-pyr CH (c-Bu) CH ₂ CHCH ₂ 3-CH ₂ -5,6-di-Cl-pyr 481 3-pyr CH ₂ (c-pentyl) MeSCH ₂ CH 3 4-CH ₂ -2,6-di-Cl-pyr 482 4-pyr CH ₂ (c-hexyl) AcSCH ₂ CH ₂ 5-CH ₂ -2-Cl-thiazolyl 483 AcSCHj 5-CH-Me-2-thiazolyl 2-CH ₂ -furyl CH ₂ CHCH ₂ CH ₂ 484 Et ₂ NCH ₂ S-CH-Br-2-thiazolyl 5,6-di-Cl 3-pyr CH ₂ C (Me) CH ₂ CH ₂ 485 c-Bu 2-CH-5-Me-thienyl 5-OMe-2-pyr ch ₃ chchch ₂ 486 c-pentyl 3-yl-CH 2-CH ₂ -pyrrolyl ch ₃ chchch ₂ ch ₂ 487 c-hexyl 4-yl-CH 3-CH ₂ -pyrrolyl Et ₂ NCH ₂ CH ₂ 488 6-F-2-pyr 5-CH ₂ -pyrazolyl 3-CH ₂ -1-Me-pyrazolyl Me ₂ NCH ₂ CH ₂ 489 6-Me-3-pyr 2-CH ₂ -5-Cl-thienyl 4-CH ₂ -1-Me-pyrazolyl 2-CH ₂ -1-Me-pyrrolyl 490 6-Br 3-pyr 2-CH, 5-Me-thienyl 5-CH ₂ -1-Me-pyrazolyl 3-CH ₂ -1-Me-pyrrolyl 491 6-F 3-pyr 3-CH ₂ -6-Me-pyr 2-CH ₂ -pyrazolyl 5-CH ₂ -thiazolyl 492 6-OMe 3-pyr 3-CH, 6-OMe-pyr 2-CH ₂ -3-Me-pyrazolyl _{2-thienyl-CH2} 493 6-Me-2-pyr 3-CH ₂ -6-Br-pyr 2-CH ₂ -5-Me-pyrazil S-CH ₂ -2-Cl-pyrimidyl 494 6-Br-2-pyr 2-CH, -6-CF ₃ -pyr 2-CH ₂ -6-Me-pyrazil 2-CH ₂ -5-Cl-pyrazyl 495 5-Cl-2-pyr 3-CH ₂ -6-F-pyr 3-CH ₂ -pyridazil 2-CH ₂ -6-OCF ₃ -pyr 496 5-Me-2-pyr 3-CH, -6-CF ₃ -pyr 3-CH ₂ -6-Me-pyridazil 2-CH ₂ -thiadiazil 497 5-Br-2-pyr 3-CH, -6-OCF ₃ -pyr 3-CH ₂ -6-Cl-pyridazyl 5-Me-2-tiadiazil 498 5-F-2-pyr 2-CH, 6-Me-pyr 4-CH ₂ -pyrimidyl 5-Cl-2-thiadiazole 1 499 6-OMe-2-pyr 2-CH, 6-OMe-pyr 5-CH ₂ -2-Me-pyrimidyl 5-CF ₂ -2-thiadiazil 500 2-thiadiazolyl 2-CH ₂ -6-Br-pyr 2-CH ₂ -5-CF ₃ -thiadiazil 2-CH ₂ -5-Me-thiadiazil 501 MeSCH ₂ 2-CH ₂ -6-F-pyr 2-CH ₂ -5-Br-thienyl 2-CH ₂ -5-Cl-thiadiazil 502 6-Cl-2-pyr 5-CH, pyrimidyl 5-CH ₂ -3-Meisoxazolyl 5-CH ₂ -3-Cl-isoxazolyl 503 6-Cl 3-pyr 2-CH, pyrimidyl 5-CH ₂ -3-F-isoxazolyl 5-CH ₂ -3-Br-isoxazole 504 6-Cl-4-pyr

-45 · «« • • «ο ο ο * * * * *

In the following Tables 15 and 16, Q is as follows: Q-1 = 6-Cl-3-pyridyl, Q-2 = 5,6-dichloro-3-pyridyl,

Q-3 = 2-chloro-5-thiazole, Q-4 = 3-chloro-5-isoxazolyl, and Q-5 = CH ₃ SCH ₂ -46 *** ♦ · · · t ♦ , · • · ···· 9 β «··« · · · - · 99

505

506

507

508

509

510

511

512

513

514

515

516

517

518

519

512

513

514

515

516

517

518

519

520

521

522

523

524

525

526

527

528

529

Table 15 Compounds of formula (15)

A = single bond; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; ^R 6 = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = single bond; R ² = H; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; A = single bond; R ² = H: R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = single bond; R ² = H; R ³ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ^h = i- Q-L Q-2 Q-3 Q 4 Q-5 Pr; A = single bond; R ² = H; R ³ = Me; R ⁴ = t-Bu; R ^s = Ph; R ^e = Ph; Q-L Q-2 Q-3 Q 4 Q-5 A = single bond; R ² = H; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R6 = Ph; Q i Q-2 3-q Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = t-Bu; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ⁵ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = CH ₂ CH; R ⁵ = Me; R ^e = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = CH ₂ CHCH ₂ ; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; ^O R = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = i-PrO; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = (CH ₂ ) ₃ ; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ CHCH; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ CC; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; ^O R = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = CH ₂ CH ₂ CHCH; R ^: = H; R ³ = Me; R ⁴ = Me; R ^s = Me; ^Delta R = Me; Q i Q-2 Q-3 Q 4 Q-5 A = CH ₂ CH ₂ CC; R ^: = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 A = p-Ph; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 4-q Q-5 A = m-Ph; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = p-Ph; R ² = H; R ^J = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 A = single bond; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; A = single bond; R ² = Me; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5

- 47 * - <- · «« - V * «* ·· β ·» 1

- ♦ «·» '* - · «*

^O R = Me; 530 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 531 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i- Q-L Q-2 Q-3 Q 4 Q-5 Pr; 532 A = valence bond; R ² = Me; R ³ = Me: R ⁴ = t-Bu; R ^s = Ph; Q-L q-2 Q-3 Q 4 Q-5 R ⁶ = Ph; 533 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = Ph; R 1 ⁼ Ph; ^H R = Ph; Q-L Q-2 Q-3 Q 4 Q-5 534 A = valence bond; R ² = H; R ³ = Me; R ⁴ = Me; ^R5 = Ph; R ^e = Ph; Q-L Q-2 Q-3 Q 4 Q-5 535 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q-L q-2 Q-3 Q 4 Q-5 536 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Me; ^R5 = Ph; ^H R = Ph; Q-1 Q-2 3-q Q 4 Q-5 537 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; R ^s = Me; Q-L Q-2 Q-3 Q 4 Q-5 538 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Ph; R ^s = Me; R ⁶ = Me; Q-1 Q-2 Q-3 Q 4 Q-5 539 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 540 A = CH ₂ ; R ^: -Me, R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 541 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 542 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Et; R ⁵ = Me; R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 543 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = CH ₂ CH; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 544 A = CH _2; R ² = Me; R ³ = Me; R ⁴ = CH ₂ CHCH ₂ ; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 545 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 546 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = i-PrO: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 547 A = CH _2; R ² = Me; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 548 A = CH _2; R ² = Me; R ³ = Me; R ⁴ = i-PrO: R ⁵ = i-PrO; R ⁶ = Me: Q-L Q-2 Q-3 Q 4 Q-5 549 A = CH _2; R ² = Me; R ³ = Me; R ⁴ = EtO: R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 550 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = MeO: R ⁵ = MeO; R ^ö = MeO; Q-L Q-2 Q-3 Q 4 Q-5 551 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = MeO: R ⁵ = MeO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 552 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = MeO: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 553 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 554 A = CH _2; R2 = Me; R ³ = Me: R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 555 A = CH ₂ CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = \ k: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 556 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 557 A = CH ₂ CHCH; R ² = Me; R ³ = Me; R = Me: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 558 A = CH ₂ CC; R ² = Me; R ³ = Me; R ⁴ = Me: R ^? = Me; R ⁶ = Me; Q-L Q-2 3-q Q 4 Q-5 559 A = CH ₂ CH ₂ CHCH; R ² = Me; R ⁵ = Me: R ⁴ = Me; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 560 A = CH ₂ CH ₂ CC; R ² = Me; R ³ = Me; R * = Me: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 561 A = o-Ph; R ² = Me; R ³ = Me; R ⁴ = Me; ^R5 = .me; R ⁶ = Me; Q-L Q-2 Q-3 Q g Q- 562 A = m-Ph; R ² = Me; R ³ = Me; R ⁴ = Me: R ⁵ = Me; R ^s = Me; Q-L Q-2 Q-3 Q 4 Q-5

563 A = p-Ph; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; Rc = Me; Q-L Q-2 Q-3 Q 4 Q-5 564 A = CH _2; R ² = H; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 565 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = MeO; R ^s = MeO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 566 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = MeO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 567 A = valence bond; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 568 A = valence bond; R ² = Et; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q- R ⁶ = Me; 569 A = valence bond; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ^e = Me; Q-1 Q-2 Q-3 Q 4 Q 570 A = valence bond; R ² = Et; R ³ = Me; R ⁴ = i-Pr; R ^S = i-Pr; R ⁶ = i- Q-L Q-2 Q-3 Q 4 Q-5 ^Pr; 571 A = valence bond; R ² = Et; R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ^e = Ph; Q-1 Q-2 Q-3 Q 4 Q-5 572 A = valence bond; R ² = Et; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 573 A = valence bond; R ² = Et; R ³ = Me: R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 574 A = CH _2; R ² = Et; R ³ = Me; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 575 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 576 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 577 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q i Q-2 Q-3 Q 4 Q-5 578 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q i q-2 Q-3 Q 4 Q-5 579 A = CH ₂ ; R ² = Et; R ⁵ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 580 A = CH ₂ : R ² = Et; R ³ = Me; R ⁴ = Et; ^R5 = Me, R = Me, ^his; Q-L Q-2 Q-3 Q 4 Q-5 581 A = _CH:; R ² = Et; R ³ = Me; R ^{4 is} CH ₂ CH; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 582 A = CH _2; R ² = Et; R ³ = Me; R ⁴ = CH ₂ CHCH ₂ ; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 583 A = CH ₂ : R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 584 A = CH _2; R ^: = Et; R ³ = Me; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me: Q-L Q-2 Q-3 Q 4 Q-5 585 A = CH _2; R ^: = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 586 A = CH _; : R ^: = Et: R ^: '= .We; R ⁴ = i-PrO; ^R5 = i-PrO; ^O R = Me: Q-L Q-2 Q-3 Q 4 Q-5 587 A = CH _2; R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 588 A = CH _2; R ² = Et; R ³ = Me; R ⁴ = MeO: R ⁵ = MeO; R ⁶ = MeO; Q-L q-2 Q-3 Q 4 Q-5 589 A = CH _2; R ² = Et; R ^? = Me; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 590 A = CH _; : R ^: = Et: R ³ = Me; R ⁴ = MeO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 591 A = CH ₂ : R ^: = Et; R is -Me; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 592 A = _CH2; R ² = Et; R ^J = Me; R ⁴ = H; R ⁵ = Et; Rc = Et; Q i Q-2 Q-3 Q 4 Q-5 593 A = CH ₂ CH _2; R ^: = Et; R ³ = Me; R ⁴ = Me; R ^s = Me; R ⁶ = Me: Q i Q-2 Q-3 Q 4 Q-5 594 A = _{(CH:) 3;} R ² = Et; R ^J = Me; R ⁴ = Me; R ⁵ = Me; R ^s = Me; Q-L Q-2 Q-3 Q 4 Q-5 595-CH = CH _2; R ^: = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 596 A = CH _: CC; R ^: = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 597 A = CH ₂ CH ₂ CHCH; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me: R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 598 A = CH ₂ CH ₂ CC; R ^: = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = .Me; Q-L Q-2 Q-3 Q 4 Q-5

599 A = o-Ph; R ² = Et; ? R = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 600 A = m-Ph; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 601 A = p-Ph; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 602 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 603 A = valence encoding; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 604 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 605 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = i-Pr; ^R5 = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 R ^e = i-Pr; 606 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; ^R5 = Ph; Q-1 Q-2 Q-3 Q 4 Q-5 R ^e = Ph; 607 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; ^R5 = Ph; Q-L Q-2 Q-3 Q 4 Q-5 R ^e = Ph; 608 A = valence bond; R * + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ^s = Ph; Q-1 Q-2 Q-3 Q 4 Q-5 ^H R = Ph; 609 A = CH ₂ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 610 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 611 A = CH ₂ ; R ² 'R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 612 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q i Q-2 Q-3 Q 4 Q-5 613 A = CH ₂ ; R ² -R ³ = -CH.CH _; -. R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 614 A = CH ₂ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph: R ⁵ = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 615 A = CH ₂ ; R ² -R ³ = -CH _; CH ₂ -; R ⁴ = Et; R ⁵ = Me; ^He R = Me; Q-L Q-2 Q-3 Q 4 Q-5 616 A = CH ₂ ; R ² -R ³ = -CH ² CH ² -; R ⁴ = CH ² CH; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 617 A = CH ₂ ; R ² -R ³ = -CH ² CH ² -; R ^{4 is} CH, CHCH 2; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 618 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 619 A = CH ₂ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = i-PrO; R ⁵ = Me; ^Delta R = Me; Q-L Q-2 Q-3 Q 4 Q-5 620 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q i Q-2 3-q Q 4 Q-5 621 A = _CH:; R ² -R ³ = -CH ₂ CH _: -; R ⁴ = i-PrO; ^R5 = i-PrO; ^He R = Me; Q-L Q-2 Q-3 Q 4 Q-5 622 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 623 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 624 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; Q i Q-2 3-q Q 4 Q-5 625 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ^s = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 626 A = CH ₂ ; R ² * R ³ = -CH ₂ CH ₂ -; R ⁴ = H; R ⁵ = Me; ^He R = Me; Q-L Q-2 3-q 4-q Q-5 627 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q i Q-2 Q-3 Q 4 Q-5 628 A = CH ₂ CH ₂ ; R ² + r '= - CH, CH ₂ -; R ⁴ = Me; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 629 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ^s = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5

630 A = CH ₂ CHCH; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 631 CC = _CH2; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; ^Delta R = Me; Q-L Q-2 Q-3 Q 4 Q-5 632 A = CH ₂ CH ₂ CHCH; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 633 A = CH ₂ CH ₂ CC; R ² + R ³ = -CH ₂ CH ₂ -; R = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 634 A = o-Ph; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me: R 1 ⁼ Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 635 A = m-Ph; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 636 A = p-Ph; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-1 Q-2 Q-3 Q 4 Q-5 637 A = valence bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 638 A = valence bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; R ^s = Me; Q-1 Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 639 A = valence bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 640 A = valence bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-Pr; ^R5 = i-Pr; Q i Q-2 Q-3 Q 4 Q-5 R ^ö = i-Pr; 641 A = valence bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; R ^s = Ph; Q-L Q-2 Q-3 Q 4 Q- R ⁶ = Ph; 642 A = valence bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; ^R5 = Ph; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Ph; 643 A = valence bond; R ² + R 1 ⁼ -CH (Me) CH _; -; R ⁴ = Me; ^R5 = Ph; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Ph; 644 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; ^R5 = Ph; ^H R = Ph; Q i Q-2 Q-3 Q 4 Q-5 645 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu: R ⁵ = Me; R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 646 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph: R ^? = Me; ^O R = Me; Q i Q-2 Q-3 Q 4 Q-5 647 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 648 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; R ³ = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 649 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph: R ⁵ = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 650 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Et: R ⁵ = Me; -Me R ^6; Q-L Q-2 Q-3 Q 4 Q-5 651 A = CH _2; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = CH ² CH; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 Rc = Me; 652 A = CH _2; R ² + R ³ = -CH (Me) CH 2 -; R ^{4 is} CH-CHCH 2; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 Rc = Me; 653 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 654 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ <R ⁴ = i-PrO; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 655 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 656 A = CH _2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; Q-L Q-2 Q-3 Q 4 Q-5 R = Me;

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A = CH ₂ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; A = CH2; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ^fl = MeO;

A = CH ₂ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; A = CH2; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = MeO; R ⁵ = Me; R ⁶ = Me; A = CH2; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; A = CH2; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; A = CH ₂ CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me;

R ⁶ = Me;

A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; A = CH2CHCH; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ^s = Me; R ⁶ = Me;

A = CH ₂ CC; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; A = CH ₂ CH ₂ CHCH; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me;

A = CH ₂ CH ₂ CC; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ^s = Me; R ^s = Me;

A = p-Ph; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Me; R ⁵ = Me; ^Delta R = Me; A = m-Ph; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; A = p-Ph; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = iPr; R ^s = iPr; ^R6 = iPr; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = Ph; R ^s = Me; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = EtO; R ⁵ = EtO; R ^e = EtO; A = (CH :) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = MeO: R ⁵ = MeO; R ⁶ = MeO; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH ² CH ² -; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = n-PrO; R ⁵ = n-PrO: R ⁶ = nPrO:

A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; ^R6 = iPrO;

A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; A = (CH 2) ₃ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = iPr; ^R5 = iPr; ^R6 = iPr; A = (CH 2) ₃ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH (Me) CH 2 -; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; A = (CH 2) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO;

R ⁶ = EtO;

Q-L Q-2 Q-3 Q 4 Q-5 Q-L Q-2 Q-3 Q 4 Q-5 Q-L Q-2 Q-3 Q 4 Q-5 Q-L Q-2 Q-3 Q 4 Q-5 Q-1 Q-2 Q-3 Q 4 Q-5 Q-L Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5 Q i Q-2 Q-3 Q 4 Q-5

687 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = MeO; 688 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 689 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = Me; R ^e = Me; Q i Q-2 Q-3 Q 4 Q-5 690 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = n-PrO; ^R5 = n-propyl; Q-L Q-2 Q-3 4-q Q-5 R = n-PrO ^his; 691 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; Q i q-2 Q-3 Q 4 Q-5 R ⁶ = i-PrO; 692 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Et; R ⁵ = Et; R ^s = Et; Q-1 Q-2 Q-3 Q 4 Q-5 693 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 694 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ⁵ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 695 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ^e = Me; Q i Q-2 3-q Q 4 Q-5 696 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q i Q-2 Q-3 Q 4 Q-5 697 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ^s = EtO; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = EtO; 698 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = MeO; 699 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 700 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 701 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q i Q-2 3-q 4-q Q-5 702 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Ph; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 703 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 704 A = CH _2; R ² + R '= - (CH ₂ ) ₃ -; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L q-2 Q-3 Q 4 Q-5 705 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 706 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 707 A = CH _2; R ² + R ³ = - (CH 2) 3 -; R ⁴ = CH ² CH; R ⁵ = Me; R ^s = Me; Q-L Q-2 Q-3 Q 4 Q-5 708 A = CH _2; R ² + R ³ = - (CH 2) 3 -; R ⁴ = CH ₂ CHCH ₂ ; R ⁵ = Me; ^Delta R = Me; Q-L Q-2 Q-3 Q 4 Q-5 709 A = CH _2; R ² + R ³ = - (CH ₂ ) j -; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 710 A = CH ₂ ; R ² + R ^j = - (CH ₂ ) ₃ -; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 711 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) _{3 -} ; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 712 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 713 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ^s = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 714 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ^s = MeO; R ⁶ = MeO; Q i Q-2 Q-3 Q 4 Q-5 715 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 716 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) j -; R ⁴ = MeO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 717 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = H; ^R5 = .me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5

718 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 719 A = CH ₂ CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 720 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 721-CH = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 722 A = CH ₂ CC; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 723 A = CH ₂ CH ₂ CHCH; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 724 A = CH ₂ CH ₂ CC; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 3-q Q 4 Q-5 725 A = o-Ph; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 726 A = m-Ph; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me: R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 727 A = p-Ph; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 728 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 729 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = iPr; R ^s = iPr; ^R6 = iPr; Q i Q-2 Q-3 Q 4 Q-5 730 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Ph; R ^s = Me; R ^e = Me; Q i Q-2 Q-3 Q 4 Q-5 731 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = tBu; R ⁵ = Me; R ^s = Me; Q i Q-2 Q-3 Q 4 Q-5 732 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i q-2 Q-3 Q 4 Q-5 733 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 734 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ^s = EtO; R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 735 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO: R ^$ = Me; R ^s = Me; Q i Q-2 Q-3 Q 4 Q-5 736 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = n-PrO: R ⁵ = n-PrO; R ⁶ = n- Q-L Q-2 Q-3 Q 4 Q-5 PrO; 737 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = i-PrO; Q-L Q-2 Q-3 Q 4 Q-5 738 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 739 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 740 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO: R ⁵ = MeO; ^He R = MeO; Q-L Q-2 Q-3 4-q Q-5 741 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 742 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 743 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 744 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 745 A = (CH ₂ ) ₃ ; R ^J = Me; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 746 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = MeO: R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 747 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 748 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 749 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 750 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 751 A = (CH ₂ ) _} ; R ² = Et; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 752 A = (CH ₂ ) ₄ ; R ² = Me; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 753 A = (CH ₂ ) ₄ ; R ² = Me; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5

754 A = (CH ₂ ) ₄ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 755 A = (CH ₂ ) ₄ ; R ² = Et; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 756 A = (CH ₂ ) ₄ ; R ² + R ³ CH ² CH ² ; R ⁴ = Me ³ Si; R ⁵ = Me ₃ Si; R ⁶ = Me ₃ Si; Q i Q-2 Q-3 Q 4 Q-5 757 A = (CH ₂ ) ₃ ; R ² + R ³ CH ² CH ² ; R ⁴ = Me ³ Si; R ⁵ = Me ₃ Si; R ⁶ = Me ₃ Si; Q-1 Q-2 Q-3 Q 4 Q-5 758 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me ₃ SiCH ₂ ; Q-L Q-2 Q-3 Q 4 Q-5 759 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ₂ CH ₂ ; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me ₃ SiCH ₂ O; Q i Q-2 3-q Q 4 Q-5 760 A = (CH ₂ ) ₃ ; R ² + R ³ CH ² CH ² ; R ⁴ = Me; R ⁵ = Me; R b = Me ₃ SiCH ₂ CH ₂ O; Q i Q-2 Q-3 Q 4 Q-5 761 A = (CH ₂ ) ₃ ; R ² + R ³ CH ² CH ² ; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me ₃ Si CH ₂ CH ₂ S; Q i Q-2 Q-3 Q 4 Q-5 762 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ₂ CH ₂ ; R 4 = Me ₃ SiCH ₂ O; R ⁵ = Me 3 SiCH 2 O; R ⁶ = Me ₃ SiCH ₂ O; Q i Q-2 Q-3 Q 4 Q-5 763 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me ³ Si (CH ₂ ) ² O; R ⁵ = Me 3 Si (CH 2) 2 O; R ^e = Me 3 Si (CH ₂ ) ₂ O; Q i Q-2 Q-3 Q 4 Q-5 764 A = (CH ₂ ) ₃ ; R ² + R ³ CH ₂ CH ₂ ; R ⁴ = MeS; ^R5 = cyclobutyl; R ⁶ = MeS; Q i Q-2 Q-3 Q 4 Q-5 765 A = (CH ₂ ) ₃ ; R ² + R ³ CH ₂ CH ₂ ; R ⁴ = Ph; ^R5 = Ph; R ^e = Me; Q i Q-2 Q-3 Q 4 Q-5 766 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ₂ CH ₂ ; R ⁴ = nBu; ^R5 = nBu; R ^ö = nBu; Q i Q-2 Q-3 Q 4 Q-5 767 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me; R ⁵ = Me ₃ SiCH ₂ ; R ⁶ = Me ₃ SiCH ₂ ; Q i Q-2 Q-3 Q 4 Q-5 768 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 769 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 770 A = CH ₂ ; R ^: = Et; R ³ = Et; R ⁴ = Me; R ⁵ = Me: R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 771 A = CH ₂ ; R ^: + R ³ = -CH ₂ CH ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 772 A = CH ₂ ; R ² + R ³ = CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5

Table 16 Chemical Formulas (16)

773 A = single bond; R ² = H; R ³ = Me; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 774 A = single bond; R ² = H; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 775 A = single bond; R ² = H; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ^s = Me; Q-L Q-2 Q-3 4-q Q-5 776 A = single bond; R ² = H; R ³ = Me; R ⁴ = i-Pr; R ^s = i-Pr; R ⁶ = i-Pr; Q i Q-2 Q-3 Q 4 Q-5

- 55 · **:. ··. ···: ··· · ». .

777 A = valence bond; R ² = H; R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 778 A = bond valuation; R ² = H; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 779 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = t-Bu; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 512 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 513 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 514 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = t-Bu; R ^s = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 515 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 516 A = CH ₃ ; R ² = H; R ³ = Me; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 517 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = CH ₂ CH; R ⁵ = Me; ^Delta R = Me; Q-L Q-2 Q-3 Q 4 Q-5 518 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = CH ₂ CHCH ₂ ; R ⁵ = Me; ^He R = Me; Q-L Q-2 Q-3 Q 4 Q-5 519 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 780 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 781 A = CH _2; R ² = H; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 782 A = CH _2; R ² = H; R ³ = Me; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 783 A = CH _2; R ² = H; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i q-2 Q-3 Q 4 Q-5 784 A = CH _2; R ² = H; R ³ = Me; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = i-PrO; Q i Q-2 Q-3 Q 4 Q-5 785 A = CH ₂ : R ² = H; R ³ = Me; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 786 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = H; R ⁵ = Et; R ^s = Et; Q i Q-2 Q-3 Q 4 Q-5 787 A = CH ₂ CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 788 A = (CH ₂ ) ₃ ; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 789-CH = CH _2; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 790 A = CH ₂ CC; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 791 A = CH ₂ CH ₂ CHCH; R ² = H; R ³ = Me; R ⁴ = Me; R ^} = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 792 A = CH ₂ CH ₂ CC; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 793 A = o-Ph; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 794 A = m-Ph; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ^s = Me; Q i Q-2 Q-3 Q 4 Q-5 795 A = p = Ph; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 796 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = Me; R ^s = Me; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 797 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 798 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5 ^Delta R = Me; 799 A = valence bond; R ² = Me; R ³ = Me: R ⁴ = i-Pr; ^R5 = i-Pr; R ^ö = i- Q i Q-2 Q-3 Q 4 Q-5 Pr; 800 A = valence bond; R ² = Me; R ³ = Me: R ⁴ = t-Bu; ^R5 = Ph; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Ph; 801 A = valence bond; R ² = Me; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5

802 A = single bond; R ² = H; R ³ = Me; R ⁴ = Me; R ^{5 is} -Ph; R ⁶ -Ph; Q-L Q-2 Q-3 Q 4 Q-5 803 A = CH ₂ ; R ² = H. R ³ = Me; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 804 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Me; R ^s = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 805 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = t-Bu; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 806 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Ph; R ³ = Me; ^He R = Me; Q-L Q-2 Q-3 Q 4 Q-5 807 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = i-Pr; R ^s = i-Pr; R ⁶ = i-Pr; Q-L Q-2 Q-3 4-q Q-5 808 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = t-Bu; R ^s = Ph; ^H R = Ph; Q-L Q-2 Q-3 Q 4 Q-5 809 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Ph; R ^s = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 810 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 811 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = CH ₂ CH; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 812 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = CH ₂ CHCH ₂ ; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 4-q Q-5 813 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = EtO; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 814 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 815 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = EtO; R ^s = EtO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 816 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 817 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = EtO; R ^s = EtO; R ^e = EtO; Q i Q-2 Q-3 Q 4 Q-5 818 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = MeO: R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 819 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = MeO; R ^s = MeO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 820 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = MeO: R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 821 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = H; R = \ IU; ^O R = Me; Q-L Q-2 Q-3 Q 4 Q-5 822 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = H; R 1 ⁼ Et; Rc = Et; Q-L Q-2 Q-3 Q 4 Q-5 823 A = CH ₂ CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 824 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 825 A = CH ₂ CHCH; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; ^Delta R = Me; Q-L Q-2 Q-3 Q 4 Q-5 826 A = CH ₂ CC; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 827 A = CH ₂ CH ₂ CHCH; R ² = Me; R ⁵ = Me: R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 828 A = CH ₂ CH ₂ CC; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 829 A = p-Ph; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 830 A = m-Ph; R ² = Me; R ³ = Me; R ⁴ = Me: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 831 A = p-Ph; R ² = Me; R ³ = Me; R ⁴ = Me: R ⁵ = x Me: R ^s = Me; Q-L Q-2 Q-3 Q 4 Q-5 832 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 833 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 834 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = MeO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 835 A = single bond; R ² = Et; R ³ = Me: R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 836 A = single bond; R ² = Et; R ³ = Me: R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 837 A = valence bond: R ² = Et; R ³ = Me: R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5

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838 A = single bond; R ² = Et; R ³ = Me; R ⁴ = i-Pr; R ⁵ -i-Pr; ^R6 -i- Pr; Q-L Q-2 Q-3 Q 4 Q-5 839 A = single bond; R ² = Et; R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 840 A = single bond; R ² = Et; R ³ = Me; R ⁴ = Ph; ^R5 = Ph; R ^e = Ph; Q i Q-2 Q-3 Q 4 Q-5 841 A = single bond; R ² = Et; R ³ = Me; R ⁴ = Me; ^R5 = Ph; R ^e = Ph; Q-L Q-2 Q-3 Q 4 Q-5 842 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = Me; ^R5 = Ph; R ^e = Ph; Q-L Q-2 Q-3 Q 4 Q-5 843 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 844 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 845 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 846 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 847 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ^s = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 848 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 849 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = CH ₂ CH; R ^s = Me; R = Me; Q i Q-2 Q-3 Q 4 Q-5 850 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = CH ₂ CHCH ₂ ; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 851 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 852 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 3-q Q 4 Q-5 853 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ^s = Me; Q i Q-2 Q-3 Q 4 Q-5 854 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 855 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 856 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 857 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; Rc = Me; Q-L Q-2 Q-3 Q 4 Q-5 858 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = MeO; R ⁵ = Me; ^O R = Me; Q-L Q-2 Q-3 Q 4 Q-5 859 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = H; R ⁵ = Me; R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 860 A = CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 861 A = CH ₂ CH ₂ ; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; Rc = Me; Q-L Q-2 Q-3 Q 4 Q-5 862 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 863 A = CH ₂ CHCH; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 864 A = CH ₂ CC; R ² = Et; R ³ = Me; R ⁴ = Me: R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 865 A = CH ₂ CH ₂ CHCH; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 866 A = CH ₂ CH ₂ CC; R ² = Et; R ³ = Me; R ⁴ = Me; R 1 ⁼ Me; ^O R = Me; Q i Q-2 Q-3 Q 4 Q-5 867 A = p-Ph; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 868 A = m-Ph; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; ^O R = Me; Q i Q-2 Q-3 Q 4 Q-5 869 A = p-Ph; R ² = Et; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 870 A = direct bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ^! = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 871 A = single bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; R ⁵ = Me; R ^s = Me; Q i Q-2 Q-3 Q 4 Q-5 872 A = single bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5

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^O R = Me; 873 A = valence bond; R ⁵ + R ³ = -CH ₂ CH ₂ -; R ⁴ = I-Pr; ^R5 = i-Pr; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = i-Pr; 874 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; ^R5 = Ph; Q-L Q-2 Q-3 Q 4 Q-5 R ^a = Ph; 875 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; ^R5 = Ph; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Ph; 876 A = valence bond; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; ^R5 = Ph; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Ph; 877 A = CH _2; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 878 A = CH _2; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; R ⁵ = Me: R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 879 A = CH ₂ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L q-2 Q-3 4-q Q-5 880 A = CH ₂ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q-1 Q-2 Q-3 Q 4 Q-5 881 A = CH _2; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 882 A = CH _2; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 883 A = CH _2; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 884 A = CH _2; R ² ^ R ³ = -CH ² CH ² -; R ⁴ = CH ² CH; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 885 A = CH ₂ ; R ² + R ³ = -CH ² CH ² -; R ^{4 is} CH ₂ CHCH ₂ ; R ⁵ = Me; R ⁶ = Me Q i Q-2 Q-3 Q 4 Q-5 886 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = Me; R ^s = Me; Q i Q-2 3-q Q 4 Q-5 887 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 888 A = CH _2; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 889 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 890 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 891 A = CH _2; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 892 A = CH _2; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; ^He R = Me; Q-L Q-2 Q-3 Q 4 Q-5 893 A = CH _2; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 894 A = _CH2; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 895 A = CH ₂ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 896 A = CH ₂ CH ₂ : R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 897 A = (CH ₂ ) ₃ ; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 The 898-CH = CH _2; R ^: -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 899 A = CH ₂ CC; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 900 A = CH ₂ CH ₂ CHCH: R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; Q-L Q-2 3-q 4-q Q-5 R ⁵ = Me; R ⁶ = Me 901 A = CH ₂ CH ₂ CC; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 902 A = o-Ph: R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; ^O R = Me; Q-L Q-2 Q-3 Q 4 Q-5 903 A = m-Ph; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 904 A = p-Ph; R ² -R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5

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905 A = single bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ -Me; ^R5-Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 906 A = single bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me Q-L Q-2 Q-3 Q 4 Q-5 907 A = single bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; R ⁵ = Me; R ^< = Me Q-L Q-2 Q-3 Q 4 Q-5 908 A = single bond; R ² + R ³ = -CH (Me) CH _r ; R ⁴ = i-Pr; R ^s = i-Pr; R ⁶ = i-Pr; Q-1 Q-2 Q-3 Q 4 Q-5 909 A = single bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 910 A = single bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 911 A = single bond; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 912 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 913 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; R ^s = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 914 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 915 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-Pr; R ^s = i-Pr; R ⁶ = i-Pr; Q i Q-2 Q-3 Q 4 Q-5 916 A = CH ₂ ; R ² -R ³ = -CH (Me) CH ₂ -; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q i Q-2 Q-3 Q 4 Q-5 917 A = CH ₂ ; R ² -R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 918 A = CH ₂ ; R ² -R ³ = -CH (Me) CH ₂ -; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 919 A = CH ₂ ; R ² -R ³ = -CH (Me) CH 2 -; R ⁴ = CH ² CH; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 920 A = CH ₂ ; R ^: -R ³ = -CH (Me) CH 1 -; R ⁴ CH ₂ CHCH ₂ ; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 921 A = CH ₂ ; R ^: -R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ^s = Me; R ^s = Me; Q i Q-2 Q-3 Q 4 Q-5 922 A = CH ₂ ; R ² -R ³ = -CH (Me) CH ₂ -; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 923 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 924 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 925 A = CH ₂ ; R ² -R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ^he = EtO; Q-L Q-2 Q-3 Q 4 Q-5 926 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ^J = MeO; R ⁵ = MeO; R ^s = MeO, Q-L Q-2 Q-3 Q 4 Q-5 927 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 928 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = .MeO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 929 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 930 A = CH ₂ ; R ² -R ³ = -CH (Me) CH ₂ -; R ⁴ = H; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 931 A = CH ₂ CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -: R ⁴ = Me; R ⁵ = Me; Q-L Q-2 Q-3 Q 4 Q-5

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932 R ^a = Me; A = (CH ₃ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q-I Q-2 Q-3 Q 4 Q-5 933 A = CH ₂ CHCH; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; Q-L Q-2 Q-3 Q 4 Q-5 934 R ⁵ = Me; R ⁶ = Me, A = CH ₂ CC; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 935 A = CH ₂ CH ₂ CHCH; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; Q-L Q-2 Q-3 Q 4 Q-5 936 R ⁵ = Me; R ⁶ = Me, A = CH ₂ CH ₂ CC; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; Q-1 Q-2 Q-3 Q 4 Q-5 937 R ⁵ = Me; R ⁶ = Me A = o-Ph; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 938 A = m-Ph; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 4-q Q-5 939 A = p-Ph; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 940 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q i Q-2 Q-3 4-q Q-5 941 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = iPr; ^R5 = iPr; R ^ö = iPr; Q i Q-2 Q-3 Q 4 Q-5 942 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 943 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 944 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i q-2 Q-3 Q 4 Q-5 945 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ^s = MeO; R ⁶ = MeO; Q i Q-2 Q-3 Q 4 Q-5 946 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO, R ⁵ = EtO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 947 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 948 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = n-PrO; ^R5 = n-propyl; R ^.delta n- Q i Q-2 Q-3 4-q Q-5 949 PrO; A = (CH ₂ ) ₃ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = i- Q i Q-2 Q-3 Q 4 Q-5 950 PrO, A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q i Q-2 Q-3 Q 4 Q-5 951 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = iPr; ^R5 = iPr; ^R6 = iPr; Q i Q-2 Q-3 Q 4 Q-5 952 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 953 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 954 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -. R ⁴ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 955 R ⁵ = EtO; R ⁶ = EtO; A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 956 R ⁵ = MeO; R ⁶ = MeO; A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 957 R ⁶ = Me; A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 958 A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = n-PrO; ^R5 = n-propyl; Q-L Q-2 Q-3 Q 4 Q-5 959 R ^ö = n-propyl; A = (CH ₂ ) ₃ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = i-PrO; ^R5 = i-PrO; Q i Q-2 Q-3 Q 4 Q-5

* · * ·

R ⁶ = i-PrO; 960 A = (CH ₂ ) ₄ ; R ² + r '= - CH ₂ CH ₂ -; R ⁴ = Et; R ^s = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 961 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 962 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = MeO; Q i Q-2 Q-3 Q 4 Q-5 963 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = EtO; R ^s = EtO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 964 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Et; R ^s = Et; R ⁶ = Et; Q-1 Q-2 Q-3 Q 4 Q-5 965 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ^s = EtO; Q-1 Q-2 Q-3 Q 4 Q-5 R ⁶ = EtO; 966 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = MeO; R ^s = MeO; Q-1 Q-2 Q-3 Q 4 Q-5 R ⁶ = MeO; 967 A = (CH ₂ ) ₄ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = EtO; R ⁵ = EtO; Q-L Q-2 Q-3 Q 4 Q-5 R ⁶ = Me; 968 A = _CH2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; ^R5 = Ph; R ^e = Ph; Q i Q-2 Q-3 Q 4 Q-5 969 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = t-Bu; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 970 A = CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Ph; R ^s = Me; R ^e = Me; Q i Q-2 Q-3 Q 4 Q-5 971 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = i-Pr; ^R5 = i-Pr; R ⁶ = i-Pr; Q i Q-2 Q-3 Q 4 Q-5 972 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = t-Bu; ^R5 = Ph; R ⁶ = Ph; Q-L Q-2 Q-3 Q 4 Q-5 973 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Ph; ^R5 = Ph; ^His R = Ph; Q i Q-2 3-q Q 4 Q-5 974 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Et; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 975 A = CH _2; R ² + R ³ = - (CH 2) 3 -; R ⁴ = CH ² CH; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 976 A = CH _2; R ² + R ³ = - (CH 2) 3 -; R ⁴ = CH ₂ CHCH ₂ ; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 977 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 978 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = i-PrO; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 979 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ^e = Me; Q i Q-2 Q-3 Q 4 Q-5 980 A = CH _2; R ^: -R ³ = - (CH ³ ), -; R ⁴ = i-PrO; ^R5 = i-PrO; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 981 A = CH _2; R ^: -R ³ = - (CH ₂ ) -; R ⁴ = EtO; R ^s = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 982 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = MeO: R ⁶ = MeO; Q i Q-2 Q-3 Q 4 Q-5 983 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = MeO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 984 A = CH _2; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 985 A = CH _2; RYr ³ = - (CH ₂ ) ₃ -; R ⁴ = H; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 986 A = CH _2; R ^: + R ³ = - (CH ₂ ) ₃ -; R ⁴ = H; R ⁵ = Et; ^He R = Et; Q i Q-2 Q-3 Q 4 Q-5 987 A = CH ₂ CH ₂ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 988 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q i Q-2 3-q Q 4 Q-5 989 A = CH ₂ CHCH R ² + R ³ = - (CH ₂ ) j -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 990 A = CH ₂ CC; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 3-q Q 4 Q-5 991 A = CH ₂ CH ₂ CHCH; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; Q i Q-2 3-q Q 4 Q-5 R ⁶ = Me; 992 A = CH ₂ CH ₂ CC; R ² + R '= - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5

-62 • ····· · · · · · · · · ············

993 A = o-Ph; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 994 A = m-Ph; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 995 A = p-Ph; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Me; R ^s = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 996 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 997 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = iPr; ^R5 = iPr; ^R6 = iPr; Q-L Q-2 3-q Q 4 Q-5 998 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 999 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = tBu; R ⁵ = Me; ^He R = Me; Q-L Q-2 Q-3 Q 4 Q-5 1000 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -j R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q-L Q-2 3-q Q 4 Q-5 1001 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = MeO; R ^e = MeO; Q-L Q-2 Q-3 Q 4 Q-5 1002 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-1 Q-2 Q-3 Q 4 Q-5 1003 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = Me: R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 1004 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = n-PrO; ^R5 = n-propyl; R ⁶ = n- Q i Q-2 Q-3 Q 4 Q-5 PrO; 1005 A = (CH ₂ ) ₃ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = I-PrO; ^R5 = i-PrO; R ⁶ = i-PrO; Q-L Q-2 Q-3 Q 4 Q-5 1006 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q i Q-2 Q-3 Q 4 Q-5 1007 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 1008 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = MeO; R ⁵ = MeO; R ^s = MeO; Q-L Q-2 Q-3 Q 4 Q-5 1009 A = (CH ₂ ) ₄ ; R ² + R ³ = - (CH ₂ ) ₃ -; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 1010 A = (CH ₂ ) ₃ : R ² = Me; R ³ = Me; R ⁴ = Et; R ⁵ = Et; R ⁶ = Et; Q-L Q-2 Q-3 Q 4 Q-5 1011 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 1012 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 1013 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 1014 A = (CH ₂ ) ₃ ; R ² = Me; R ³ = Me; R ⁴ = MeO; R ⁵ = MeO; ^He R = MeO; Q i Q-2 Q-3 Q 4 Q-5 1015 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = Et; R ^s = Et; ^He R = Et; Q-L Q-2 Q-3 Q 4 Q-5 1016 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 1017 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 1018 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = EtO; R ⁵ = EtO; R ⁶ = EtO; Q i Q-2 Q-3 Q 4 Q-5 1019 A = (CH ₂ ) ₃ ; R ² = Et; R ³ = Me; R ⁴ = MeO: R ⁵ = MeO; R ⁶ = MeO; Q-L Q-2 Q-3 Q 4 Q-5 1020 A = (CH ₂ ) ₄ ; R ² = Me; R ³ = Me; R ⁴ = Ph; ^R5 = Me, R ^e = Me; Q-L Q-2 Q-3 Q 4 Q-5 1021 A = (CH ₂ ) ₄ ; R ² = Me; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q-L Q-2 Q-3 Q 4 Q-5 1022 A = (CH ₂ ) ₄ ; R ² = Et; R ³ = Me; R ⁴ = Ph; R ⁵ = Me; ^He R = Me; Q i Q-2 Q-3 Q 4 Q-5 1023 A = (CH ₂ ) ₄ ; R ² = Et; R ³ = Me; R ⁴ = tBu; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 1024 A = (CH ₂ ) ₄ ; R ² + R ³ CH ² CH ² ; R ⁴ = Me ³ Si; R ⁵ = Me ₃ Si; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me ₃ Si; 1025 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me ³ Si; R ⁵ = Me ₃ Si; Q i Q-2 Q-3 Q 4 Q-5 R ⁶ = Me ₃ Si; 1026 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = .Me; R ^s = Me; R ⁶ = Me ₃ SiCH ₂ ; Q i Q-2 Q-3 Q 4 Q-5 1027 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ₂ CH ₂ ; R ⁴ = Me; R ⁵ = Me; Q i Q-2 Q-3 Q 4 Q-5

1028 R ^s = Me ₃ SiCH ₂ O; A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me ₃ SiCH ₂ CH ₂ O; Q-L Q-2 Q-3 Q 4 Q-5 1029 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me ₃ SiCH ₂ CH ₂ S; Q-L Q-2 Q-3 Q 4 Q-5 1030 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me ₃ SiCH ₂ O; R ⁵ = Me 3 SiCH 2 O; R ⁶ = Me ₃ SiCH ₂ O; Q-1 Q-2 Q-3 Q 4 Q-5 1031 A = (CH ₂ ) ₃ ; R ² -R ³ = CH ² CH ² ; R ⁴ = Me ³ Si (CH ₂ ) ₂ O; R ⁵ = Me 3 Si (CH 2) 2 O; ^O R = Me 3 Si _{(CH2) 2} O; Q-1 Q-2 Q-3 Q 4 Q-5 1032 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ₂ CH ₂ ; R ⁴ = MeS; ^R5 = cyclobutyl; R ⁶ = MeS; Q i Q-2 Q-3 Q 4 Q-5 1033 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ₂ CH ₂ ; R ⁴ = Ph; ^R5 = Ph; R ⁶ = Me; Q i Q-2 3-q Q 4 Q-5 1034 A = (CH ₂ ) ₃ ; R ² + R ³ CH ₂ CH ₂ ; R ⁴ = nBu; ^R5 = nBu; ^R6 = nBu; Q-L Q-2 Q-3 Q 4 Q-5 1035 A = (CH ₂ ) ₃ ; R ² + R ³ = CH ² CH ² ; R ⁴ = Me; R ⁵ = Me ₃ SiCH ₂ ; R ⁶ = Me ₃ SiCH ₂ ; Q i Q-2 Q-3 Q 4 Q-5 1036 A = CH ₂ ; R ² = H; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 1037 A = CH ₂ ; R ² = Me; R ³ = Me; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 1038 A = CH ₂ ; R ² = Et; R ³ = Et; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 1039 A = CH ₂ ; R ² + R ³ = -CH ₂ CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ⁶ = Me; Q i Q-2 Q-3 Q 4 Q-5 1040 A = CH ₂ ; R ² + R ³ = -CH (Me) CH ₂ -; R ⁴ = Me; R ⁵ = Me; R ^ü = Me; Q i Q-2 Q-3 Q 4 Q-5

- 64 Preparations / Applications

The compounds of the present invention are generally administered in the form of their formulations together with an agriculturally suitable carrier which is a liquid or solid diluent. The formulations may be in the form of powders, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowable materials, etc., which correspond to the physical properties of the active ingredient, application method, environmental factors such as soil type. , humidity and temperature. Sprayable formulations may be diluted with a suitable medium and the applied spray volume will generally be in the range of one to hundreds of liters per hectare. High strength formulations are generally used as starting materials for further formulations. The formulations generally contain an effective amount of the active ingredient in admixture with a diluent and a surfactant, which together form 100% by weight.

weight Percent

agent thinner Material surfactant material Wettable powders 5-90 0-70 1-10 Oily suspensions, emulsions, solutions (including emulsifiable concentrates) 5-50 40-95 0-15 powders 1-25 70-99 0-5 Granules, baits, pellets 0.01-99 5-99.99 0-15 High strength formulations 90-99 0-10 0-2

Solid diluents are described, for example, in Watkins et al., Handbook of Insecticide Diluents and Carriers, 2nd edition, Dorland Books, Caldwell, New Jersey. Liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950 McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corpl., Ridgewood, New Jersey, and surfactants and various applications are described in Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publication Co., Inc., New York, 1964. Any composition may contain small amounts of various additives for foaming, lumping, corrosion, microbiological growth, etc. inhibition.

The solutions are obtained by simple mixing of the ingredients. A fine solid composition is obtained by mixing and generally milling in a hammer mill or fluidization mill. Water-dispersible granules are obtained by agglomeration of fine powder (Cross et al., Pesticide Formulations, Washington, D.C., 1988, 251-259). The suspensions are obtained by wet milling (e.g., US 3,060,084). Granules and pellets, for example, are prepared by spraying or pre-agglomerating the active ingredient on a preformed granular carrier (Browning, Agglomeration, Chemical Engineering, December 4, 1967, 147-148, Perry's Chemical Engineer's Handbook, 4th Edition). , McGraw-Hill, New York, 8-3, 1963, and WO 91/13546).

- 66 For example, reference is made to US 3 235 361 (Column 6, line 16 to column 7, line 19 and Examples 10-41) for the preparation of various brewings.

US 3,309,192 (column 5, line 43 to column 7, line 62 and 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140), Examples 162-164, 166, 167, and 169-182), US 2,891,855 (Column 3, Line 66 to Column 5, Line 17 and Examples 1-4), and (Klingman, Weed Control as Science, John Wiley and Sons, Inc., New York, 1961, 81-96; and Hance et al., Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford, 1989).

The following examples illustrate the composition of some of the formulations prepared in the conventional manner. The number of compounds refers to Table A.

The example

Wettable Powder Compound 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium glycol lignin sulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%

Example B Granule Compound 10.0% Attapulgite Granules (Low Volatility 0.71 / 0.30 mm,

ÜSS No. 25-50 Sieve 90.0%

Example C

Extruded pellets

- 67 Compound 25.0% Sodium Sulfate Anhydrous 10.0% Crude Calcium Lignin Sulfonate 5.0% Sodium Alkyl Naphthalene Sulfonate 1.0% Calcium Magnesium Benton 59.0%

Example D

Emulsifiable Concentrate Compound 20.0% Mixture of Oily Soluble Sulfonates and Polyethyleneoxy Ethers 10.0% Isophorone 70.0%

The compounds of the present invention exhibit a broad spectrum of activity against arthropods, foliar, arthropods attacking foliage, fruit attack, stem or root, seed attack, water or soil, and the term "arthropods" includes insects, mites and nematodes cultivated and stored agricultural crops, forests, greenhouses, ornamental plants, seedlings, stored food and fiber products, livestock, households, and human and animal health. It will be apparent to those skilled in the art that not all compounds are equally effective against different growth stages of pests. However, all of the compounds of the invention are effective against insects, which include: eggs, larvae, and adult parrots of the genus Lepidoptera; eggs of the genus Coleoptera, larvae and adult larvae and adult specimens of the genus 68, eggs of the genus Hemiptera and Homoptera, immature and adult forms, eggs and larvae of the genus Acari, larvae and larvae and the eggs, immature and adult forms of the genus Dermaptera, the eggs, the immature and adult forms of the genus Diptera, and the eggs, juveniles and adult forms of Phylum Nematoda. The compounds of the present invention are also effective against the following pests: Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; Pests of the Class Arachnida and Phylum Platyhelminthes. The compounds of the invention are particularly active against the following pests: Diabrotica undecimpunctata howardi, Mascrosteles fascifrons, Anthonomus grandis, Tetranychus urticae, Spodoptera frugiperda, Aphis fabae,

Myzus persica, Aphis gossypii, Diuraphis noxia, Sitobion avenae, Heliothis virescens, Lissorhoptrus oryzophilus, Oulema oryzae, Sogatella furcifera, Nephotettix cincticeps, Nilaparvata lugens, Laodelphax striatellus, Chilo suppressalis

Cnaphalocrocis medinalis, Scotinophara lurida, Oebalus pugnax, Leptocorisa chinensis, Cletus puntiger, Nezara viridula. The compounds are active against mites and exhibit ovicidal, larval, and chemosterilic activity against the following pests: Tetranychidae family, including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacifcus, Panetrianchia, Tetranychus turkestani, Eotetranychus, hicoriae, Eotetranychus

- 69 • · »·

sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensv, family Tenuipalpidae such as Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatu; Eriophyidae such as Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. WO 90/10623 and WO 92/00673 provide an even more detailed description of pests.

The compounds of the present invention may also be admixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, plant growth regulators, chemosterilics, semiochemicals, insecticides, bait agents, other active substances and other biocidal agents, Component A, a broader spectrum pesticide is obtained. Examples of useful agricultural agents with which the active compounds of the present invention can be formulated together include insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, phonophos, isofenphos, methidathion, phha terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, tefluthrin, fenpropathrin, fluvalinate, flucythrinate,

tralomethrin, imidacloprid, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanyl, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, oxtafol, , myclobutanyl, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper, isoprothiolane, iprobenfos, mepronil, neo-azosine, pencycuron, probenazole, pyroquilone, tricyclazole, validamycin, and flutolanyl; nematocides such as aldoxycarb, fenamiphos fosthietan; bactericides such as oxytetracyline, streptomycin

Copper sulfate 3, acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as entopathogenic bacteria, viruses and fungi.

In some cases, combinations with anti-anthropod agents that act on similar pests but have a different mechanism of action are particularly beneficial in preventing resistance.

The control of arthropod pests and the protection of agricultural, horticultural and specialty crops, and the protection of animal and human health by applying an effective amount of one or more compounds of the invention to the environment of the pests, such as agricultural and / or non-agricultural infected areas. , directly to the areas you want to protect, or the pest you want to destroy. Thus, the invention also encompasses a method for controlling arthropod and nematode pests on foliage or soil, and for protecting agricultural and / or non-agricultural crops, comprising applying an effective amount of one or more compounds of the invention or one or more such compounds. such as the agricultural and / or non-agricultural infected area, the area to be protected or directly the pest to be destroyed. A preferred method of application is spraying. Alternatively, granular formulations may be applied to the foliage of plants or to the soil. Other methods include direct spraying, aerial spraying, seed coating, microcapsulation, systemic application of bait materials, bolus formulations, mist and smoke formulations, aerosols, powders, and the like. The compounds may also be incorporated into bait materials which are consumed by arthropods or made into various devices such as traps, etc.

The compounds of the present invention may be administered alone, but will most often be administered in the form of compositions comprising one or more compounds in association with suitable carriers, diluents, surfactants, optionally diets, depending on the intended use. Preferred methods include spraying aqueous dispersions or oily solutions. Combination 72 -

Spray oils, sprayable oil concentrates, dispersants, adjuvants, and synergists and other solvents such as piperidone butoxide often increase the potency of the compounds.

The following test examples illustrate the efficacy of the compounds of the invention against particular pests. "Effectiveness of killing" refers to the inhibition of the development of arthropods (including killing) caused by significantly reduced food intake. However, the pesticidal activity of the compounds of the invention is not limited to these varieties. See Tables A-E for compounds.

The following table shows compounds of formula (1/1)

Dry. number R ¹ r ² + r ³ mp (° C) config. (the) 1 _3-CH2 6-Cl-pyr -CH (CH ₃ ) CH ₂ - ^(b) 112-115 racemic 2 3-CH ₂ 6 -Cl-pyr -CH (CH ₃ ) CH ₂ - ^(b) 145-147 R 3 3-CH ₂ 6 -Cl-pyr -CH ₂ CH ₂ - 145.5 to 147.0 achiral 4 5-CH ₂ -2-Cl-thiazole -ch ₂ ch ₂ - 148-151 achiral 5 5-CH ₂ -2-Cl-thiazole -CH (CH ₃ ) CH ₂ - ^(b) 133-137 racemic 6 MaSCH ₂ CH ₂ -CH ₂ CH ₂ - 105-107 achiral 7 MaSCH ₂ CH ₂ -CH (CH ₃ ) CH ₂ - ^(b) oil racemic 8 3-CH ₂ -pyr -CH ₂ CH ₂ - 158.5 to 160.0 achiral 9 3-CH ₂ -pyr -CH (CH ₃ ) CH ₂ - ^(b) 155.0 to 156.5 racemic 10 3-CH ₂ -5,6-di-Cl-pyr -CH ₂ CH ₂ - 162.5 to 164.0 achiral 11 3-CH ₂ -6-Cl-pyr - (CH ₂ ) ₃ - 89-93 achiral 12 5-CH ₂ -3-Meisoxazil -ch ₂ ch ₂ - 116-118 achiral

Dry. R ¹ R ² R ³ op (° C) config.

sama

3-CH ₂ -6-Cl-pyr Et Me oil acylic (a) The configuration refers to the configuration of the chiral carbon atom. The "R" designation was determined by the Cahn, Ingold, and Prelog method. The term "racemic" refers to a compound containing substantially the same amount of R and S enantiomers. The term "achiral" means that the compound does not contain a chiral center.

(b) the CH carbon atom linked to the nitrogen atom carrying the R ¹ substituent.

Table B Compounds of Formula 1/2

Dry. number R THE R ⁴ R ⁵ R ⁶ mp (° C) config / 14 H (CH ₂ ) ₃ EtO EtO EtO 140-142 achiral 15 H (CH ₂ ) ₃ Sample check Sample check Sample check 87-90 akirláis 16 H (CH ₂ ) ₃ EtO EtO Me 112-114 achiral 17 H (CH ₂ ) ₄ EtO EtO Me 97-98 achiral 18 Me (CH ₂ ) ₃ EtO EtO EtO 138-140 racemic 19 H ch ₂ Ph Me Me 147-149 achiral 20 Me ch ₂ Ph Me Me oil racemic 21 Me ch ₂ Ph Me Me oil R 22 Me (CH ₂ ) j Ph Me Me 81-85 racemic 23 H (CH ₂ ) ₃ Ph Me Me 133-136 achiral

24 H (CH ₂ ) ₃ Bu Me Me 152-153 25 H (CH ₂ ) ₃ Wt et et 148-150 26 H (ch ₂ ) ₃ Ph Ph Ph 144-149

airiral airiral airiral (a) The configuration refers to the configuration of the chiral carbon atom. The "R" designation was determined by the Cahn, Ingold, and Prelog method. The term "racemic" refers to a compound containing substantially the same amount of R and S enantiomers. The term "achiral" means that the compound does not contain a chiral center.

In the following table, the symbols are as follows: Q1 = 6-Cl-3-pyridyl, Q-2 = 5,6-dichloro-3-pyridyl, Q-3 = 2-chloro-5-thiazole and Q-5 = CH ₃ SCH ₂ -.

Table C Compounds of formula (1/3)

Dry. number Q R THE X R ⁴ R ⁵ R ⁶ mp (° C) 27 Q-3 H CH Ski Ph Me Me oil 28 Q-L H (CH ₂ ) ₃ G nBu nBu nBu 104 from 106 29 Q-5 Me ^(a ' ch ₂ Ski Ph Me Me oil 30 Q-1 H ch ₂ Ski et Me Me 152,5- 154.0 31 Q-L Me ^(bl ch ₂ Ski et Me Me 108- 110 32 Q-2 H ch ₂ Ski et Me Me 134 DEG

141

- 75 • ··

Q-2 H CH ₂ Si Et Me Me 98-104 (a), ¹ 'racem

Table D Compounds of formula (1/4)

Dry. number R ¹ THE X R ⁴ R ⁵ R ⁶ mp (° C) 34 3-CH ₂ -6-Cl-pyr ch ₂ Ski et Me Me 115- 117 35 3-CH ₂ -6-Cl-pyr ch ₂ Ski Ph Me Me oil

Table E

NMR (CDC1 ₃₎ Data ⁰⁰

Dry.

number

4.47-4.36 (m, 1H), 4.02 (d, 2H), 3.90-3.73 (m, 4H), 3.49 (dt, 1H),

3.22 (dd, 1H), 2.82-2.68 (m, 2H), 2.12 (s, 3H), 2.08 (ABq, 2H), 1.39 (d, 3H), 0 10 (s, 9H);

8.30 (d, 1H), 7.69 (dd, 1H), 7.32 (d, 1H), 4.50 (d, 1H), 4.18 (d, 1H),

3.60-3.40 (m, 5H), 3.323.21 (m, 1H), 2.99 (s, 3H), 1.97 (s, 2H), 1.19 (t, 3H), 0, 10 (s, 9H), (300MHz) 8.31 (d, 1H), 7.78 (dd, 1H), 7.50 (dd, 2H), 7.407.32 (m, 3H), 7.30 ( d, 1H), 5.08 (d, 1H), 4.65 (d, 1H), 3.933.65 (m, 5H), 3.18 (t, 1H), 2.83 (dd, 1H) ), 2.19 (ABq, 2H), 1.19 (d, 3H), 0.39 (s, 3H), 0.35 (s, 3H), (300MHz) 8.32 (d, 1H) , 7.79 (dd, 1H), 7.52 (dd, 2H), 7.427.35 (m, 3H), 7.30 (d, 1H), 5.07 (d, 1H), 4.66 ( d, 1H), 3.933.65 (m, 5H), 3.17 (t, 1H), 2.83 (dd, 1H), 2.19 (ABq, 2H), 1.19 (d, 3H) ), 0.39 (s, 3H), 0.35 (s, 3H);

- 76 (300MHz) 8.30 (s, 1H), 7.80 (d, 1H), 7.50-7.40 (m, 2H), 7.407.30 (m, 3H), 7, 30 (d, 1H), 5.00 (d, 1H), 4.75 (d, 1H), 3.903.65 (m, 6H), 3.20-3.10 (m, 1H), 2.40 -2.30 (m, 2H), 1.60l, 45 (m, 2H), 1.24 (d, 3H), 0.80-0.70 (m, 2H), 0.28 (s, 6H) )

8.35 (s, 1H), 7.85 (d, 1H), 7.60 (d, 1H), 7.55-7.50 (m, 6H), 7.437.35 (m, 9H), 4 79 (s, 2H), 3.84 (s, 2H);

3.78 (s, 2H), 3.51 (s, 4H), 2.5 (t, 2H), 1.80-1.65 (m, 2H), 1.45l, 35 (m, 2H) , (300 MHz) 7.52 (dd, 2H), 7.45 (s, 1H), 7.427.35 (m, 3H), 4.93 (s, 2H), 3.81 (s, 2H), 3 , 78 (s, 2H), 3.54 (distorted t, 2H), 3.14 (distorted t, 2H), 2.28 (s, 2H), 0.38 (s, 6H), (300 MHz) 7.57 (dd, 2H), 7.39 (m, 2H), 4.40 (dt, 1H), 3.933.82 (m, 4H), 3.72 (d, 1H), 3.45 ( m, 1H), 3.34 (t, 1H), 2.85 (dd, 1H), 2.8-2.6 (m, 2H), 2.35 (ABq, 2H), 2.10 (s , 3H), 1.31 (d, 3H), 0.40 (s, 3H), 0.36 (s, 3H), (300 MHz) 8.26 (s, 1H), 8.07 (s) 1H), 4.85 (s, 2H), 3.91 (s, 2H), 3.78 (s, 2H), 3.63 (m, 4H), 2.07 (s, 2H), 0, 96 (t, 3H), 0.58 (q, 2H), 0.09 (s, 6H) (300 MHz) 8.27 (s, 1H), 8.05 (s, 1H), 7.55 ( m, 2H), 7.40 (m, 3H), 4.82 (s, 2H), 3.82 (s, 2H), 3.79 (s, 2H), 3.46 (m, 2H), 3.15 (distorted t, 2H), 2.31 (s, 2H), 0.40 (s, 6H),

8.30 (s, 1H), 7.64 (d, 1H), 7.54 (m, 2H), 7.38 (m, 3H),

7.31 δ (d, 1H), 4.59 (br s, 2H), 3.72 (m, 4H), 3.27 (m, 2H),

3.11 (t, 2H), 2.17 (s, 2H), 1.97 (m, 2H), 0.39 (s, 6H) ^(a), unless otherwise noted

Was recorded in CDCl ₃ at 400 MHz. Chemical shift values (δ) were compared to Me ₄ Si = 0.00 ppm.

- 77 s = singlet, d = doublet, t = triplet, q-quartet and m = multiplet.

Biological tests

A) Spodoptera frugiperda

For high impact styrene, a 16-well assay plate was prepared. Lime bean leaves were placed in 12 such cells on moist filter paper with an area of about 8 cm. A 0.5 cm layer of wheat germ was placed in the 4 remaining cells. Third-order larvae of Spodoptera frugiperda were placed in 15 to 20-mL plastic cups. A solution of 75/25 = acetone / distilled water from each test compound was sprayed onto the trays and into the dish. Spraying was accomplished by transferring the tray and cup onto a conveyor belt directly under a hydraulic nozzle through which the formulation was sprayed at a rate of 0.55 kg of active ingredient / ha at 207 kPa. The insects were transferred from the 230 ml vessel to the plastic tray with 1 insect per cell. The trays were then covered and maintained at 27 ° C and 50% relative humidity for 48 hours, and then cell 22 was examined for lime bean leaves. Among the test compounds, efficacy was 80% or greater in the following cases: 1, 2, 3, 4 *, 5 *, 6, 14 *, 19 *, 27 *, 28 *, 29 *, 30 *, 31 * and * 27.

* = 0.14 kg / ha.

- 78 Β)

Diabrotica undecimpunctata howardi

Assay units were prepared, each containing 230 ml plastic containers covered with wheat germ at 2.54 cm. The test units were sprayed with a solution of the test compounds as described in Test A. After the spray juice had dried on the vessel, 5 second larval stage Diabrotica undecimpunctata howard insects were placed in each vessel. The vessels were maintained at 27 ° C and 50% relative humidity for 48 hours, and the mortality rate was then determined. Among the tested compounds, the following compounds were 80% or more effective: 1, 2, 3, 4, 5, 6, 7, 8, 9,10,11,13,14 *, 15 *, 16 *, 20 * , 21 *, 22 *,

24 *, 26 *, 27 *, 28 *, 30 *, 32 * and 34 *.

* = 0.14 kg / ha.

C.)

Mascrosteles fascifrons

Assay flasks of 350 ml were prepared, each containing oat seedlings (Avena sativa) on sterilized soil 2.54 cm thick. The test units were sprayed with a solution of the test compounds as described in Test A). After the oats had dried, 10-15 adult Mascrosteles fascifrons insects were placed on each. The vessels were covered with a ventilated lid and stored at 27 ° C and 50% relative humidity for 48 hours, and mortality was determined. Among the tested compounds, the following were found to be 80% or more effective: 1, 2, · «· ·

- 79 3, 4, 5, 6, 7,10,11,13,14 * and 16 *, 19 *, 20 *, 21 *, 23 *, 24 *, 25 *, 26 *, 27 *, 28 * , 29 *, 30 *, 31 *, 32 * and 34 *.

* = 0.14 kg / ha.

D)

Aníhonomus grandis grandis

Adult Anionomus grandis grandis insects were placed in 290 ml test vessels and sprayed with a solution of the test compounds as described in Example A). The vessels were covered with a vented lid and maintained at 27 ° C and 50% relative humidity for 48 hours and mortality was determined. The following compounds have a mortality rate of 80% or more: 2, 3, 4, 5, 6, 7,10 and 16 *.

* = 0.14 kg / ha.

E)

Aphis fabae

Nocturnal leaves were inoculated with 10-15 insects (various growth stages of Aphis fabae), and the upward-facing lower leaf surface was sprayed as described in Test A). The leaves were then placed in 0.94 cm diameter vials containing 4 ml of sugar solution (about 1.4 g / l) and covered with a transparent plastic container of 29 ml volume to prevent insects from leaving the leaves. The dishes were stored at 27 ° C and 50% relative humidity for 48 hours and then the death rate was determined. Among the compounds tested, mortality was 80% or greater: 1, 2, 3, 4, 5, 6, 7, 8,

9,10,13,14 *, 15 * and Ib *, 19 *, 21 *, 22 *, 23 *, 24 *, 25 *, 26 *,

28 *, 29 *, 30 *, 31 *, 32 * and 34 *.

- 80 * = 0.14 kg / ha.

F)

Contact activity against Nephotettix cincticeps puppets

Three rice {Oryza sativa) seedlings with 1.5 leaf condition and approx.

cm, placed in a 14 ml plastic container containing Rubber Brown artificial soil. 7 ml of distilled water was added to each vessel. The test compounds were prepared by first dissolving in acetone and then adding water to give an acetone / water ratio of 75/25. Four plastic containers, which were nailed in parallel, are placed on the rotating tray of the spray chamber. The vessels were sprayed with 50 ml of said solution for 45 seconds at a pressure of 2 kg / cm air through a spray nozzle. The rotary table performed 7.5 rotations during the 45 minute spray time. After application, the treated vessels were dried for 2 hours under ventilation. After drying, the dishes were placed in a conical test unit and the soil surface was covered with 2 to 3 mm thick quartz sand. 8-10 third larvae of Nephotettix cincticeps were introduced into the test vessel so formed. The dishes were maintained at 27 ° C and 65% relative humidity, and the number of live and dead pupae was determined 24 and 48 hours after infection. Insects that did not move were considered dead. Among the test compounds, the following were found to have a mortality rate of 80% or greater after 48 hours at an application rate of 0.05 kg / ha: 1,2,3,4,5,6,7 and 8.

- 81G)

Contact activity against Nilaparvata lugens puppets

1.5 leaves and approx. Three rice seedlings (Oryza sativa) 10 cm high were placed in a 14 ml plastic container containing Kumiai Brown artificial soil. To each flask was added 7 mL of distilled water. A solution of the test compounds was prepared by first dissolving the compounds in acetone and then adding water to a ratio of 75/25 acetone / water. Four plastic pots, each serving as a parallel, were placed on a rotating table of a spray chamber. The vessels were sprayed with 50 ml of the test solution for 45 seconds at a pressure of 2 kg / cm ² through an air jet valve. The turntable was rotated 7.5 turns during the 45 minute spraying interval. After application of the chemical, the treated vessels were dried for 2 hours under aeration. After drying, the dishes were placed in a conical test vessel and the soil surface was covered with 2 to 3 mm thick quartz sand. Then 8-10 third larvae of Nilaparvata lugens pupae were placed in the test units. The test units were maintained at 27 ° C and 65% relative humidity, and after 24 and 48 hours respectively, the number of live and dead larvae was determined. Insects that did not move were classified as dead. Among the test compounds, the following showed 80% or greater lethal activity at 0.05 kg / ha after 48 hours: 1,2,3,4,5,6,7,8 and 9.

Claims (8)

Claims Compounds of the formula I in the formula: X is Si or Ge, A is (C 1 -C 20) alkylene, (C 2 -C 20) alkenylene, (C 2 -C 20) alkynylene, (C 3 -C 8) cycloalkylene, (C 7 -C 10) aralkylene or phenylene, each optionally having 1 to 3 times May be substituted with W, or A may be a bond, R ¹ and R ³ are independently H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, or C 2 -C 10 alkynyl, each optionally substituted 1-2 times with halogen, CN, C (O) R ⁷ , C (S) R ⁷ , NO ₂ , OH, SC (O) R ⁷ , SC (S) R ⁷ , OC (O) R ⁷ , OC (S) R ⁷ , NR ⁸ C ( O) R ⁷ , NR ⁸ C (S) R ⁷ , SH, Si (R ⁸ ) (R ⁹ ) (R ¹⁰ ), C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, (C 1 -C 4) alkylamino, (C 2 -C 8) dialkylamino, (C 3 -C 8) cycloalkyl, or phenyl substituted with ^{1 to} 3 times W ¹ ; it may further be C3-C8 cycloalkyl, which may be optionally substituted with 1 to 3 times halogen, C1-C2 alkyl or C1-C2 haloalkyl; C (O) R ^U ; C (S) R ^U ; phenyl optionally substituted 1 to 3 times with W ¹ ; C 1-3 alkyl, which Substituted with a 5- or 6-membered aromatic ring attached through its carbon or nitrogen atom and containing 1 to 4 heteroatoms selected from 0 to 4 nitrogen atoms, 0 to 1 oxygen atom and 0 to 1 atom the sulfur atom and the ring are optionally substituted ^{1 to} 3 times with W ¹ ; and may also be a 5- or 6-membered aromatic ring linked through its carbon or nitrogen atom containing 1 to 4 heteroatoms selected from 0 to 4 nitrogen atoms, 0 to 1 oxygen and 0 to 1 sulfur, and the ring may be optionally It may be -3 times substituted with W ¹ ; R is H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 2-6 haloalkynyl -, C3-C7 cycloalkyl, C3-C7 halo-cycloalkyl or C4-C7-cycloalkylalkyl, each of which is optionally It may be 1 to 3 times substituted with W; obsession R and R taken together are CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ , each of which may be optionally substituted with 1 to 2 CH ₃ ; R ⁴ is H or C 3 -C 6 trialkylsilyl or C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, phenyl, phenoxy, phenylthio, or naphthyl, each optionally substituted with ^{1 to} 3 times W ¹ may; - 84 • «« «« ··· · R ⁵ and R ⁶ are independently C 1-10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, phenyl, phenoxy, phenylthio or naphthyl, each of which is optionally 1- It may be substituted 3 times with W ¹ ; or OH or C 3-6 trialkylsilyl; R ⁷ is H, NH ₂ , OH, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-6 alkylthio C 1-4 alkylamino, C 2-8 dialkylamino or phenyl optionally substituted with 1 to 3 times W ¹ ; R ⁸ is H or may be C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, phenoxy, phenyl or naphthyl, each of which is optionally 1-3 carbon atoms. -substituted with W ¹ ; R ⁹ and R ¹⁰ are C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, phenoxy, phenyl or naphthyl, each of which is optionally 1-3 carbon atoms. -substituted with W ¹ ; they may also represent OH; R ¹¹ is H, NH ₂ , OH, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-2 alkylthio C1-C4 alkylamino, C2-C8 dialkylamino · 85- or phenyl, which may be optionally substituted ^{1 to} 3 times with W1; W is halogen, CN, NO ₂ , OH, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy or C 1-6 haloalkoxy, and W ¹ is halogen, CN, NO ₂ , C 1-2 alkyl, C 1-2 haloalkyl, C 1-2 alkoxy, C 1-2 haloalkoxy, C 1-2 alkylthio, C 1-2 haloalkylthio, C 1-2 alkyl -Sulfonyl, C 1 -C 2 haloalkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, or C 3 -C 6 trialkylsilyl. Compounds of formula (I) according to claim 1, wherein A is C 1-6 alkylene, R ¹ is C 1-3 alkyl substituted with a 5- or 6-membered aromatic ring attached through the carbon or nitrogen atom and containing 1-4 heteroatoms selected from 0-4 nitrogen, 0-1 oxygen and 0-. 1 sulfur atom and the ring is optionally substituted ^{1 to 3 times} with W ¹ ; R ⁴ is C 1 -C 10 alkyl or phenyl, each of which is optionally substituted with ^{1 to} 3 times W ¹ ; ^R5 and ^R6 are independently C1-10 alkyl or phenyl, each of which is optionally substituted by 1-3 of a W ¹ group; and · -86 "♦ W ¹ is halogen or C 1 -C 2 haloalkyl. A compound of formula (I) according to claim 2, wherein X is Si, R ¹ is CH ₂ substituted with pyridyl, thiazole or isoxazole and optionally substituted with 1 to 2 halogens or 1 to 2 methyl groups; R ² and R ³ together are CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ , each optionally substituted with 1 to 2 CH ₃ groups, and R ⁴ , R ⁵ and R ⁶ are each independently C 1-3 alkyl, C 1-3 alkoxy or phenyl. A compound of formula (I) according to claim 2, wherein X is Si; R ¹ is CH ₂ substituted with pyridyl, thiazole or isoxazole and optionally substituted with 1 to 2 halogens; R is H or (1-3C) alkyl; and R ⁴ , R ⁵ and R ⁶ are each independently C 1-3 alkyl, C 1-3 alkoxy, or phenyl. 5. Compounds of formula I according to claim 3, which are: l - [( 6-chloro-3-pyridinyl) methyl] -1,2,3,5,6,7-hexahydro-2-methyl-8-nitro-6 - [(trimethylsilyl) methyl] imidazo [1, 2-c] pyrimidine. ·· »· - 87 6. The following compounds of the formula (I) according to claim 3: l - [(6-chloro-3-pyridinyl) methyl] -1,2,3,5,6,7-hexahydro-8-8-nitro-6 - [(trimethylsilyl) methyl] imidazo [ l, 2-c] pyrimidine. An arthropod composition comprising an effective amount of a compound of claim 1 in association with a carrier, in an effective amount against an arthropod. 8. A method of killing arthropods comprising contacting the arthropod or an environment thereof with an effective amount of a compound of claim 1 against arthropods.