WO2012034403A1 - Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof - Google Patents

Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof Download PDF

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WO2012034403A1
WO2012034403A1 PCT/CN2011/073810 CN2011073810W WO2012034403A1 WO 2012034403 A1 WO2012034403 A1 WO 2012034403A1 CN 2011073810 W CN2011073810 W CN 2011073810W WO 2012034403 A1 WO2012034403 A1 WO 2012034403A1
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alkyl
ih
dc
formula
ηΐ
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PCT/CN2011/073810
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Chinese (zh)
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窦花妮
陈杰
郑昀红
许天明
邢家华
郑志文
彭伟立
许勇华
董德臻
魏优昌
孔小林
袁静
刘刚
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中化蓝天集团有限公司
浙江省化工研究院有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in positions 3 or 5
    • C07D231/22One oxygen atom attached in positions 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Abstract

Fluoromethoxypyrazole anthranilamide compounds of formula (I) or agrochemical salts thereof, as well as synthesization methods and uses thereof. The compounds of formula (I) have broad-spectrum insecticidal activities and are effective to pests of lepidopteron (such as Plutella xylostella), hemipteran (such as Aphis medicaginis), homopteran (such as Nilaoarvata lugens) and the like. Agricultural preparations including compounds of formula (I) and methods of preventing and controlling pests are involved.

Description

 Instruction manual

 O-formylaminobenzamide compound containing monofluoromethoxypyrazole, synthesis method and application thereof

 The present invention provides an o-formylaminobenzamide compound. Background technique

 O-formylaminobenzamides (Finedine Receptor Inhibitors) are effective insecticides developed in recent years to control pests without ridges.

 The PCT patent application WO2003/015519 discloses the following compounds having insecticidal activity:

Figure imgf000003_0001

R=CF 3 , Cl, Br or OCH 2 CF 3

 The PCT patent application WO2004/033468 discloses the following compounds having insecticidal activity:

Figure imgf000003_0002

 PCT patent application WO2004/067528 discloses the following compounds having insecticidal activity:

Figure imgf000003_0003

PCT patent application WO2006/080311 discloses compounds having insecticidal activity as follows:

Figure imgf000004_0001
Figure imgf000004_0002

 The PCT patent application WO 2008/134969 discloses the following compounds having insecticidal activity:

Figure imgf000004_0003

 All of the compounds disclosed in the above PCT patent application have certain similarities with the compounds of the present invention, but none of them have a homologous one containing a fluoromethoxypyrazole represented by the formula (I) of the present invention. Formylaminobenzamides. Although many products for controlling invertebrate pests can be purchased, there is still a need for new compounds that are more effective, less toxic, less costly, and environmentally safe. Summary of the invention

 The object of the present invention is to provide a novel pest control agent which can prevent various pests which are problems in the field of agriculture and horticulture, or pests which are parasitic on animals, and which have high pests at low doses. Control effect.

 To achieve the above object, the present invention provides the following technical means:

A fluoromethoxypyrazole-containing orthoamidobenzamide compound represented by the formula (I) or an agriculturally applicable salt thereof,

Figure imgf000005_0001

 Its towel:

 A is N or CH;

R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;

R 2 is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;

R 3 is hydrogen, alkyl or alkoxy;

R 4 is hydrogen, cyano, alkyl, alkoxy, alkylamino, alkyl, alkoxy, alkylamino, cyanoalkyl, cycloalkyl, cycloalkyl, hydroxy An alkyl group, an alkoxycarbonylmethyl group, an alkoxyamide group, an alkylamido group, an alkylalkylamide group, a cyano substituted alkylamido group or an arylheterocyclic methyl group;

Or R 3 and R 4 form a ternary, quaternary, five- or six-membered ring with the N-linked group;

 m is an integer from 0 to 4;

 n is an integer of 0 to 4. In a preferred embodiment, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I):

R 1 is hydrogen, halogen, cyano, nitro, d-Ce fluorenyl, d-Ce haloalkyl, cyano d-Ce alkyl, C 2 _C 6 alkenyl,

C 2 -C 6 haloalkenyl, C 2 -C 6 block, halo C 3 -C 6 block, (-(: 6 alkoxy, dC 6 cyanoalkoxy, dC 6 haloalkoxy) , d-Ce alkylthio, d-Ce haloalkylthio, d-Ce alkylsulfonyl, CfCe alkylcarbonyl, halogenated CfCe alkylcarbonyl, (ce alkoxycarbonyl, ^dC 6 alkoxycarbonyl) Or an amino dC 6 alkyl group;

R 2 is hydrogen, halogen, d-Ce alkyl, halogenated d-Ce alkyl, d-Ce alkoxy, halogenated CfCe alkoxy or cyano;

R 3 is hydrogen or an alkyl group;

R 4 is hydrogen, cyano, d-Ce alkyl, d-Ce alkoxy, d-Ce alkylamino, halogenated CfCe alkyl, halogenated CfCe alkoxy, halo (-(: 6 alkylamino, Cyano dC 6 alkyl, (: 3 _(: 6 cycloalkyl, halo (: 3 _: 6 cycloalkyl, hydroxy (-(: 6 alkyl, dc 6 alkoxycarbonylmethyl, (^ -(: 6 alkoxyamido group, dc 6 alkyl amide group, ^ dc 6 alkyl amide group, cyano substituted dc 6 alkyl amide group or aryl heterocyclic methyl group;

 m is 2;

n is 1. In a further preferred embodiment, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I):

 A is N;

R 1 is hydrogen, halogen, cyano, CfCe alkyl, d-haloalkyl or d-alkylcarbonyl;

R 2 is halogen, cyano, d-Ce alkyl or halogenated dC 3 alkyl.

 In a still further preferred mode, the monofluoroamidobenzoylamine compound containing a monofluoromethoxypyrazole represented by the formula (I):

R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;

R 2 is a halogen or a cyano group.

 As a most preferred mode, the fluoroformylpyrazole-containing o-formylaminobenzamide represented by the formula (I)

Figure imgf000006_0001

In the above A, RR 2 , R 3 , R 4 and R 5 groups:

Examples of the halogen in the RR 2 or R 4 or the halogen as the substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogens as a substituent may be 1 or 2 or more, and when it is 2 or more, each halogen may be the same or different. In addition, the halogen substitution position can be at any position.

The alkyl or alkyl moiety in RR 2 , R 3 or R 4 may be straight or branched. Specific examples thereof include a d- 6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group or a hexyl group.

The alkenyl or alkenyl moiety in R 1 may be either a straight chain or a branched chain. Specific examples thereof include C 2 such as a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 1, 3-butadienyl group, and a 1-hexenyl group. 6 The block group or the block group portion in R 1 may be either a straight chain or a branched chain. Specific examples thereof include acetylene group, 2-block group, 2-block basis, a block group such as 3-hexyl C 2 - 6 group of blocks.

 In the orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I), an isomer such as an optical isomer or a geometric isomer may be present, and the present invention encompasses various forms. Both the conformation and the mixture of isomers. Further, the present invention also encompasses various isomers other than the above within the scope of technical knowledge in the technical field. Further, although a chemical structure different from the above structural formula (I) may be formed depending on the kind of the isomer, as long as those skilled in the art can fully recognize that the isomer exists, it is apparent that Within the scope of the invention.

 The present invention also provides an orthoylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I), which has the following structural formula (Π):

Figure imgf000007_0001

Among them, A, R 1 and R 2 groups and! ! ! with! Corresponding to a group in the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I), namely:

 A is N or CH;

R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;

R 2 is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;

 m is an integer from 0 to 4;

 n is an integer of 0 to 4.

 In a preferred embodiment, the compound represented by the structural formula (Π) is:

 A is N;

R 1 is hydrogen, halogen, cyano, nitro, C r C 6 alkyl, C r C 6 haloalkyl, cyano C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 block, halogenated C 3 -C 6 block, -C 6 alkoxy, dC 6 cyanoalkoxy, -C 6 haloalkoxy, ^-alkyl thio, CC 6 ^ substituting alkylthio, C r C 6 alkylsulfonyl group, a C r C 6 alkylcarbonyl, C r C 6 substituting ^ alkylcarbonyl, -C 6 alkoxycarbonyl group, -C ^ substituting 6 alkoxycarbonyl or amino-C 6 alkyl;

R 2 is hydrogen, halogen, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy or cyano; m is 2; n is 1.

 As a further preferred mode, among the compounds represented by the structural formula (Π):

R 1 is hydrogen, halogen, cyano, dC 6 alkyl, dC 6 haloalkyl or dC 6 alkylcarbonyl;

R 2 is halogen, cyano, CfCe alkyl or halogenated dC 3 alkyl.

 In a more preferred manner, among the compounds represented by the structural formula (Π):

R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;

R 2 is a halogen or a cyano group.

 The present invention also provides a method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I).

 A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I), comprising the steps of:

 (1) In an aprotic solvent, a compound represented by the formula (VI) is reacted with a monofluoromethane bromide under an action of an acid binding agent to give a structural formula (W) to represent a compound;

 (2) In a protic solvent, the structural formula (W) indicates that the compound is hydrolyzed under a base to give a monofluoromethoxypyrazolecarboxylic acid represented by the formula (III);

 CHPF

Yesterday

Figure imgf000008_0001

 (VI) (VD) (III)

 (3) In a non-protic solvent, a base and an alkylsulfonyl chloride are added, and the monofluoro-aminopyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid represented by the formula (V) are reacted to obtain a structural formula ( 4 ) represented by a monofluoro-pyridazole-containing 4H-benzo[1,3]oxazin-4-one compound;

Figure imgf000008_0002

(4) A 4-fluorenyl-benzo[Z,3-oxazin-4-one-based compound containing a monofluoromethoxypyrazole represented by the formula (Π) and a compound represented by the formula (IV) in an aprotic solvent Reacting the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I);

Figure imgf000009_0001

 (II) (IV) (I)

The definitions and preferred forms of the A, RR 2 , R 3 , R 4 and R 5 groups and m and n in the compounds represented by the formulae (II) to (YD) are as defined above for the monofluoromethoxy group represented by the formula (I). An orthoformylbenzamide compound of pyrazole, wherein the compound represented by the formula (VI) is in the compound! ^ is ^ -6 alkyl.

 The compound represented by the above formula (VI) is a known compound, and its preparation method can be referred to PCT Patent Application No. WO03015519 and WO2006023783.

 In a preferred embodiment, in the step (1) of the synthesis method, the ratio of the compound represented by the formula (VI) to the material of the monofluoromethane bromide and the acid binding agent is 1: 1.1 to 2: 1.1 to 2, further preferably 1: 1.1~1.5: 1.1~1.5; The aprotic solvent is selected from one or a combination of two or more of tetrahydrofuran, acetonitrile, 1,4-dioxane or acetone; the reaction temperature is 10 to 90 ° C Further preferably 20 to 80° (:.

 Step (1) The post-treatment of the compound represented by the structural formula (W) is: filtration, the filter cake is washed with a small amount of an organic solvent, and the filtrate is combined and concentrated. The hydrolysis reaction is carried out directly in the step (2) without isolation and purification.

 In a preferred embodiment, in the step (2) of the above synthesis method, the structural formula (W) represents an amount ratio of the compound to the base material to be 1:1 to 1.5, further preferably 1:1 to 1.2; and the protic solvent is Methanol and/or ethanol; reaction temperature is 10 to 90 ° C, further preferably 20 to 80 ° (:.

 The post-treatment of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III) in the step (2) is: after evaporating the organic solvent, adding water, extracting with diethyl ether, and then adding acidic hydrochloric acid to the aqueous phase to make it acidic. A large amount of solid precipitated, filtered, washed with water, and dried by an infrared lamp to give the above formula (III) a solid containing a monofluoromethoxypyrazolecarboxylic acid.

 In a preferred embodiment, in the step (3) of the above synthesis method, the fluorine-containing methoxypyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid and alkylsulfonyl chloride represented by the structural formula (V) are charged. The amount ratio of the substance is 1:1 to 1.5: 2 to 3, further preferably 1:1 to 1.2: 2 to 2.5; the alkylsulfonyl chloride is methylsulfonyl chloride; and the aprotic solvent is selected from tetrahydrofuran and acetonitrile. One or a combination of two or more of 1, 4-dioxane, diethyl ether or toluene; the base is an organic base, and the organic base is further preferably one selected from the group consisting of triethylamine, pyridine or 3-methylpyridine. Or a combination of two or more; the reaction temperature is -30 to 80 ° C, and more preferably -15 to 30 ° C. The volume of the organic base is 1 to 4 times (ml/g), preferably 1 to 2 times (ml/g), based on the mass of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III).

The post-treatment of the step (3) is: the end of the reaction, filtration, the filter cake is washed with water, a mixed solvent of an organic solvent and water, and a small amount of an organic solvent to obtain a first solid; the filtrate is distilled off, and then extracted with an organic solvent, After the sodium sulfate is dried, Filtration, concentration, recrystallization from ethanol to give a second crop of solids; and two batches of solids combined to give the compound of formula (II).

 The substituted anthranilic acid represented by the structural formula (V) is a known compound and can be produced by a number of methods, and can be referred to the following literature: Organic Synthesis, Coll. Vol. 79, pl 96 (2002); Vol. l0, p23 (2004); Adv. Heterocycl. Chem. 1975, 18, 1-58; Journal of the Brazilian Chemical Society 2001, 12(3), 273-324; Angew. Chem. Int. Ed. Engl. 1980, 19, 222-223 .

 In a preferred embodiment, in the step (4) of the above synthesis method, a tetrafluoromethoxypyrazole-containing 4H-benzo[1,3]oxazin-4-one compound represented by the formula (Π) and a structural formula ( The amount of the compound to be represented by IV) is 1:1 to 5, more preferably 1:1 to 2; the aprotic solvent is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, diethyl ether, toluene One or a combination of two or more of dichloromethane or chloroform. The volume of the aprotic solvent is 5 to 60 times the mass of the 4H-benzo[1,3]oxazin-4-one compound containing the monofluoromethoxypyrazole represented by the structural formula (Π) (ml/ g ) is preferably 5 to 20 times (ml/g).

 Below, the invention is involved

Figure imgf000010_0001

The following abbreviations used in the following Table 1 are as follows: t is unterminated, n is positive, i is hetero, s is secondary, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl; corresponding i- Pr is an isopropyl group or the like. In the index table 1, R 2 = 3_C1, n = 1, R : and R 4 may be independent substituents, or may be connected as a whole.

Figure imgf000010_0002

Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001

The following index table 2 shows the physical and chemical properties and nuclear magnetic data of some of the compounds described in Table 1. Note: The numbers described in Index Table 2 correspond to the compound numbers described in Table 1. Where s is a single peak, d is a doublet, t is a triplet, q is a quartet, m is a multiplet, and brs is a broad singlet. Index table 2

No. Melting point / °c 3⁄4 NMR (Reagents are CDC1 3 unless otherwise stated)

 0. 95-0. 98 (m, 3H) , 1. 58-1. 62 (m, 2H) , 2. 19 (s, 3H) ,

 3. 32-3. 37 (m, 2H), 5. 83— 5. 96 (d, 2H), 6. 12 (s, 1H),

 1

 6. 66 (s, 1H) , 7. 22 (s, 1H) , 7. 33-7. 37 (m, 1H) ,

 7. 82-7. 84 (d, 1H) , 8· 45- 8· 46 (d, 1H) , 10. 00 (s, 1H)

 1. 20-1. 22 (d, 6H) , 2. 18 (s, 3H) , 4. 15-4. 20 (m, 1H) ,

 5. 83-5. 96 (d, 2H), 5. 92-5. 94 (d, 1H), 6. 71 (s, 1H),

 2

 7. 19-7. 36 (m, 3H) , 7· 82- 7· 84 (d, 1H) , 8. 46 (s, 1H),

 10. 06 (s, 1H)

 2. 16 (s, 3H) , 2. 67 (s, 3H) , 5. 85-5. 99 (d, 1H), 6. 93 (brs,

3 (Example 2) 236-237 1H), 7. 34 (s, 1H), 7. 45 (s, 1H), 7. 54-7. 57 (m, 1H),

 8. 10-8. 47 (m, 3H) , 10. 18 (brs, 1H)

 1. 16-1. 20 (t, 3H) , 2. 17 (s, 3H) , 3. 37-3. 44 (m, 2H) ,

4 5. 83-5. 96 (d, 2H) , 6. 15 (s, 1H) , 6. 75 (s, 1H) , 7. 19-7. 36

 (m, 3H) , 7. 82-7. 84 (d, 1H) , 8. 44-8. 46 (m, 1H) ,

 10. 00 (s, 1H)

 0. 91-0. 95 (m, 3H) , 1. 34-1. 60 (m, 4H) , 2. 18 (s, 3H) ,

 3. 34-3. 39 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 12 (s, 1H),

5 6. 71 (s, 1H) , 7. 19-7. 36 (m, 3H), 7·81—7· 83 (d, 1H),

 8. 44-8. 45 (d, 1H),

 10. 00 (s, 1H)

 1. 14-1. 96 (m, 10H), 1. 59 (s, 3H), 2. 18 (s, 3H), 3. 85-3. 87 (d, 1H), 5, 82-5. 96 (d, 2H) , 5. 96 (s, 1H), 6. 69 (s, 1H) ,

 6 252-253

 7. 19-7. 36 (m, 3H) , 7. 81-7· 83 (d, 1H) , 8. 44-8· 45 (d, 1H) , 10. 03 (s, 1H)

 2. 34 (s, 3H) , 4. 54-4. 56 (d, 2H) , 5. 83-5. 97 (d, 2H) ,

 6. 28-6. 64

 7

 (m, 3H) , 7. 34-7. 36 (d, 2H) , 7· 81- 7· 83 (d, 1H) ,

8. 44-8. 45 (d, 1H) , 9. 89 (s, 1H) (Ηΐ 's)28 "6 '(Ηΐ 'P)ff SZ "8

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9S "Ζ ' (HS 'ω) 20 "Ζ-86 "9 ' (Η2 'Ρ) 06 "9-ΖΖ "9 ' (Η2 '^) 2ΐ w, ' m ) z τ-ιζ τ '(HS ' s)go τ '(m <IU )T61-WT

 (Ηΐ 's)^8 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'Ρ)98 " -S8 Ί

 ' (HS 'ω) 9£ "Ζ ' (Η2 99 "9-69 ·9 ' (Η2 'Ρ)

 Ϊ́ΐ

96 -9-£8 "9

 '(Η 'Ρ)8Ζ · - ΐ · '(HS 's)T2 '(Η£ '冚)££ ·ΐ- 62 ·ΐ

 (Ηΐ 'Ρ)00 Όΐ-96 ·6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ)

8 "Ζ-08 "Ζ '(Η ' εΉ6·9 '(Η2 'P)f6 "9-ΐ8 "9 ' (Η^ '^)

 98ΐ- 8ΐ Οΐ

'(HS 's)207 '(Η2 'ω)ΐ9 "ΐ- ε 'ΐ ' (HS '^) 96 Ό-Τ6 Ό

 (Ηΐ 's)20 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 ' (Ηΐ 'Ρ) 8 ·Ζ

 '(Η2 'ω) ε "Ζ '(Ηΐ 's)89 "9 ' (Ηΐ 's) £ "9 ' (Η2 'Ρ)

 6

96 -9-£8 "9

 '(HS 's)6T 7 '(H9 )6S ·ΐ-εε ·ΐ ' (Η£ ' ) 06 ·0-68 Ό

 (Ηΐ 's)OT Όΐ '(Ηΐ 'Ρ)9 8—

 '(Ηΐ ·8-0ΐ ·8 ' (Η^ 'ω) 89 "Ζ ' (Ηΐ 's)S6 "9

 822- LZZ

'(Η2 'Ρ)Ζ6 "9-^8 "9 ' (HS 's)9T 7 '(H6' s )92 "ΐ :9 Ρ - OSMI

L\

OT8C.0/llOZN3/X3d co o Ζ OAV

Figure imgf000020_0001

 81

Ol8C.0/llOZN3/X3d co o Ζ OAV 6. 73-6. 74 (d, IH), 7. 27-7. 86 (m, 5H), 8. 44-8. 45 (d, IH),

7. 77-7. 79 (d, IH)

 214-215

DMS0-d 6 : 0. 81-0. 85 (m, 3H) , 1. 40-1. 45 (m, 2H) , 2. 16

(s, 3H) , 3. 06-3. 09 (m, 2H) , 5. 85— 5. 98 (d, 2H) , 6. 93 (s, IH) ,

7. 44-7. 59 (m, 3H) , 8. 10-8. 46 (m, 3H) , 10. 14 (s, IH)

 0. 95-2. 22 (m, 10H) , 2. 11 (s, 3H) , 3. 32-3· 75 (m, 2H) ,

4. 62-5. 02 (m, 2H) , 5. 82-5. 95 (d, 2H) , 6. 91-7. 35 (m, 4H) ,

7. 80-7. 82 (d, IH) , 8. 42 (s, IH) , 9. 88 (s, IH)

 0. 64-2. 43 (m, 14H) , 2. 05 (s, 3H) , 3. 39-3. 75 (m, 2H) ,

135-136

 4. 69-5. 03 (m, 2H) , 5. 81-5. 94 (d, 2H) , 6. 88-7. 35 (m, 4H) ,

7. 80-7. 82 (d, IH) , 8. 42 (s, IH) , 9. 69 (s, IH)

 2. 23 (s, 3H) , 2. 62 (s, 3H) , 2. 89 (s, 3H) , 5. 85— 5. 99 (d, 2H) , 6. 92 (s, IH) , 7 58-8. 49 (m, 5H) , 10. 46 (s, IH)

DMS0-d 6 : . 89-0. 95 (m, 3H) , 1. 11-1. 97 (m, 9H) , 2. 20 (s, 3H) ,

3. 60-3. 62 (m, IH) , 5. 83-5. 97 (d, 2H) , 6· 67- 6· 68 (d, IH) , 7. 21-7. 37 (m, 3H ) , 7· 82- 7· 84 (d, IH) , 8· 45- 8· 46 (d, IH) , 10. 05 (s, IH)

DMS0-d 6 : . 71-0. 79 (m, 3H) , 0·99- 1· 79 (m, 9H) , 2. 22 (s, 3H) ,

252-253

 3. 26-3. 33 (m, IH) , 5. 85- 5. 98 (d, 2H) , 6. 95- 6. 97 (d, IH), 7. 54-8. 45 (m, 5H ) , 10. 05 (s, IH)

DMS0-d 6 : 1. 08-1. 74 (m, 10H) , 2. 22 (s, 3H) , 3. 59-3. 61 (m, IH) , 5. 86-5. 99 (d, 2H) , 6. 99 (s, IH) , 7. 56-8. 46 (m, 5H) ,

 10. 38 (s, IH)

DMS0-d 6 : 0. 83-0. 86 (m, 3H) , 1. 25-1. 45 (m, 6H) , 2. 21 (s, 3H) , 3. 11-3. 16 (m, 2H) , 5. 86—5. 99 (d, 2H) , 6. 95 (s, IH) , 7. 55-8. 47 (m, 6H) , 10. 42 (s, IH)

DMS0-d 6 : 1. 27 (s, 9H) , 2. 21 (s, 3H) , 5. 85— 5. 98 (d, 2H) ,

233-237

 6. 96 (s, IH) , 7. 55-8. 47 (m, 6H) , 10. 33 (s, IH)

DMS0-d 6 : 2. 22 (s, 3H) , 4. 34-4. 36 (d, 2H) , 5· 86- 5· 99 (d, 2H) ,

142-143

 6. 26-6. 37 (d, 2H) , 6. 92 (s, IH) , 7. 53- 8. 85 (m, 7H),

 10. 41 (s, IH)

DMS0-d 6 : l. 41-1. 50 (m, 4H) , 2. 30 (s, 3H) , 2. 91-3. 47 (m, 6H) , 5. 85-5. 98 (d, 2H) , 6. 97 (s, IH) , 7. 57- 7. 82 (m, 3H), 8. 13-8. 15 (d, IH) , 8· 46- 8· 47 (d, IH)

 181-182

 0. 91-0. 96 (m, 3H) , 1. 37-1. 64 (m, 2H) , 2. 03 (s, 3H) ,

 2. 92-3. 39 (m, 4H) , 5. 81-5. 94 (d, 2H) , 6. 93-7. 35

 (m, 4H) , 7. 80-7. 82 (d, IH) , 8. 42- 8. 43 (d, IH)

234. 5-24 1. 14-1. 96 (m, 10H) , 2. 36 (s, 3H) , 3. 82-3. 87 (m, IH) , 0 5. 83-5. 96 (d , 2H) , 6. 67 (s, IH) , 7. 33-7. 40 (m, 3H) ,

 7. 81-7. 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 10. 04 (s, IH)

 223-224 2. 17 (s, 3H) , 2. 93-2. 94 (d, 3H) , 5· 83- 5· 96 (d, 2H) ,

6. 16 (s, IH), 99 τ

 S9

(H2 'ω) ζζ τ-οζ τ (m <s )so '' (m ")99 "ΐ-ΐ9 "ΐ 902-^02

(Ηΐ 's)06 "6 '(Ηΐ c P)Z S-Zf "8 '(Ηΐ 'Ρ) 28 "Ζ-08 "Ζ

 ' (Η2 'ω) 9£ ·Ζ- "Ζ ' (Ηΐ 's) 0ΐ "Ζ ' (Ηΐ 's) 6 ·9 ' (Η2 'Ρ)

 F6 "9-08 "9

 29

(Η ' ) 8 ε-εο ·ε '(HS 's)go 7 '(Η9 6ΐ ·ΐ- ε6·ο 99Τ-29Ϊ

 (Ηΐ 'Ρ) 90 ΌΙ-fO Όΐ ' (Ηΐ 9 S- ·8

 ' (Ηΐ 'ω) S8 "Ζ-Ϊ8 "Ζ ' (HS 'ω) 0 ' ' (Ηΐ 'Ρ) £L '9-2 ·9

 ' (Η2 'Ρ) 96 "9-28 "9 ' (Ηΐ 'Ρ) 09 Τ-89 Τ ' (HS 's) 8ΐ ·Ζ

Ϊ́9 (Ηΐ 'Ρ) 6 ·ΐ- 06 ·ΐ '(Η6 ' m )SL 'l-6fl ' (HS '^) S6 Ό-98 Ό

 (Ηΐ 's) ZO Όΐ

 (Ηΐ 'P)S ·8- ·8

 (Η2 'Ρ) £8 "Ζ-Ϊ8 "Ζ '(Ηΐ 's) ·9

(Ηΐ 's)8T ·9 '(Η2 'Ρ)96 "9-28 "9 {wz ' m )i£ τ-ζ£ τ

 09

'OK 's)9T ·Ζ (Η9 ")99 ·ΐ— ΐε ·ΐ (HS ' ΐ6 Ό-88 Ό

 (Ηΐ 's)00 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 (Ηΐ 'Ρ) 8 "Ζ-Ϊ8 ·

 (HS 'ω) If ' -εε ' '(HI 's^q)80 "9 {W, 'Ρ)96 "9-28 "9 9 "Ζ

 69 (HS '^)£Ζ ·ΐ- 6ΐ ·ΐ

 (Ηΐ 's)ZO Όΐ '(Ηΐ 'Ρ)9^ S-ff "8 ' (Ηΐ 'Ρ) S8 "Ζ-ΐ8"Ζ

 ' (HS 'ω) S "Ζ ' (Ηΐ 's) fL ·9 ' (Ηΐ 's) 96 "9 ' (Η2 'Ρ)

 96 "9-28" 9 9

 89

(Ηΐ 'ω)6ΐ 'f-fl 'f '(HS 's) T τ '(Η9'Ρ)0Ζ ·ΐ-6ΐ ·ΐ "9ΐ2-9ΐ2

 (Ηΐ 's)8T Όΐ

 (Ηΐ 'P)ff S-Z ·8

 (Η2 'Ρ)28 "Ζ-08"Ζ (HS 'ω)9ε - - 6 '9 '(Ηΐ 'sjq)TO ·9

Ζ9 {W, 'Ρ)96 "9-28 "9 '(H6' S )9S ·ΐ Z-9ZZ

 (Ηΐ 'sjq)T2 Όΐ '(Ηΐ 'Ρ)8 ·8- '(Ηΐ 'Ρ)9ΐ '8-εΐ "8 '(HS 'ω)69 " -SS ' ' (Ηΐ 's)06 "9 9

99 (Η2 'Ρ)86 "9-^8 "9 ' (HS 's)88 'Ζ ' (HS 's)297 : 9 Ρ- OSMI '9 -ε

(Ηΐ 's)W ·0ΐ '(Ηΐ 'Ρ)9 8—S 8 '(Ηΐ : s)8T ·8

:(Ηΐ 'Ρ)Οΐ ·8- 60 ·8 ' (HS '^) 89 'L-£ "Ζ '(Ηΐ : s)26 ·9

 ' (Η2 'Ρ) 86 "9-98 "9 ' (Η2 9ΐ ·ε- Όΐ '£ :(Η£ 's)

ΐ 'Ζ (m <lu ) W\-ZZ '\ ' (HS 'ω) 98 Ό-28 Ό : 99

 'P-OSHQ 1 Ζ

 (Ηΐ 'Ρ)8 ·8- 9 ·8

 (Ηΐ 'ΡΡ)9ΐ ·8- Π ·8 ' (Η£ ' ) £8 ·Ζ ' (Ηΐ 'Ρ) 9ΐ ·8- Π ·8

 ' (HS 'ω) S8 "Ζ-Ζ9 "Ζ ' (Ηΐ 's) Ζ6 ·9 ' (Η2 'Ρ) 86 "9-98 "9 ζ

(Η^ 'ω)οε -ε-ζο τ '(HS'S)9 '(Η '冚) ·Ϊ- 9 ·Ϊ: 9 Ρ- OS I LZ- 'ΟΙΖ

 (Ηΐ 'Ρ)9 ·8- ·8

 '(Ηΐ 'Ρ)ΖΙ "8-0ΐ "8 ' (Η£ ' ) 06 ·Ζ— ·Ζ '(Ηΐ 's)Z6 "9

S9 (Η2 'Ρ) 66 "9-98 "9 ' (HS 's)29 Τ ' (HS 's)6T 7 : 9 Ρ- OSMI

 (Ηΐ 's) ·0ΐ ' (Ηΐ 'Ρ) Lf ·8- 9 ·8 ' (Ηΐ 'Ρ) fl '8~ΖΙ ·8

 (HS 'ω) S8 "Ζ-99 'ί ' (Ηΐ 's) £6 ·9 ' (Η2 'Ρ) Ζ6 "9-£8 "9 ' (Η 9

 Ζ

Ζ ε ε ΐ 6 · Ζ ' (HS 's) 02 · Ζ ' (Η9 ) W) · Η 8 Ό : 9 Ρ - OSMI '0ΖΖ-ί\Ζ

 (Ηΐ 's)86 ·6 (Ηΐ 'Ρ)

 8- ·8

(Ηΐ 'Ρ) 8 Ί-Ζ8 'ί (Ηε 'ω)6ε '(ΗΤ S )0Z ·9

Figure imgf000022_0001

Ol8C.0/llOZN3/X3d co o ζ OAV

Figure imgf000023_0001

Ol8C.0/llOZN3/X3d co o Ζ OAV

Figure imgf000024_0001

(Ηΐ 's) l ·6

 ' (Ηΐ ' ) '(Ηΐ 'ω)^8 Ί-ZS 'ί ' (Η2 '^) Ιζ Ί~η 'ί

 '(Ηΐ 's)92 'I '(Ηΐ 's) 8 '9 ' (Ηΐ 'Ρ) 80 ·9_90 ·9

 '(Η2 'Ρ)96 "9-28 "9 ' (Ηΐ '^)^8 '£~Ζ8 '£ ' (Η2 '^) 06 "ΐ-Ζ8"ΐ

 '(Η£ ' ) ^ΐ- 99 ·ΐ '(Η2 'ω) "ΐ-^ε "ΐ '(Η£ ' )8ΐ ·ΐ- 80 ·ΐ S6

(Ηΐ 's)g0 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 (Ηΐ 'Ρ)ΖΙ ·8- Οΐ ·8

 '(Ηΐ 's)Z6 "Ζ '(Ηΐ 'ω)89 "Ζ-99"Ζ (Ηΐ 'P)S -L-£ 'I

 '(Ηΐ 'P)2S ' -θε "Ζ '(HI 'S)96 "9 (Η2 'Ρ)66 "9-98 "9

 '(Ηΐ ' )09·ε '(HS 's)027 (Η^ '^) l "ΐ-99 "ΐ

(Ηΐ 'ω)89 "ΐ-99 "ΐ '(Η9 "ΐ-ΖΟ "ΐ : 9 Ρ - OSMI 26

 (Ηΐ 's)0T Όΐ '(Ηΐ 'Ρ)9 ·8- ·8

 '(Ηΐ 'Ρ)ΖΙ "8-ΐΐ "8 '(Ηΐ 's)T0 '8 ' (Ηΐ 's)g '

 (Η2 'ω) 9 " -1⁄2 "Ζ '(HT 's) 96 "9 ' (Η2 'Ρ) 86 "9-98 "9

 '(Ηΐ 'ω)09 Τ-89 '£ '(HS 's)gT '(Η ) εΖ'ΐ-99 'ΐ

'(Ηΐ 'ω)89 "ΐ-99 "ΐ '(Η9 LZ "ΐ-ΖΟ "ΐ : 9 Ρ - OSMI ΐ 6

 (Ηΐ 's)Tg ΐ '(Η2 'ω)ΐ9 ·8- ^ "8

 '(Ηΐ 'Ρ)06 "Ζ-88 "Ζ ' (Η£ ' ) 6£ ·Ζ '(Ηΐ 'ω)ΐΐ 'Z-80 "Ζ

 '(Ηΐ 's)99 "9 '(Ηΐ 'P)fl -9-ΖΙ "9 '(Η2 'Ρ) 86 "9-98 "9

(Ηΐ ' )ΐΟ ·卜 66 Έ ' (Η2 'ω) ΖΟ 7-90 'Ζ ' (Η2 '^) 28 "ΐ-6Ζ"ΐ

'(Η2 'ω)2 "ΐ-Ζ9 "ΐ '(1Ε · τ — '(Η2 ·ΐ- 02 ·ΐ 06

 (Ηΐ 's)06 "6 '(Ηΐ 'Ρ) ·8

 -£f ·8

 '(ΗΪ 'ρ)^8 -L-ZS · ' ΟΕ '冚) 9ε ·ζ-οε ·Ζ '(Ηΐ 's)\Z 'I

(HT 's) 86 ·9 ' (Ηΐ 's)ZO "9 '(Η2 'P)f6 "9-ΐ8 "9 '(H6' S )SS "ΐ 68

 (Ηΐ 's)0^ Όΐ

 (Ηΐ 'P)S ·8- ·8 '(Ηΐ 'P)S8 "Ζ-Ϊ8 "Ζ '(Ηΐ

(Ηΐ 'Ρ) 02 "Ζ-8ΐ ·ί ' (Ηΐ 'Ρ) ΖΟ "Ζ-90 ·ί ' (Ηΐ 's) 26 ·9

 '(Ηΐ 's)96 "9

'(Η2 'Ρ)96 "9-28 "9 ' (HS 's)9T '(H6' S )9S "ΐ 88

 (Ηΐ 's)T2 ΐ '(Η2 'Ρ)ΐ9 "8-6^ "8

 (Ηΐ 'Ρ) 06 "Ζ-88 "Ζ ' (Η£ ' ) 9£ ·Ζ '(Ηΐ 'ω) 60 "Ζ-90"Ζ

 ' (Ηΐ 's)g9 ·9

 Ζ8

' (Ηΐ 's)60 "9 '(Η2 'Ρ)86 "9-98 "9 '(H6' s )09 "ΐ

 (Ηΐ „ ·8- ' (IE '冚) 8£ ·8—

 1 (Η2 'ω) 8ΐ "8-80 "8 ' (Ηΐ '^)09 " -1⁄2 ' ' (Ηΐ 's)gO "Ζ

98 (Η2 'Ρ)00 "9-^8 "9 '(HS 's)9g '(H6' S )9S "ΐ : 9 Ρ- OSMI 29Τ-09Ϊ

 (Ηΐ 's)9T Όΐ

 '(Ηΐ 'Ρ)^ S-£ "8 '(Ηΐ 'P)S8 "Ζ-Ϊ8 "Ζ '(Ηΐ 's)T9

(Ηΐ 's)l 'I '(Ηΐ 'ω)9ε ' ' (Ηΐ 's)26 "9 ' (Ηΐ 's)86 "9

98 '(Η2 'Ρ)96 "9-28 "9 ' (HS 's)gT '(H6' S )9S "ΐ

 (Ηΐ 's)T ·0ΐ '(Ηΐ 'Ρ) Lf ·8- 9 ·8

 ' (Ηΐ 'ω) Π ·8- Οΐ ·8 ' (Ηΐ 's) 8Ζ ' ' (Η2 89 "Ζ-ΐ9 '

 '(Ηΐ 's)g6 ·9

 (Ηΐ 's) 0 ·9 ' (Η2 'Ρ) 86 "9-98 "9 ' (Η2 Π - 80 '

 ^8

(Η2 'P)f6 '£-Z6 '£ '(HS 's)ZZ 'Ζ '(HS '^)92 "ΐ-9ΐ "ΐ : 9 Ρ - OSMI

Ol8C.0/llOZN3/X3d co o Ζ OAV '(Ηΐ 's)L ''(HS's)U"Z'(Ηΐ's)1⁄2"9'(HT's)8 ·9

 W, 'P)TS "9-92 "9 W, 'P)S8 "9-Ϊ8 "9 '(Η2 'P)Z9 ^-29 f£Z-Z£Z LOT

(Ηΐ 's)66 "6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ)28 "Ζ-08"Ζ

 '(Ηΐ '^)η 'ί ' (Η2 'ω) 90 "Ζ-86 "9 ' (Η2 'Ρ) S6 "9-08 "9

 '0κ' )8ε·ε ' (Η2 'ω) go -ε-ε6 τ ' κ ΐ9 Ί- Ί

 '(Ηΐ 8ΐ ·ΐ- ΐ ·ΐ ' (HS 'ω) 96 Ό-26 Ό '(Ηΐ 'ω)0 Ό-99 Ό SLI-LLI 90ΐ

(Ηΐ 's)69 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'P)S8 "Ζ-ΐ8 "Ζ '(Η2

< lu )gg "Ζ '(Ηΐ 's)S8 "9 '(Ηΐ 's)62 "9 ' (Η2 'P)f6 "9-ΐ8 "9

 '(Η2 'ω)ΐε τ-9ζ τ 'ΟΕ'^ Ή ·ΐ ' (Hd) ε6 ·Ο-06 ·ο ΐΖΐ-ΟΖΐ 90ΐ

 (