US 2010O210574A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0210574 A1 Maienfisch et al. (43) Pub. Date: Aug. 19, 2010

(54) AVERMECTIN B1 ANDAVERMECTIN B1 (57) ABSTRACT MONOSACCHARDE DERVATIVES HAVING ANALKOXYMETHYL SUBSTITUENT IN What is described are a compound of the formula THE 4'-OR4'-POSITION (I) / / (75) Inventors: Peter Maienfisch, Stein (CH): O Fiona Murphy Kessabi, Basel (CH); Jerome Cassayre, Stein O ... I Oil II . . (CH); Laura Quaranta, Stein (CH); Thomas Pitterna, Stein Mp-( O O R2 R3 (CH); Ottmar Franz Hueter, Stein (CH); Pierre Jung, Stein (CH)

Correspondence Address: SYNGENTACROP PROTECTION, INC. PATENT AND TRADEMARK DEPARTMENT 410 SWING ROAD GREENSBORO, NC 27409 (US)

(73) Assignee: SYNGENTACROP PROTECTION, INC., Greensboro, NC (US)

(21) Appl. No.: 12/768,280 wherein (22) Filed: Apr. 27, 2010 n is 0 or 1: A-B is CH-CH or CH2—CH2—, R is C-C2-alkyl, C-Cs-cycloalkyl or C-C2-alkenyl; R is for example C-C2-alkyl, C-C2-alkenyl or C-C2 Related U.S. Application Data alkinyl; which are optionally substituted with one to five Substituents selected from the group consisting of OH, (63) Continuation of application No. 10/539.274, filed on halogen, CN, - N - NO, C-C-Cycloalkyl, nor Mar. 9, 2006, now Pat. No. 7,737.261, filed as appli bornylenyl-, C-C-Cycloalkenyl: C-C-halocy cation No. PCT/EP2003/014613 on Dec. 19, 2003. cloalkyl, C-C2-alkoxy, C-C-alkoxy-C-C-alkoxy, C-Cs-cycloalkoxy, C-C-haloalkoxy, C-C2-alky lthio, C-C-cycloalkylthio. C-C-haloalkylthio. C-C2-alkylsulfinyl, C-Cs-cycloalkylsulfinyl, C-C- (30) Foreign Application Priority Data haloalkylsulfinyl, C-C-halocycloalkylsulfinyl, C-C2-alkylsulfonyl, C-Cs-cycloalkylsulfonyl, C-C-haloalkylsulfonyl, C-Cs-halocycloalkylsulfo Dec. 20, 2002 (GB) ...... O2298.04.O nyl, —NRR —X—C(=Y)—R —X C(=Y) Z—R —P(=O)(OC-C-alkyl), aryl, heterocyclyl, Publication Classification aryloxy, arylthio and heterocyclyloxy; R is for example H, C-C2-alkyl or C-C2-alkyl which is (51) Int. Cl. optionally substituted and, where applicable, to E/Z iso AOIN 43/16 (2006.01) mers, mixtures of E/Z isomers and/or tautomers, in each C07H 17/08 (2006.01) case in free form or in salt form; AOIP 7/00 (2006.01) a process for preparing and using these compounds and their tautomers; pesticides whose active compound is Selected from these compounds and their tautomers; and a process for preparing these compounds and composi (52) U.S. Cl...... 514/30; 536/7.1 tions, and the use of these compounds and compositions. US 2010/0210574 A1 Aug. 19, 2010

AVERMECTIN B1 AND AVERMECTIN B1 one to five Substituents selected from the group consisting of MONOSACCHARDE DERVATIVES HAVING OH, halogen, CN, NO, C-C2-alkyl, C-Cs-cycloalkyl, ANALKOXYMETHYL SUBSTITUENT IN C-C-haloalkyl, C-C2-alkoxy, C-C-haloalkoxy, THE 4'-OR4'-POSITION C-C2-alkylthio, C-C-haloalkylthio, C-C-alkoxy-C- Co-alkyl, dimethylamino-C-C-alkoxy, C-Cs-alkenyl, C-C-alkinyl, methylendioxy, aryl, aryloxy heterocyclyl and 0001. The invention relates to (1) a compound of formula heterocyclyloxy;

(I)

/ ?

O III Oil III. III. Oil III III . . . .

Mp-( O O w R2 R3

0002 wherein 10008 R is H. C-C-alkyl or C-C-alkyl which is sub 0003 n is 0 or 1: stituted with one to five substituents selected from the group consisting of OH, halogen, CN, - N - NO, C-C-Cy 0004 A-B is -CH=CH- or -CH-CH : cloalkyl that is optionally substituted with one to three C-C- 0005 R is C-C-alkyl, C-C-cycloalkylor C-C-alk alkyl groups; norbornylenyl-; C-C-Cycloalkenyl that is enyl: optionally substituted with one to three methyl groups; 0006 R2 is C-C2-alkyl, C-C2-alkenyl, C-C2-alkinyl: C-Cs-halocycloalkyl, C-C2-alkoxy, C-C-alkoxy-C-C- or C-C2-alkyl, C-C2-alkenyl or C-C2-alkinyl, which are alkoxy, C-Cs-cycloalkoxy, C-C-haloalkoxy, C-C- substituted with one to five substituents selected from the alkylthio, C-C-cycloalkylthio, C-C-haloalkylthio. group consisting of OH, halogen, CN, - N - NO, C-C- C-C2-alkylsulfinyl, C-C-cycloalkylsulfinyl, C-C-ha cycloalkyl that is optionally substituted with one to three loalkylsulfinyl, C-Cs-halocycloalkylsulfinyl, C-C2-alkyl C-C-alkyl-groups, C-Cs-cycloalkenyl that is optionally Sulfonyl, C-Cs-cycloalkylsulfonyl, C-C-haloalkylsulfo Substituted with one to three C-C-alkyl-groups, nor nyl, C-C-halocycloalkylsulfonyl, —NRR —X-C bornylenyl, C-C-halocycloalkyl, C-C2-alkoxy, C-C- (—Y)—R —X—C(=Y)—Z R —P(=O)(OC-C- alkoxy-C-C-alkoxy, C-C-cycloalkoxy, C-C-ha alkyl), aryl, heterocyclyl, aryloxy, arylthio and loalkoxy, C-C2-alkylthio, C-Cs-cycloalkylthio, C-C2 heterocyclyloxy; wherein the aryl, heterocyclyl, aryloxy, haloalkylthio. C-C2-alkylsulfinyl, C-Cs arylthio and heterocyclyloxy groups are optionally—depend cycloalkylsulfinyl, C-C-haloalkylsulfinyl, C-Cs ing on the Substitution possibilities on the ring—Substituted halocycloalkylsulfinyl, C-C2-alkylsulfonyl, C-Cs with one to five substituents selected form the group consist cycloalkylsulfonyl, C-C-haloalkylsulfonyl, C-C- ing of OH, Halogen, CN, NO, C-C2-alkyl, C-C-Cy halocycloalkylsulfonyl, —NRR —X—C(=Y)—R. cloalkyl, C-C-Haloalkyl, C-C2-alkoxy, C-C-Ha -X-C(=Y)-Z-R - P(=O)(OC-C-alkyl), aryl, heterocy loalkoxy, C-C2-alkylthio. C-C-haloalkylthio, C-C- clyl, aryloxy, arylthio and heterocyclyloxy; wherein the aryl, alkoxy-C-C-alkyl, C-Cs-alkenyl, C-Cs-alkinyl, Si(C- heterocyclyl, aryloxy, arylthio and heterocyclyloxy groups C2-alkyl). —X—C(=Y)—R —X—C(=Y)—Z—R. are optionally—depending on the Substitution possibilities aryl, aryloxy, heterocyclyl and heterocyclyloxy; or on the ring substituted with one to five substituents selected 0009 R and R together are a three- to seven-membered form the group consisting of OH. Halogen, CN, NO, C-C- alkylen- or a four- to seven-membered alkenylenbridge, alkyl, C-C-Cycloalkyl, C-C-Haloalkyl, C-C2-alkoxy, wherein one or two CH2-groups may independently of each C-C-Haloalkoxy, C-C2-alkylthio, C-C-haloalkylthio. other be replaced by a group—C(=O)— —C(=S)—, O, S, C-C-alkoxy-C-C-alkyl, C-Cs-alkenyl, C-Cs-alkinyl, - NRs , —OC(=O)-O-, - OC(=O)S , —OC(=O) Si(C-C2-alkyl). X C(=Y)—R, X C(=Y) N(Rs)— —C(=O)C)— —C(=O)S , —C(=O)N(Rs)—, Z—R, aryl, aryloxy, heterocyclyl and heterocyclyloxy; or —N(Rs)C(=O)S , —N(Rs)C(=O)N(Rs)—, and wherein 0007 R is aryl, heterocyclyl C-C-cycloalkyl, C-C- the alkylene or alkenylenbridge may be independently of cycloalkenyl; or aryl, heterocyclyl C-C-Cycloalkyl or each other substituted with one or two substituents selected C-C-Cycloalkenyl, which are optionally—depending on from the group consisting of C-C-alkyl, which is optionally the substitution possibilities on the ring substituted with substituted with one to five substituents independently US 2010/0210574 A1 Aug. 19, 2010 selected from the group consisting of OH, Halogen, CN, which reason there is a need to provide further compounds NO. —N and C-C-alkoxy; having pesticidal properties, especially for the control of 0010 X is O, NRs or a bond; insects and members of the order Acarina. That problem is 0011 Y is O or S; solved according to the invention by the provision of the 0012 Z is O, S or NR present compounds of formula (I). 0013 R is H. C-C2-alkyl which is optionally substi 0023 The compounds claimed according to the invention tuted with one to five substituents selected from the group are derivatives of avermectin. Avermectins are known to the consisting of halogen, hydroxy, C-C-alkoxy and CN: person skilled in the art. They are a group of structurally C-C-alkenyl, C-C-alkinyl, aryl, heterocyclyl, aryl-C- closely related pesticidally active compounds which are C2-alkyl, heterocyclyl-C-C2-alkyl, or aryl, heterocyclyl, obtained by fermentation of a strain of the microorganism aryl-C-C2-alkyl or heterocyclyl-C-C2-alkyl, which are— Streptomyces avermitilis. Derivatives of avermectins can be depending on the Substitution possibilities—optionally Sub obtained via conventional chemical syntheses. stituted in the ring with one to five substituents selected from 0024. The avermectins obtainable from Streptomyces the group consisting of halogen, C-C-alkoxy, C-C-ha avermitilis are designated A1a, Alb, A2a, A2b, Bla, B1b, loalkyl and C-C-haloalkoxy; B2a and B2b. Compounds with the designation 'A' have a 0014 Rs is H. C-C-alkyl, C-Cs-cycloalkyl, C-C-alk methoxy radical in the 5-position; those compounds desig enyl, C-C-alkinyl, benzyl or —C(=O)—C-C2-alkyl; nated “B” have an OH group. The “a” series comprises com 0015 R is H. C-C2-alkyl which is optionally substi pounds wherein the Substituent R (in position 25) is a sec tuted with halogen, C-C-alkoxy, CN, C-C-alkenyl, butyl radical; in the “b' series there is an isopropyl radical in C-Cs-haloalkenyl, C-C-alkinyl, C-C-Haloalkenyl, the 25-position. The number 1 in the name of a compound X—C(=Y)—R —X—C(=Y)—Z-Ro. —SC, R, indicates that atoms 22 and 23 are bonded by a double bond; aryl, heterocyclyl, aryl-C-C2-alkyl, heterocyclyl-C-C- the number 2 indicates that they are bonded by a single bond alkyl; or aryl, heterocyclyl, aryl-C-C2-alkyl or heterocy and carbon atom 23 carries an OH group. The above desig clyl-C-C-alkyl, which are—depending on the Substitution nations are retained in the description of the present invention possibilities—optionally Substituted in the ring with one to in order in the case of the non-natural avermectin derivatives five Substituents selected from the group consisting of halo according to the invention to indicate the specific structural gen, C-C-alkoxy, C-C-haloalkyl or C-C-haloalkoxy; or type corresponding to natural avermectin. There are claimed 0016 Ra and R together are a three- to five membered according to the invention derivatives of compounds of the B1 alkylene bridge, wherein one of the methylene groups may be and B2 series, more especially mixtures of derivatives of replaced by O.S or SO; and avermectin B1a, B1b, B2a and B2b or the corresponding 0017 R is H. C-C-alkyl which is optionally substi monosaccharides having, at the 4- or 4"-position (c-posi tuted with one to five substituents selected from the group tion), either the S- or the R-configuration. consisting of halogen, hydroxy, C-C-alkoxy and CN: 0025. Some of the compounds of formula (I) may be in the C-Cs-alkenyl, C-Cs-alkinyl, aryl, heterocyclyl, aryl-C- form of tautomers. Accordingly, any reference to the com C2-alkyl, heterocyclyl-C-C2-alkyl, or aryl, heterocyclyl, pounds of formula (I) hereinbefore and hereinafter is to be aryl-C-C-alkyl or heterocyclyl-C-C-alkyl, which are— understood, where applicable, as including also correspond depending on the Substitution possibilities—optionally Sub ing tautomers, even if the latter are not specifically mentioned stituted in the ring with one to five substituents selected from in every case. the group consisting of halogen, C-C-alkoxy, C-C-ha 0026. The compounds of formula (I) and, where appli loalkyl and C-C-haloalkoxy; cable, their tautomers can form salts, for example acid addi 0018 and, where applicable, to E/Z isomers, mixtures of tion salts. These acid addition salts are formed, for example, E/Z isomers and/or tautomers, in each case in free form or in with Strong inorganic acids, such as mineral acids, for salt form; example Sulfuric acid, a phosphoric acid or a hydrohalic acid; 0019 with the proviso, that the compound is not an Aver with strong organic carboxylic acids, such as unsubstituted or mectin B1 derivative wherein n is 1, R is H, and R is substituted, for example halo-substituted, —CH2—CH2—OCH or —CH2—CH2—O-phenyl: is not C-C alkanecarboxylic acids, for example acetic acid, unsat the B1 derivative wherein n is 2, R is H, and R is —CH2— urated or saturated dicarboxylic acids, for example oxalic CH-O-phenyl; and is not the B1 derivative wherein A-B is acid, malonic acid, maleic acid, fumaric acid orphthalic acid, —CH2—CH2—, n is 1, R is H. and R is —CH2—OH hydroxycarboxylic acids, for example ascorbic acid, lactic OCH: acid, malic acid, tartaric acid or citric acid, or benzoic acid; or 0020 to a process for the preparation of and to the use of with organic Sulfonic acids, such as unsubstituted or Substi those compounds and their isomers and tautomers; to starting tuted, for example halo-substituted, C-C alkane- or aryl materials and intermediates for the preparation of the com Sulfonic acids, for example methane- or p-toluene-Sulfonic pounds of formula (I); to pesticidal compositions in which the acid. Compounds of formula (I) that have at least one acidic active ingredient has been selected from the compounds of group can furthermore form salts with bases. Suitable salts formula (I) and their tautomers; to a method for preparing the with bases are, for example, metal salts, such as alkali metal said compositions; and to a method of controlling pests using salts or alkaline earth metal salts, for example Sodium, potas those compositions. sium or magnesium salts; or salts with ammonia or with an 0021 Hereinbefore and hereinafter, the bond marked by organic amine, Such as morpholine, piperidine, pyrrolidine, a the symbol VVVVinformulae (I), (II) and (IV) indicates that at mono-, di- or tri-lower alkylamine, for example ethylamine, the c-position the S- as well as the R-isomer is meant. diethylamine, triethylamine or dimethylpropylamine, or a 0022. Certain macrollide compounds are proposed for pest mono-, di- or trihydroxy-lower alkylamine, for example control in the literature. The biological properties of those mono-, di- or tri-ethanolamine. Corresponding internal salts known compounds are not entirely satisfactory, however, for may also be formed where appropriate. The free form is US 2010/0210574 A1 Aug. 19, 2010 preferred. Among the salts of the compounds of formula (I), polyhalogenation for the halogen Substituents to be the same the agrochemically advantageous salts are preferred. Herein or different. Examples of haloalkyl as a group perse and as before and hereinafter, any reference to the free compounds a structural element of other groups and compounds. Such as of formula (I) or their salts is to be understood as including, haloalkoxy and haloalkylthio—are methyl substituted from where appropriate, also the corresponding salts or the free one to three times by fluorine, chlorine and/or bromine, such compounds of formula (I), respectively. The same applies to as CHF, or CF; ethyl substituted from one to five times by tautomers of compounds of formula (I) and salts thereof. fluorine, chlorine and/or bromine, such as CHCF, CFCF 0027. Unless defined otherwise, the general terms used CFCC1, CFCHC1, CFCHF, CFCFC1, CFCHBr, hereinbefore and hereinafter have the meanings given below. CFCHCIF, CFCHBrFor CCIFCHCIF; propyl or isopropyl 0028. Unless defined otherwise, carbon-containing substituted from one to seven times by fluorine, chlorine groups and compounds each contain from 1 up to and includ and/or bromine, such as CHCHBrCHBr, CFCHFCF, ing 6, preferably from 1 up to and including 4, especially 1 or CHCFCF or CH(CF); butyl or an isomer thereof substi 2, carbon atoms. tuted from one to nine times by fluorine, chorine and/or 0029 Halogen—as a group perse and as a structural ele bromine, such as CF(CF)CHFCF or CH (CF) CF; pentyl ment of other groups and compounds, such as haloalkyl, or an isomer thereof substituted from one to eleven times by haloalkoxy and haloalkylthio is fluorine, chlorine, bromine fluorine, chlorine and/or bromine, such as CF(CF)(CHF) oriodine, especially fluorine, chlorine or bromine, more espe CF or CH (CF)CF; and hexyl or an isomer thereof sub cially fluorine or chlorine. stituted from one to thirteen times by fluorine, chlorine and/or 0030 Alkyl as a group perse and as a structural element bromine, such as (CH2)CHBrCHBr, CF (CHF)CF, CH of other groups and compounds, such as haloalkyl, alkoxy (CF)CF or C(CF)(CHF)CF. and alkylthio—is, in each case giving consideration to the 0036) Aryl is especially phenyl, naphthyl, anthracenyl or number of carbonatoms contained in the group or compound perylenyl, preferably phenyl. in question, either straight-chained, i.e. methyl, ethyl, propyl. 0037. Heterocyclyl is especially pyridyl, pyrimidyl, s-tri butyl, pentyl, hexyl, heptyl or octyl, or branched, e.g. isopro azinyl, 1,2,4-triazinyl, thienyl, furyl, tetrahydrofuranyl, pyra pyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or nyl, tetrahydropyranyl, pyrrolyl pyrazolyl, imidazolyl, thia isohexyl. Zolyl, triazolyl, tetrazolyl, oxazolyl, thiadiazolyl, 0031 Cycloalkyl as a group per se and as a structural oxadiazolyl, benzothienyl, quinolinyl, quinoxalinyl, benzo element of other groups and compounds, such as halocy furanyl, benzimidazolyl, benzopyrrolyl, benzothiazolyl, cloalkyl, cycloalkoxy and cycloalkylthio is, in each case indolyl, coumarinyl or indazolyl, which are preferably giving due consideration to the number of carbon atoms con bonded via a carbon atom; preference is given to thienyl, tained in the group or compound in question, cyclopropyl. thiazolyl, benzofuranyl, benzothiazolyl, furyl, tetrahydropy cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooc ranyl and indolyl; especially pyridyl or thiazolyl. tyl. 0038. Within the scope of the present invention, prefer 0032 Alkenyl as a group perse and as a structural ele ence is given to ment of other groups and compounds—is, giving due consid 0039 (2) a compound according to group (1) of formula eration to the number of carbon atoms and conjugated or (I) in the free form: isolated double bonds contained in the group in question, 0040 (3)a compound according to anyone of groups (1) or either straight-chained, e.g. vinyl, allyl, 2-butenyl, 3-pente (2) of formula (I) wherein R is H: nyl, 1-hexenyl, 1-heptenyl, 1.3-hexadienyl or 1.3-octadienyl, 0041 (4)a compound according to anyone of groups (1) or or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pen (2) of formula (I) wherein R is C-C-alkyl; tenyl, isohexenyl, isoheptenyl or isooctenyl. Alkenyl groups 0042 (5) a compound according to anyone of groups (1) to having from 3 to 12, especially from 3 to 6, more especially 3 (4) of formula (I) wherein R is C-C-alkyl, especially or 4, carbon atoms are preferred. methyl; 0033 Alkynyl as a group perse and as a structural ele 0043 (6) a compound according to anyone of groups (1) to ment of other groups and compounds—is, in each case giving (5) of formula (I) wherein R is C-Cs-alkyl, especially pro due consideration to the number of carbon atoms and conju pylor isopropyl; gated or isolated triple bonds contained in the group or com 0044 (7) a compound according to anyone of groups (1) to pound in question, either straight-chained, e.g. ethynyl, pro (5) of formula (I) wherein R is a branched C-C-alkyl, pargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, especially isobutyl, sec-butyl or tert-butyl: 3-hexen-1-ynyl or 1.5-heptadien-3-ynyl, or branched, e.g. 0045 (8) a compound according to one of groups (1) to (4) 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2- of formula (I) wherein R is C-Cs-alkoxy-C-C-alkyl; ynyl or 2-methylhept-3-ynyl. Alkynyl groups having from 3 0046 (9) a compound according to anyone of groups (1) to to 12, especially from 3 to 6, more especially 3 or 4, carbon (4) of formula (I) wherein R is C-C-alkyl which is substi atoms are preferred. tuted with one to five substituents selected from the group 0034 Alkylene and alkenylene are straight-chained or consisting of OH, halogen, CN, - N - NO, C-C-cy branched bridge members, especially —CH2—CH2— cloalkyl which is optionally substituted with one to three C-C-alkyl groups; norbornylenyl: C-C-Cycloalkenyl which is optionally substituted with one to three methyl groups: C-C-halocycloalkyl, C-Cs-cycloalkoxy, C-C2 CH or —CH-CH=CH-CH CH . haloalkoxy, C-C2-alkylthio, aryl, heterocyclyl, arylthio or 0035 Halo-substituted carbon-containing groups and heterocyclyloxy; wherein the aryl, heterocyclyl, arylthio and compounds. Such as alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyloxy groups are optionally—depending on the alkoxy or alkylthio Substituted by halogen, may be partially substitution possibilities on the ring substituted with one to halogenated or perhalogenated, it being possible in the case of five substituents selected form the group consisting of OH, US 2010/0210574 A1 Aug. 19, 2010

Halogen, CN, NO, C-C2-alkyl, C-Cs-cycloalkyl, C-C2 0052 (14) a compound according to anyone of groups (1) haloalkyl, C-C2-alkoxy, C-C-haloalkoxy, C-C2-alky to (12) of the formula (I), in which n is 1: lthio, C-C-haloalkylthio, C-C-alkoxy-C-C-alkyl, 0053 (15) a compound according to anyone of groups (1) C-C-alkenyl, C-C-alkinyl, Si(C-C2-alkyl). —X—C to (12) of the formula (I), in which n is 0; (=Y)—R —X—C(=Y)—Z-Ra, aryl, aryloxy, heterocy 0054 (16) a compound according to anyone of groups (1) clyl and heterocyclyloxy; more especially wherein to (15) of the formula (I), in which A-B is —CH2—CH2—, 0047 R is C-C-alkyl which is substituted with one sub 0055 (17) a compound according to anyone of groups (1) stituent selected from the group consisting of C-C-cy cloalkylthio. C-C-haloalkylthio. C-C2-alkylsulfinyl, to (15) of the formula (I), in which A-B is —CH=CH-: C-Cs-cycloalkylsulfinyl, C-C-haloalkylsulfinyl, C-Cs 0056 (18) a compound according to anyone of groups (1) halocycloalkylsulfinyl, C-C2-alkylsulfonyl, C-C-cy to (17) of the formula (I) having the R-configuration in the cloalkylsulfonyl, C-C-haloalkylsulfonyl, C-Cs-halocy e-position; cloalkylsulfonyl, —NRR —X—C(=Y)—R —X—C 0057 (19) a compound according to anyone of groups (1) (—Y)—Z R —P(=O)(OC-C-alkyl); to (17) of the formula (I) having the S-configuration in the 0.048 (10) a compound according to anyone of groups (1) e-position; to (4) of formula (I) wherein R is C-C-alkyl which is 0.058 (20) a compound according to anyone of groups (1) substituted with one or two substituents selected from the to (19) of the formula (I) with the further proviso that the group consisting of OH, halogen, CN, - N - NO, C-C- compound is not the Avermectin B1 derivative wherein n is 1, alkylsulfinyl, C-C2-alkylsulfonyl, C-C-haloalkylsulfo and R and R together are unsubstituted —CH2—CH2— nyl. —NRR-X—C(=Y)—R —X—C(=Y)—Z—R. CH2—CH2—. aryl or heterocyclyl, wherein the aryland heterocyclyl groups 0059 Especially preferred are the compounds of the are optionally—depending on the Substitution possibilities tables. on the ring substituted with one or two substituents selected 0060. The invention further relates to a process for the form the group consisting of OH. Halogen, CN, NO, C-C- preparation of the compounds of formula (I) as defined above alkyl, -Cs-cycloalkyl, C-C-haloalkyl, C-C2-alkoxy, under (1) and, where applicable, tautomers thereof, which C-C-haloalkoxy, C-C2-alkylthio, C-C-haloalkylthio. comprises C-C-alkoxy-C-C-alkyl, C-Cs-alkenyl, C-Cs-alkinyl, 0061 (A) reacting a compound of formula

(II)

O O

HOVVA ... I IOI. . . III Oil III III I. . . pi O O * w

Si(C-C2-alkyl). X C(=Y)—R, X C(=Y) 0062 wherein R, n and the grouping A-B are as defined Z—R, aryl, aryloxy, heterocyclyl and heterocyclyloxy; above under group (1) for formula (I) and Q is a protecting 0049 (11) a compound according to anyone of groups (1) group, and which is known or can be prepared by methods to (4) of formula (I) wherein RandR together area three- to known perse, with a compound of formula five-membered alkenylenbridge, wherein one two CH group may be replaced by a group —C(=O)— —C(=S)—, O, S or - NRs , and wherein the alkylene or alkenylen (III) bridge may be independently of each other substituted with O Hal one or two Substituents selected from the group consisting of C-C-alkyl; 0050 (12) a compound according to anyone of groups (1) to (11) of formula (I) wherein R is isopropyl or sec-butyl, preferably wherein a mixture of the isopropyl and the sec 0063 wherein R and R are as defined above for formula butyl derivative is present; (I) and Hal is a halogen atom, preferably bromine or iodine, 0051 (13) a compound according to anyone of groups (1) and which is known or can be prepared by known methods, to to (11) of formula (I) wherein R is cyclohexyl; form a compound of formula US 2010/0210574 A1 Aug. 19, 2010

(IV)

O

O I I IOIII. I. III II. Oil III III . . . . pi p-( O O R4 R3 w

0064 wherein Q, R. R. and R are as defined for formula 0068 wherein R is as defined for formula (I) and R, is H. (II); and C-C-alkyl or C-C-halogenalkyl, or R are R, together 0065 (B) removing the protecting group Q of the com are a three- to six-membered alkylen- or a four- to six-mem pound of formula (IV) so obtained. bered alkenylen, wherein one CH-group is optionally 0066. The invention further relates to a process for the replaced by a group selected from C(=O), —C—S, O, S, preparation of the compounds of formula (I) as defined above - NRs –OC(=O)C) , —OC(=O)S , —OC(=O) undergroup (1), wherein R is —CHR, NRs , —C(=O)C)— —C(=O)S , —C(=O)NRs , —NRC(=O)S and —NRCONRs , and wherein alk 0067 (C) reacting a compound of formula (II) with a enylen is optionally substituted with one or two substituents compound of formula which are selected form the group consisting of C-C-alkyl, C-C-alkoxy and C-Ca-halogenalkyl, and wherein the said substituents are independent of each other; 0069 (D) In particular, compounds of the formula (I), (V) wherein R is CHHal and Hal is a halogen can be prepared by deprotection of compounds of the formula (IV), wherein R is CHHal. The latter can be prepared by haloacetalization of compounds of the formula

(VI)

O O

III IOIII. I. III. Oili II II . . . . . pi O O * w US 2010/0210574 A1 Aug. 19, 2010

0070 Compounds of the formula (VI) can be prepared by dimethyl sulfoxide; or mixtures of the mentioned solvents. vinylation of compounds of the formula (II). Preference is given to amides, such as dimethylformamide 0071 Compounds of the formula (IV), wherein R is and dimethylacetamide, especially dimethylacetamide. CHHal can in particular be used to prepare other compounds of the formula (IV), wherein R is CHRs, wherein Rs is CN, I0081 Protecting groups Q in the compounds of formulae NRR - NHC(=O)R. NHNH2, NHNHR, NRNRR, (II) and (IV) include: alkyl ether radicals, such as methoxym OR or SR ethyl, methylthiomethyl, tert-butylthiomethyl, benzyloxym 0072 Compounds of the formula (IV) are preferred com ethyl, p-methoxybenzyl, 2-methoxyethoxymethyl, 2.2.2- pounds for the preparation of compounds of the formula (I). trichloroethoxymethyl, 2-(trimethylsilyl)ethoxymethyl, 0073. Furthermore compounds of formula (I) bearing a tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-(2- functional group in its free or protected form can be used as chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, 1-methyl-1- starting materials for the preparation of further compounds of benzyloxyethyl, trichloroethyl 2-trimethylsilylethyl, tert-bu formula (I). For Such manipulations methods known to the tyl, allyl, p-methoxyphenyl, 2,4-dinitrophenyl, benzyl, person skilled in the art can be applied. p-methoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, triphenylm 0074 For example a compound of formula (I) wherein R ethyl; trialkylsilyl radicals, such as trimethylsilyl, triethylsi is CHCHOC(=O)CH can be converted to a compound of lyl, dimethyl-tert-butylsilyl dimethyl-isopropylsilyl dim formula (I) wherein R is CHCH-OH. Further standard reac ethyl-1,1,2-trimethylpropylsilyl, diethyl-isopropylsilyl, tions can deliver compounds of formula (I) wherein R is dimethyl-tert-hexylsilyl, but also phenyl-tert-alkylsilyl CHCHOCHO-Alkyl, CHCHOC(=O)R CHCHOC groups, such as diphenyl-tert-butylsilyl; esters, such as for (=O)ZR and CHCHN. A compound of formula (I) mates, acetates, chloroacetates, dichloroacetates, trichloroac wherein R is CHCHN can be converted to a compound of etates, trifluoroacetates, methoxyacetates, phenoxyacetates, formula (I) wherein R is CHCH-NH. Treatment of such a compound of formula (I) with Hal-C(=O)R or Hal-C(=O) pivaloates, benzoates; alkyl carbonates, such as methyl-, ZR gives compounds of formula (I) wherein R is 9-fluorenylmethyl-, ethyl-, 2.2.2-trichloroethyl-, 2-(trimeth CHCH-NHC(=O)R and CHCH-NHC(=O)ZR respec ylsilyl)ethyl-, vinyl-, allyl-, benzyl-, p-methoxybenzyl-, o-ni tively trobenzyl-, p-nitrobenzyl-, but also p-nitrophenyl-carbonate. 0075. The reactions described hereinbefore and hereinaf I0082 Preference is given to trialkylsilyl radicals, such as ter are carried out in a manner known perse, for example in trimethylsilyl, triethylsilyl, dimethyltert-butylsilyl, diphenyl the absence or, customarily, in the presence of a Suitable tert-butylsilyl esters, such as methoxyacetates and phenoxy solvent or diluent or of a mixture thereof, the reactions being acetates, and carbonates, such as 9-fluorenylmethylcarbon carried out, as required, with cooling, at room temperature or ates and allylcarbonates. Dimethyl-tertbutylsilyl ether is with heating, for example in a temperature range of approxi especially preferred. mately from -80°C. to the boiling temperature of the reaction I0083. The reactions are advantageously carried out in a medium, preferably from approximately 0° C. to approxi temperature range of from approximately -70° C. to 50° C. mately +150° C., and, if necessary, in a closed vessel, under preferably at from -10° C. to 25° C. pressure, under an inert gas atmosphere and/or under anhy I0084 Examples P1 and P2 provide in more detail the drous conditions. Especially advantageous reaction condi reaction conditions. tions can be found in the Examples. 0076. The reaction time is not critical; however a reaction I0085 Process Variant (B): time of from approximately 0.1 to approximately 72 hours, I0086 Examples of solvents and diluents are the same as especially from approximately 0.5 to approximately 24 those mentioned under Process variant A. In addition, alco hours, is preferred. hols, such as methanol, ethanol or 2-propanol, and water are 0077. The product is isolated by customary methods, for suitable. example by means of filtration, crystallisation, distillation or I0087. The reactions are advantageously carried out in a chromatography, or any suitable combination of Such meth temperature range of approximately from -70° C. to 100°C., ods. preferably at from -10° C. to 25° C. 0078. The starting materials mentioned hereinbefore and I0088. There are suitable for the removal of the protecting hereinafter that are used for the preparation of the compounds group Lewis acids, such as hydrochloric acid, methane of formula (I) and, where applicable, their tautomers are sulfonic acid, BF*OEt, HF in pyridine, Zn(BF)*HO, known or can be prepared by methods known per se, e.g. as p-toluenesulfonic acid, AlCls. HgCl2, ammonium fluoride, indicated below. Such as tetrabutylammonium fluoride; bases, such as ammo 0079 Process Variant (A): nia, trialkylamine or heterocyclic bases; hydrogenolysis with 0080 Examples of solvents and diluents include: aro a catalyst, Such as palladium-on-carbon; reducing agents, matic, aliphatic and alicyclic hydrocarbons and halogenated such as sodium borohydride or tributyltin hydride with a hydrocarbons. Such as benzene, toluene, Xylene, mesitylene, catalyst, such as Pd(PPh3)4, or also Zinc with acetic acid. tetralin, chlorobenzene, dichlorobenzene, bromobenzene, I0089 Preference is given to acids, such as methane petroleum ether, hexane, cyclohexane, dichloromethane, sulfonic acid or HF in pyridine: sodium borohydride with trichloromethane, tetrachloromethane, dichloroethane, Pd(0); bases, such as ammonia, triethylamine or pyridine; trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert especially acids, such as HF in pyridine or methanesulfonic butyl methyl ether, ethylene glycol monomethyl ether, ethyl acid. ene glycol monoethyl ether, ethylene glycol dimethyl ether, 0090 Especially preferred conditions for the reaction are dimethoxydiethyl ether, tetrahydrofuran or dioxane; esters of described in Example P.1, P2, P3, P4 and P5. carboxylic acids, such as ethyl acetate; amides, such as dim (0091 Process Variant (C): ethylformamide, dimethylacetamide or 1-methyl-2-pyrroli 0092. Examples of solvents and diluents are the same as dinones; nitriles. Such as acetonitrile; Sulfoxides, such as those mentioned under Process variant A. US 2010/0210574 A1 Aug. 19, 2010

0093. The reactions are advantageously carried out in a 0105. In the processes of the present invention it is pref temperature range of approximately from -70° C. to 100° C. erable to use those starting materials and intermediates which preferably at from -10° C. to 55° C. result in the compounds of formula (I) that are especially 0094. The reaction is preferably performed in the presence preferred. of an acid or Lewis acid. Typical acids and Lewis acids are 0106 The invention relates especially to the preparation especially mineral acids, e.g. Sulfuric acid, a phosphoric acid processes described in the Examples. or a hydrohalic acid, especially hydrochloric acid, methane 0107 The invention further relates to the compounds of Sulfonic acid, e.g. halo-substituted, C-C alkanecarboxylic formula (IV) and, where applicable, E/Z isomers, mixtures of acid, for example acetic acid, a saturated or unsaturated dicar E/Z isomers and/or tautomers, in each case in free form or in boxylic acid, for example oxalic acid, malonic acid, maleic salt form. acid, fumaric acid orphthalic acid, a hydroxycarboxylic acid, 0108. In the area of pest control, the compounds of for for example ascorbic acid, lactic acid, malic acid, tartaric acid mula (I) according to the invention are active ingredients or citric acid, or benzoic acid, or BF*OEt. exhibiting valuable preventive and/or curative activity with a 0095 Process Variant (D): very advantageous biocidel spectrum and a very broad spec 0096. Examples of solvents and diluents are the same as trum, even at low rates of concentration, while being well those mentioned under Process variant A. tolerated by warm-blooded animals, fish and plants. They are, 0097. The reactions are advantageously carried out in a Surprisingly, equally Suitable for controlling both plant pests temperature range of approximately from -70° C. to 150° C. and ecto- and endo-parasites in humans and more especially preferably at from -20° C. to 120° C. in productive livestock, domestic animals and pets. They are effective against all or individual development stages of nor 0.098 Preferred reaction conditions for the haloacetaliza mally sensitive animal pests, but also of resistant animal tion and the vinylation are as such as described in the litera pests, such as insects and representatives of the order Acarina, ture known to a person skilled in the art. nematodes, cestodes and trematodes, while at the same time 0099. The compounds of formula (I) may be in the form of protecting useful organisms. The insecticidal or acaricidal one of the possible isomers or in the form of a mixture thereof, activity of the active ingredients according to the invention in the form of pure isomers or in the form of an isomeric may manifest itself directly, i.e. in the mortality of the pests, mixture, i.e. in the form of a diastereomeric mixture; the which occurs immediately or only after some time, for invention relates both to the pure isomers and to the diaste example during moulting, or indirectly, for example in reomeric mixtures and is to be interpreted accordingly here reduced oviposition and/or hatching rate, good activity cor inabove and hereinbelow, even if stereochemical details are not mentioned specifically in every case. responding to a mortality of at least 50 to 60%. 0109 Successful control within the scope of the subject of 0100. The diastereomeric mixtures can be resolved into the invention is possible, in particular, of pests from the orders the pure isomers by known methods, for example by recrys Lepidoptera, Coleoptera, Orthoptera, Isoptera, Psocoptera, tallisation from a solvent, by chromatography, for example Anoplura, Mallophaga, Thysanoptera, Heteroptera, high pressure liquid chromatography (HPLC) on acetylcellu Homoptera, Hymenoptera, Diptera, Siphonaptera, Thysa lose, with the aid of Suitable microorganisms, by cleavage with specific, immobilised enzymes, or via the formation of nura and Acarina, mainly Acarina, Diptera, Thysanoptera, inclusion compounds, for example using crown ethers, only Lepidoptera and Coleoptera. Very especially good control is one isomer being complexed. possible of the following pests: 0110 Abagrotis spp., Abraxas spp., Acantholeucania 0101 Apart from by separation of corresponding mixtures spp., Acanthoplusia spp., Acarus spp., Acarus spp., Aceria of isomers, pure diastereoisomers can be obtained according spp., Aceria Sheldoni, Acleris spp., AcOloithus spp., Acomp to the invention also by generally known methods of stereo sia spp., Acossus spp., Acria spp., Acrobasis spp., Acrocer selective synthesis, for example by carrying out the process Cops spp., Acrolepia spp., Acrolepiopsis spp., Acronicta spp., according to the invention using starting materials having Acropolitis spp., Actebia spp., Aculus spp., Aculus Schlecht correspondingly suitable stereochemistry. endali, Adoxophyes spp., Adoxophyes reticulana, Aedes spp., 0102. In each case it is advantageous to isolate or synthe Aegeria spp., Aethes spp., Agapeta spp., Agonopterix spp., sise the biologically more active isomer, where the individual Agriopis spp., Agriotes spp., Agriphila spp., Agrochola spp., components have different biological activity. Agroperina spp., Alabama ssp., Alabama argillaceae, Agrotis 0103) The compounds of formula (I) may also be obtained spp., Albuna spp., Alcathoe spp., Alcis spp., Aleimma spp., in the form of their hydrates and/or may include other sol Aletia spp., Aleurothrixus spp., Aleurothrixus floccosus, Aley vents, for example solvents which may have been used for the rodes spp., Aleyrodes brassicae, Allophyes spp., Alsophila crystallisation of compounds in Solid form. spp., Amata spp., Amathes spp., Amblyomma spp., Amblyp 0104. The invention relates to all those embodiments of tilia spp., Ammoconia spp., Amorbia spp., Amphion spp., the process according to which a compound obtainable as AmphipOea spp., Amphipyra spp., Amyelois spp., Anacamp starting material or intermediate at any stage of the process is todes spp., Anagrapha spp., Anarsia spp., Anatrychyntis spp., used as starting material and all or some of the remaining Anavitrinella spp., Ancylis spp., Andropolia spp., Anhinella steps are carried out, or in which a starting material is used in spp., Antheraea spp., Antherigona spp., Antherigona Soc the form of a derivative and/or a salt and/or its diastereomers, cata, Anthonomus ssp., Anthonomus grandis, Anticarsia spp., or, especially, is formed under the reaction conditions. For Anticarsia gemmatalis, Aonidiella spp., Apamea spp., Aph instance compounds of formula (I) bearing a functional group ania spp., Aphelia spp., Aphididae, Aphis spp., Apotomis in its free or protected form can be used as starting materials spp., Aproaerema spp., Archippus spp., Archips spp., for the preparation of further compounds of formula (I). For Acromyrmex, Arctia spp., Argas spp., Argolamprotes spp., Such manipulations methods known to the person skilled in Argyresthia spp., Argyrogramma spp., Argyroploce spp., the art can be applied. Argyrotaenia spp., Arotrophora spp., Ascotis spp., Aspidiotus US 2010/0210574 A1 Aug. 19, 2010 spp., Aspilapteryx spp., Asthenoptycha spp., Aterpia spp., spp., Euellidia spp., Eueosma spp., Euchistus spp., Eucosmo Athetis spp., Atomaria spp., Atomaria linearis, Atta spp., morpha spp., Eudonia spp., Eufidonia spp., Euhyponomeu A typha spp., Autographa spp., Axylia spp., Bactra spp., Bar toides spp., Eulepitodes spp., Eulia spp., Eulithis spp., Eupi bara spp., Batrachedra spp., Battaristis spp., Bembecia spp., thecia spp., Euplexia spp., Eupoecilia spp., Eupoecilia Bemisia spp., Bemisia tabaci, Bibio spp., Bibio hortulanis, ambiguella, Euproctis spp., Eupsilia spp., Eurhodope spp., Bisigna spp., Blastesthia spp., Blatta spp., Blatella spp., Ble Eurois spp., Eurygaster spp., Eurythmia spp., Eustrotia spp., pharosis spp., Bleptina spp., Boarmia spp., Bombyx spp., Euxoa spp., Euzophera spp., Evergestis spp., Evippe spp., Bomolocha spp., Boophilus spp., Brachnia spp., Bradina Exartema spp., Fannia spp., Faronta spp., Feltia spp., Fila spp., Brevipalpus spp., Brithys spp., Bryobia spp., Bryobia tima spp., Fishia spp., Frankliniella spp., Fumibotys spp., praetiosa, Bryotropha spp., Bupalus spp., Busseola spp., Gaesa spp., Gasgardia spp., Gastrophilus spp., Gelechia Busseola fisca, Cabera spp., Cacoecimorpha spp., Cadra spp., Gilpinia spp., Gilpinia polytoma, Glossina spp., Glyph spp., Cadra cautella, Caenurgina spp., Calipitrimerus spp., ipterix spp., Glyphodes spp., Gnorimoschemini spp., Gon Callierges spp., Callophpora spp., Callophpora erythro Odonta spp., Gortyna spp., Gracillaria spp., Graphania spp., cephala, Calophasia spp., Caloptilia spp., Calybites spp., Grapholita spp., Grapholitha spp., Gravitarmata spp., Capnoptycha spp., Capua spp., Caradrina spp., Caripeta Gretchena spp., Griselda spp., Gryllotalpa spp., Gynaephora spp., Carmenta spp., CarpOsina spp., CarpOsina nipponen spp., GvpsOnoma spp., Hada spp., Haematopinus spp., Hal sis, Catamacta spp., Catelaphris spp., Catoptria spp., Caus isidota spp., Harpipteryx spp., Harrisina spp., Hedya spp., toloma spp., Celaena spp., Celypha spp., Cenopis spp., Helicoverpa spp., Heliophobus spp., Heliothis spp., Hellula Cephus spp., Ceramica spp., Cerapteryx spp., Ceratitis spp., spp., Helotropa spp., Hemaris spp., Hercinothrips spp., Her Ceratophyllus spp., Ceroplaster spp., Chaetocnema spp., culia spp., Hermonassa spp., Heterogenea spp., Holomelina Chaetocnema tibialis, Chamaesphecia spp., Charanvca spp., spp., Homadaula spp., Homoeosoma spp., Homoglaea spp., Cheinophila spp., ChersOtis spp., Chiasmia spp., Chilo spp., Homohadena spp., Homona spp., Homonopsis spp., Hoplo Chionodes spp., Chorioptes spp., Choristoneura ssp., campa spp., Hoplodrina spp., Hoshinoa spp., Hylomma spp., Chrysaspidia spp., Chrysodeixis spp., Chrysomya spp., Hydraecia spp., Hydriomena spp., Hyles spp., Hyloicus spp., Chrysomphalus spp., Chrysomphalus distyospermi, Chry Hypagyrtis spp., Hypatina spp., Hyphantria spp., somphalus aonidium, Chrysoteuchis spp., Cix spp., Cimex Hyphantria cunea, Hypocala spp., Hypocoena spp., Hypo spp., Clysia spp., Clysia ambiguella, Clepsis spp., Cnaemi dema spp., Hyppobasca spp., Hypsipyla spp., Hyssia spp., dophorus spp., Cnaphalocrocis spp., Cnephasia spp., Coccus Hysterosia spp., Idaea spp., Idia spp., Ipimorpha spp., Isia spp., Coccus hesperidum, Cochylis spp., Coleophora spp., spp., Isochorista spp., Isophricitis spp., Isopolia spp., Isotrias Colotois spp., commophila spp., Conistra spp., Conopomor spp., Ixodes spp., Itame spp., Jodia spp., Jodis spp., Kawabea pha spp., Corcyra spp., Cornutiplusia spp., Cosmia spp., spp., Keiferia spp., Keiferia lycopersicella, Labdia spp., Cosmopolites spp., Cosmopterix spp., Cossus spp., Costae Lacinipolia spp., Lambdina spp., Lamprothritpa spp., Lao onvexa spp., Crambus spp., Creatonotos spp., Crocidolomia delphax spp., Lasius spp., Laspeyresia spp., Laptinotarsa spp., Crocidolomia binotalis, Croesia spp., Cry modes spp., spp., Leptinotarsa decemlineata, Leptocorisa spp., Lep Cryptaspasma spp., Cryptoblabes spp., Cryptocala spp., tostales spp., Lecanium spp., Lecanium COmi, Lepidosaphea Cryptophlebia spp., Cryptophlebia leucotreta, Cryptoptila spp., Lepisma spp., Lepisma Saccharina, Lesmone spp., Leu spp., Ctenopseudtis spp., Ctenocephalides spp., Cuculia cania spp., Leucinodes spp., Leucophaea spp., Leucophaea spp., Curculio spp., Culex spp., Cuterebra spp., Cydia spp., maderae, Leucoptera spp., Leucoptera scitella, Linognathus Cydia pomonella, Cymbalophora spp., Dactylethra spp., spp., LipOscelis spp., Lissorhoptrus spp., Lithacodia spp., Dacus spp., Dadica spp., Damalinea spp., Dasychira spp., Lithocolletis spp., Lithomoia spp., LIthophane spp., Lix Decadarchis spp., Decodes spp., Deilephila spp., Deltodes Odessa spp., Lobesia spp., Lobesia botrana, Lobophora spp., spp., Dendrolimus spp., Depressaria spp., Dermestes spp., Locusta spp., Loman altes spp., Lomographa spp., LOxagrotis Dermanyssus spp., Dermanyssus gallinae, Diabrotica spp., spp., LOXOstege spp., Lucilla spp., Lymantria spp., Lymnaecia Diachrysia spp., Diaphania spp., Diarisia spp., Diasemia spp., Lyonetia spp., Lyriomyza spp., Macdonnoughia spp., spp., Diatraea spp., Diceratura spp., Dichomeris spp., Dich Macrauzata spp., Macronoctua spp., Macrosiphus spp., rocrocis spp., Dichrorampha spp., Dicycla spp., Dioryctria Malacosoma spp., Maliarpha spp., Mamestra spp., spp., Diparopsis spp., Diparopsis Castanea, Dipleurina spp., Mamastra brassicae, Manduca spp., Manduca sexta, Maras Diprion spp., Dipriondae, Discestra spp., Distantiella spp., mia spp., Margaritia spp., Matratinea spp., Matsumuraeses Distantiella theobroma, Ditula spp., Diurnea spp., Doratop spp., Melanagromyza spp., Melipotes spp., Melissopus spp., teryx spp., Drepana spp., Drosphila spp., Drosphila melano Melittia spp., Melolontha spp., Meristis spp., Meritastis spp., gaster; Dysauxes spp., Dysderus spp., Dysstroma spp., Eana Merophyas spp., Mesapamea spp., Mesogona spp., Meso spp., Earias spp., Ecclitica spp., Ecdytolopha spp., Ecpyr leuca spp., Metanema spp., Metendothenia spp., Metzneria rhorrhoe spp., Ectomyelois spp., Eetropis spp., Egira spp., spp., Micardia spp., Microcorses spp., Microllen spp., Mne Elasmopalpus spp., Emmelia spp., mpoasca spp., Empy sictena spp., Mocis spp., Monima spp., Monochroa spp., reuma spp., Enargia spp., Enarmonia spp., Endopiza spp., Monomorium spp., Monomorium pharaonis, Monopsis spp., Endothenia spp., Endotricha spp., Eoreuma spp., Eotetrany Morrisonia spp., Musca spp., Mutuuraia spp., Myelois spp., Chus spp., Eotetranychus Carpini, Epagoge spp., Epelis spp., Mythinna spp., Myzuz spp., Naranga spp., Nedra spp., Ephestia spp., Ephestiodes spp., Epiblema spp., Epiehoris Nemapogon spp., Neodiprion spp., Neosphleroptera spp., todes spp., Epinotia spp., Epiphyas spp., Epiplena spp., Nephelodes spp., Nephotettix spp., Nezara spp., Nilaparvata Epipsestis spp., Epirrhoe spp., Episimus spp., Epityimbia spp., Niphonympha spp., Nippoptilia spp., Noctua spp., Nola spp., Epillachna spp., Erannis spp., Erastria spp., Eremnus spp., Notocelia spp., Notodonta spp., Nudaurelia spp., spp., Ereunetis spp., Eriophyes spp., Eriosoma spp., Erio Ochropleura spp., Ocnerostoma spp., Oestrus spp., Olethreu Soma lanigerum, Erythroneura spp., Estigmene spp., Ethmia tes spp., Oligia spp., Olindia spp., Olygonychus spp., Olygo spp., Etiella spp., Euagrotis spp., Eucosma spp., Euehlaena nychus gallinae, Oncocnemis spp., Operophtera spp., US 2010/0210574 A1 Aug. 19, 2010

Ophisma spp., Opogona spp., Oraesia spp., Orniodoros spp., spp., Teleiodes spp., Telorta spp., Tenebrio spp., Tephrina Orgvia spp., Oria spp., Orseolia spp., Orthodes spp., spp., Teratoglaea spp., Terricula spp., Tethea spp., Tetrany Orthogonia spp., Orthosia spp., Oryzaephilus spp., Oscinella chus spp., Thaipophila spp., Thaumetopoea spp., Thiodia spp., Oscinella frit, Osminia spp., Ostrinia spp., Ostrinia spp., Thrips spp., Thrips palmi, Thrips tabaci, Thyridopteryx nubilalis, Otiorhynchus spp., Ourapteryx spp., Pachetra spp., spp., Thyris spp., Tineola spp., Tipula spp., Tortricidia spp., Pachysphinx spp., Pagyda spp., Paleacrita spp., Paliga spp., Tortrix spp., Trachea spp., Trialeurodes spp., Trialeurodes Palthis spp., Pammene spp., Pandemis spp., Panemeria spp., vaporariorum, Triatoma spp., Triaxomera spp., Tribolium spp., Tricodectes spp., Trichoplusia spp., Trichoplusia ni, Panolis spp., Panolis flammea, Panonychus spp., Parargy Trichoptilus spp., Trioza spp., Trioza erytreae, Triphaenia resthia spp., Paradiarsia spp., Paralobesia spp., Paranthrene spp., Triphosa spp., Trogoderma spp., Tvria spp., Udea spp., spp., Parapandemis spp., Parapediasia spp., Parastichtis Unaspis spp., Unaspis citri, Utetheisa spp., Valeriodes spp., spp., Parasyndemis spp., Paratoria spp., Pareromeme spp., Vespa spp., Vespanima spp., Vitacea spp., Vitula spp., Witle Pectinophora spp., Pectinophora gossypiella, Pediculus spp., sia spp., Xanthia spp., Xanthorhoe spp., Xanthotype spp., Pegomyia spp., Pegomyia hyoscyami, Pelochrista spp., Pen Xenomicta spp., Xenopsylla spp., Xenopsylla cheopsis, Xes nisetia spp., Penstemonia spp., Pemphigus spp., Peribatodes tia spp., Xylena spp., Xylomyges spp., Xyrosaris spp., spp., Peridroma spp., Perileucoptera spp., Periplaneta spp., Yponomeuta spp., Ypsolopha spp., Zale spp., Zanclognathus Perizona spp., Petrova spp., Pexicopia spp., Phalonia spp., Phalonidia spp., Phaneta spp., Phlyctaenia spp., Phlyctinus spp., Zeiraphera spp., Zenodoxus spp., Zeuzera spp., Zyga spp., Phorbia spp., Phragmatobia spp., Phricanthes spp., ena spp., Phthorimaea spp., Phthorimaea operculella, Phyllocnistis 0111. It is also possible to control pests of the class Nema spp., Phylocoptruta spp., Phylocoptruta oleivora, Phyl toda using the compounds according to the invention. Such lonorycter spp., Phyllophila spp., Phylloxera spp., Pieris pests include, for example, spp., Pieris rapae, Piesma spp., Planococus spp., Planotor 0112 root knot nematodes, cyst-forming nematodes and trix spp., Platyedra spp., Platynota spp., Platyptilia spp., also stem and leafnematodes; Platysenta spp., Plodia spp., Plusia spp., Plutella spp., Plu 0113 especially of Heterodera spp., e.g. Heterodera tella xylostella, Podosesia spp., Polia spp., Popillia spp., Schachtii, Heterodora avenae and Heterodora trifolii; Glo Polymixis spp., Polyphagotarisonemus spp., Polyphagotar bodera spp., e.g. Globodera rostochiensis, Meloidogyne sonemus latus, Prays spp., Prionoxystus spp., Probole spp., spp., e.g. Meloidogyne incognita and Meloidogyne javanica, Proceras spp., Prochoerodes spp., Proeulia spp., Proschistis Radopholus spp., e.g. Radopholus similis, Pratylenchus, e.g. spp., Proselena spp., Proserpinus spp., Protagrotis spp., Pro Pratylenchus neglectans and Pratylenchus penetrans, Tilen teoteras spp., Protobathra spp., Protoschinia spp., Pselno chulus, e.g. Tvlenchulus semipenetrans, Longidorus, Tri phorus spp., Pseudaletia spp., Pseudanthonomus spp., Pseu chodorus, Xiphinema, Dity lenchus, Apheen.choides and daternelia spp., Pseudaulacaspis spp., Pseudexentera spp., Anguina, especially Meloidogyne, e.g. Meloidogyne incog Pseudococus spp., Pseudohermenias spp., Pseudoplusia nita, and Heterodera, e.g. Heterodera glycines. spp., Psoroptes spp., Psylla spp., Psylliodes spp., Pteropho 0114. An especially important aspect of the present inven rus spp., Ptycholoma spp., Pulvinaria spp., Pulvinaria aethi tion is the use of the compounds of formula (I) according to opica, Pyralis spp., Pyrausta spp., Pyrgotis spp., Pyrreferra the invention in the protection of plants against parasitic spp., Pyrrharctia spp., Ouadraspidiotus spp., Rancora spp., feeding pests. Raphia spp., Reticultermes spp., Retinia spp., Rhagoletis spp. 0115 The action of the compounds according to the inven Rhagoletis pomonella, Rhipicephalus spp., Rhizoglyphus tion and the compositions comprising them against animal spp., Rhizopertha spp., Rhodnius spp., Rhophalosiphum spp., pests can be significantly broadened and adapted to the given Rhopobota spp., Rhyacia spp., Rhyacionia spp., Rhyncho circumstances by the addition of other insecticides, acari pacha spp., Rhyzosthenes spp., Rivula spp., Rondotia spp., cides or nematicides. Suitable additives include, for example, Rusidrina spp., Rynchaglaea spp., Sabulodes spp., Sahlber representatives of the following classes of active ingredient: gella spp., Sahlbergella singularis, Saissetia spp., Samia organophosphorus compounds, nitrophenols and derivatives, spp., Sannina spp., Sanninoidea spp., Saphoideus spp., Sar formamidines, ureas, carbamates, pyrethroids, chlorinated coptes spp., Sathrobrota spp., Scarabeidae, Sceliodes spp., hydrocarbons, neonicotinoids and Bacillus thuringiensis Schinia spp., Schistocerca spp., Schizaphis spp., Schizura preparations. spp., Schreckensteinia spp., Sciara spp., Scirpophaga spp., 0116 Examples of especially suitable mixing partners Scirthrips auranti, Scoparia spp., Scopula spp., Scotia spp., include: azamethiphos; chlorfenvinphos; cypermethrin, Scotinophara spp., Scotogramma spp., Scrobipalpa spp., cypermethrin high-cis, cyromazine; diafenthiuron; diazinon; Scrobipalipopsis spp., Semiothisa spp., Sereda spp., Sesamia dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluaZuron; spp., Sesia spp., Sicya spp., Sideridis spp., Simyra spp., furathiocarb; isazofos; iodfenphos; kinoprene; lufenuron; Sineugraphe spp., Sitochroa spp., Sitobion spp., Sitophilus methacriphos; methidathion; monocrotophos; phosphami spp., Sitotroga spp., Solenopsis spp., Smerinthus spp., Soph don; profenofos; diofenolan; a compound obtainable from the ronia spp., Spaelotis spp., Spargaloma spp., Sparganothis Bacillus thuringiensis strain GC91 or from strain spp., Spatalistis spp., Sperchia spp., Sphecia spp., Sphinx NCTC 11821; pymetrozine; bromopropylate; methoprene: spp., Spilonota spp., Spodoptera spp., Spodoptera littoralis, disulfoton; quinallphos; tauflu valinate; thiocyclam; thiome Stagmatophora spp., Staphyllinochrous spp., Stathmopoda ton; aldicarb; azinphos-methyl; benfuracarb: bifenthrin; spp., Stenodes spp., Sterrha spp., Stomoxys spp., Strophedra buprofezin; carbofuran: dibutylaminothio; cartap: chlorflua spp., Sunira spp., Sutyna spp., Swammerdamia spp., Syllo Zuron; chlorpyrifos; clothianidin: cyfluthrin; lambda-cyhalo matia spp., Sympistis spp., Synanthedon spp., Synaxis spp., thrin; alpha-cypermethrin; Zeta-cypermethrin; deltamethrin; Syncopacma spp., Syndemis spp., Syngrapha spp., Synth diflubenzuron; endosulfan; ethiofencarb; fenitrothion; Omeida spp., Tabanus spp., Taeniarchis spp., Taeniothrips fenobucarb; fenvalerate; formothion; methiocarb; hepteno spp., Tannia spp., Tarsonemus spp., Tegulifera spp., Tehama phos; imidacloprid; isoprocarb; methamidophos; methomyl; US 2010/0210574 A1 Aug. 19, 2010 mevinphos; parathion; parathion-methyl; phosalone; pirimi 0119 Further areas of use of the compounds according to carb; propoxur, teflubenzuron; terbufos; triazamate; fenobu the invention are the protection of stored goods and store carb: tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fen rooms and the protection of raw materials, and also in the pyroximate; pyridaben; pyridalyl; fenazaquin; pyriproxyfen; hygiene sector, especially the protection of domestic animals pyrimidifen, nitenpyram; acetamiprid; emamectin; emamec and productive livestock against pests of the mentioned type, tin-benzoate; spinosad; a plant extract that is active against more especially the protection of domestic animals, espe insects; a preparation that comprises nematodes and is active cially cats and dogs, from infestation by fleas, ticks and nema against insects; a preparation obtainable from Bacillus subti todes. lis, a preparation that comprises fungi and is active against 0.120. The invention therefore relates also to pesticidal insects; a preparation that comprises viruses and is active compositions, such as emulsifiable concentrates, Suspension against insects; abamectin, chlorfenapyr; acephate; acrinath concentrates, directly sprayable or dilutable Solutions, rin; alanycarb: alphamethrin; amitraz: AZ60541;azinphos A: spreadable pastes, dilute emulsions, wettable powders, azinphos M. azocyclotin; bendiocarb; benSultap; beta-cy soluble powders, dispersible powders, wettable powders, fluthrin; BPMC; brofenprox: bromophos A: bufencarb; buto dusts, granules and encapsulations of polymer Substances, carboxin; butylpyridaben; cadusafos; carbaryl; carbophe that comprise at least one of the compounds according to the nothion; chloethocarb; chlorethoxyfos; chlormephos; cis invention, the choice of formulation being made in accor resmethrin; clocythrin; clofentezine; cyanophos: dance with the intended objectives and the prevailing circum cycloprothrin; cyhexatin; demeton M, demeton S: demeton StanceS. S-methyl; dichlofenthion; dicliphos; diethion; dimethoate: I0121 The active ingredient is used in those compositions dimethylvinphos; dioxathion; edifenphos; esfenvalerate; in pure form, a solid active ingredient, dient, for example, in ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos: a specific particle size, or preferably together with at least one fenbutatin oxide; fenothiocarb; fempropathrin; fenpyrad; of the adjuvants customary in formulation technology, Such fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxu as extenders, e.g. solvents or solid carriers, or Surface-active ron; flufenprox; fonophos; fosthiazate; fubfenprox: HCH: compounds (surfactants). In the area of parasite control in hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofen humans, domestic animals, productive livestock and pets it phos; isoxathion; ivermectin: malathion; mecarbam; will be self-evident that only physiologically tolerable addi meSulfenphos; metaldehyde; metolcarb; milbemectin; moX tives are used. idectin; naled; NC 184: nithiazine; omethoate; oxamyl; oxy I0122) Solvents are, for example: non-hydrogenated or demethon M, oxydeprofos; permethrin; phenthoate; phorate; partly hydrogenated aromatic hydrocarbons, preferably frac phosmet; phoxim; pirimiphos M. pirimiphos E.; promecarb; tions Cs to C of alkylbenzenes, such as Xylene mixtures, propaphos; prothiofos; prothoate; pyrachlophos; pyr alkylated naphthalenes or tetrahydronaphthalene, aliphatic or adaphenthion; pyresmethrin; pyrethrum, tebufenozide; cycloaliphatic hydrocarbons, such as paraffins or cyclohex salithion; sebufos; sulfotep: sulprofos; tebufenpyrad; tebupir ane, alcohols, such as ethanol, propanol or butanol, glycols imphos; tefluthrin; temephos; terbam; tetrachlorvinphos: and ethers and esters thereof. Such as propylene glycol, dipro thiacloprid; thiafenox; thiamethoxam; thiodicarb; thiofanox; pylene glycol ether, ethylene glycol or ethylene glycol thionazin; thuringiensin; tralomethrin; triarathene; triazo monomethylor-ethyl ether, ketones, such as cyclohexanone, phos; triaZuron; trichlorfon; triflumuron; trimethacarb; vami isophorone or diacetone alcohol, strongly polar solvents, dothion: xylylcarb; YI 5301/5302; Zetamethrin; DPX such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N.N- MP062 indoxacarb: methoxyfenozide: bifenazate. XMC dimethylformamide, water, non-epoxidized or epoxidized (3.5-xylyl methylcarbamate); or the fungus pathogen Metar plant oils, such as non-epoxidized or epoxidized rapeseed, hizium anisopliae. castor, coconut or Soya oil, and silicone oils. 0117 The compounds according to the invention can be I0123. The solid carriers used, for example for dusts and used to control, i.e. to inhibit or destroy, pests of the men dispersible powders, are as a rule natural rock powders. Such tioned type occurring on plants, especially on useful plants as calcite, talc, kaolin, montmorillonite or attapulgite. Highly and ornamentals in agriculture, in horticulture and inforestry, disperse silicic acids or highly disperse absorbent polymers or on parts of such plants, such as the fruits, blossoms, leaves, can also be added to improve the physical properties. Granu stems, tubers or roots, while in Some cases plant parts that lar adsorptive granule carriers are porous types, such as pum grow later are still protected against those pests. ice, crushed brick, Sepiolite or bentonite, and non-Sorbent 0118 Target crops include especially cereals, such as carrier materials are calcite or sand. A large number of granu wheat, barley, rye, oats, rice, maize and Sorghum, beet, Such lar materials of inorganic or organic nature can furthermore as Sugar beet and fodderbeet; fruit, e.g. pomes, stone fruit and be used, in particular dolomite or comminuted plant residues. Soft fruit, Such as apples, pears, plums, peaches, almonds, 0.124 Surface-active compounds are, depending on the cherries and berries, e.g. Straw-berries, raspberries and black nature of the active compound to be formulated, nonionic, berries; leguminous plants, such as beans, lentils, peas and cationic and/or anionic Surfactants or Surfactant mixtures Soybeans; oil plants, such as rape, mustard, poppy, olives, with good emulsifying, dispersing and wetting properties. Sunflowers, coconut, castor oil, cocoa and groundnuts; cucur The surfactants listed below are to be regarded only as bitaceae. Such as marrows, cucumbers and melons; fibre examples; many other Surfactants which are customary in plants, such as cotton, flax, hemp and jute; citrus fruits. Such formulation technology and are suitable according to the as oranges, lemons, grapefruit and mandarins; vegetables, invention are described in the relevant literature. Such as spinach, lettuce, asparagus, cabbages, carrots, onions, 0.125 Nonionic surfactants are, in particular, polyglycol tomatoes, potatoes and paprika; lauraceae, such as avocado, ether derivatives of aliphatic or cycloaliphatic alcohols, Satu cinnamon and camphor, and tobacco, nuts, coffee, aub rated or unsaturated fatty acids and alkylphenols, which can ergines, Sugar cane, tea, pepper, Vines, hops, bananas, natural contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms rubber plants and ornamentals. in the (aliphatic) hydrocarbon radical and 6 to 18 carbon US 2010/0210574 A1 Aug. 19, 2010

atoms in the alkyl radical of the alkylphenols. Substances Emulsifiable Concentrates: which are furthermore suitable are water-soluble polyethyl ene oxide adducts, containing 20 to 250 ethylene glycol ether 0129 and 10 to 100 propylene glycol ether groups, on propylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbonatoms in the alkyl active ingredient: 1 to 90%, preferably 5 to 20% chain. The compounds mentioned usually contain 1 to 5 eth Surfactant: 1 to 30%, preferably 10 to 20% ylene glycol units per propylene glycol unit. Examples are solvent: 5 to 98%, preferably 70 to 85% nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tribu tylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other substances are fatty Dusts: acid esters of polyoxyethylene Sorbitan, Such as polyoxyeth ylene sorbitan trioleate. O130 0126 The cationic Surfactants are, in particular, quater nary ammonium salts which contain, as Substituents, at least one alkyl radical having 8 to 22 C atoms and, as further active ingredient: 0.1 to 10%, preferably 0.1 to 1% Substituents, lower, non-halogenated or halogenated alkyl, solid carrier: 99.9 to 90%, preferably 99.9 to 99% benzyl or lower hydroxyalkyl radicals. The salts are prefer ably in the form of halides, methyl-sulfates or ethyl-sulfates. Examples are Stearyltrimethyl-ammonium chloride and ben Suspension Concentrates: Zyl-di-(2-chloroethyl)-ethyl-ammonium bromide. 0127 Suitable anionic surfactants can be both water 0131) soluble soaps and water-soluble synthetic Surface-active compounds. Suitable soaps are the alkali metal, alkaline earth metal and Substituted or unsubstituted ammonium salts of active ingredient: 5 to 75%, preferably 10 to 50% higher fatty acids (Co-C), such as the sodium or potassium Water: 94 to 24%, preferably 88 to 30% salts of oleic or stearic acid, or of naturally occurring fatty Surfactant: 1 to 40%, preferably 2 to 30% acid mixtures, which can be obtained, for example, from coconut oil or tall oil; and furthermore also the fatty acid methyl-taurine salts. However, synthetic Surfactants are more Wettable Powders: frequently used, in particular fatty Sulfonates, fatty Sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. (0132 The fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubsti tuted ammonium salts and in general have an alkyl radical of active ingredient: 0.5 to 90%, preferably 1 to 80% 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl Surfactant: 0.5 to 20%, preferably 1 to 15% radicals; examples are the Sodium or calcium salt of lignin solid carrier: 5 to 99%, preferably 15 to 98% sulfonic acid, of dodecylsulfuric acid ester or of a fatty alco hol Sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of sulfuric acid esters and Granules: sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 0.133 Sulfonic acid groups and a fatty acid radical having about 8 to 22C atoms. Alkylarylsulfonates are, for example, the Sodium, calcium or triethanolammonium salts of dodecylbenzene active ingredient: 0.5 to 30%, preferably 3 to 15% sulfonic acid, of dibutylnaphthalenesulfonic acid or of a solid carrier: 99.5 to 70%, preferably 97 to 85% naphthalenesulfonic acid-formaldehyde condensation prod uct. Corresponding phosphates. Such as salts of the phospho ric acid ester of a p-nonylphenol-(4-14)-ethylene oxide I0134. The compositions according to the invention may adduct or phospholipids, can further also be used. also comprise further Solid or liquid adjuvants, such as stabi 0128. The compositions as a rule comprise 0.1 to 99%, in lisers, e.g. Vegetable oils or epoxidised vegetable oils (e.g. particular 0.1 to 95%, of active compound and 1 to 99.9%, in epoxidised coconut oil, rapeseed oil or soybean oil), anti particular 5 to 99.9%, of -at least - one solid or liquid auxil foams, e.g. silicone oil, preservatives, viscosity regulators, iary, it being possible as a rule for 0 to 25%, in particular 0.1 binders and/or tackifiers as well as fertilisers or other active to 20%, of the composition to be surfactants (% is in each case ingredients for obtaining special effects, e.g. acaricides, bac per cent by weight). While concentrated compositions are more preferred as commercial goods, the end user as a rule tericides, fungicides, nematicides, molluscicides or selective uses dilute compositions which comprise considerably lower herbicides. concentrations of active compound. Preferred compositions 0.135 The crop protection products according to the inven comprise ingredients within the following ranges (% per tion are prepared in known manner, in the absence of adju cent by weight): Vants, e.g. by grinding, sieving and/or compressing a solid US 2010/0210574 A1 Aug. 19, 2010

active ingredient or mixture of active ingredients, for example for that reason, usually only the bands of the B1a derivative to a certain particle size, and in the presence of at least one can be detected in the NMR spectrum. adjuvant, for example by intimately mixing and/or grinding 0141 Since the compounds are in most cases in the form the active ingredient or mixture of active ingredients with the of mixtures of the avermectin B1a and B1b derivative, char adjuvant(s). The invention relates likewise to those processes acterisation by means of the customary physical data Such as for the preparation of the compositions according to the melting point or refractive index is of little use. For that invention and to the use of the compounds of formula (I) in the reason, the compounds are characterised by means of NMR preparation of those compositions. spectroscopy following purification by chromatography, or 0136. The invention relates also to the methods of appli by reference to the retention times determined in analysis by cation of the crop protection products, i.e. the methods of means of HPLC (high-resolution liquid chromatography). controlling pests of the mentioned type, such as spraying, The term “Bla' in the physical data on the Preparation atomising, dusting, coating, dressing, scattering or pouring, Examples refers to the main component, wherein R is sec which are selected in accordance with the intended objectives butyl. “B1b' represents the secondary component, wherein and the prevailing circumstances, and to the use of the com R is isopropyl. In the case of the compounds for which a positions for controlling pests of the mentioned type. Typical retention time is given only for the B1a derivative, it is not rates of concentration are from 0.1 to 1000 ppm, preferably possible to determine the retention time for the B1b compo from 0.1 to 500 ppm, of active ingredient. The rates of appli nent owing to the small proportion of B1b derivative. Alloca cation per hectare are generally from 1 to 2000 g of active tion of the correct structures of the B1a and B1b components ingredient per hectare, especially from 10 to 1000 g/ha, pref is carried out by mass spectrometry. erably from 20 to 600 g/ha; more especially 20 to 100 g/ha. 0142. The following method is used for the HPLC analy 0.137. A preferred method of application in the area of crop protection is application to the foliage of the plants (foliar sis: application), the frequency and the rate of application being dependent upon the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) when the locus of the HPLC gradient conditions plants is impregnated with a liquid formulation or when the active ingredient is incorporated in Solid form into the locus solvent A: 0.01% trifluoroacetic acid in H2O of the plants, for example into the soil, e.g. in granular form solvent B: 0.01% trifluoroacetic acid in CHCN (Soil application). In the case of paddy rice crops, such gran flow rate ules may be applied in metered amounts to the flooded rice time min A% B% ulmin field. 0.138. The crop protection products according to the inven O 8O 2O 500 tion are also Suitable for protecting plant propagation mate O.1 50 50 500 rial, e.g. seed, Such as fruits, tubers or grains, or plant cuttings, against animal pests. The propagation material can be treated 10 5 95 500 with the composition before planting: seed, for example, can 15 O 1OO 500 be dressed before being sown. The active ingredients accord 17 O 1OO 500 ing to the invention can also be applied to grains (coating), 17.1 8O 2O 500 either by impregnating the seeds in a liquid formulation or by 22 8O 2O 500 coating them with a solid formulation. The composition can column: YMC-Pack ODS-AQ also be applied to the planting site when the propagation column length: 125 mm material is being planted, for example to the seed furrow during sowing. The invention relates also to Such methods of column internal diameter: 2 mm treating plant propagation material and to the plant propaga temperature: 40° C. tion material so treated. 0.139. The following Examples serve to illustrate the 0143. The YMC-Pack ODS-AQ columnused for chroma invention. They do not limit the invention. Temperatures are tography of the compounds is produced by YMC, Alte Raes in degrees Celsius; mixing ratios of solvents are given in parts by volume. In the data relating to NMR spectra, DMSO felderstrasse 6, 46514 Schermbeck, Germany. denotes dimethyl sulfoxide, S denotes singlet, t denotes trip 0144. The abbreviations used in the physical data infor let, d denotes doublet, q denotes quartet and m denotes mul mation have the following meanings: tiplet. 0145 s: singlet, MHz: megahertz, brs: broad singlet: t: triplet; m: multiplet; d. doublet: J: coupling constant; ba: PREPARATION EXAMPLES broad doublet; LCMS: liquid chromatography mass spec trometry: t: retention time in minutes; M+H: mass peak 0140. In the following Examples, the preparation of aver plus H; M+Na: mass peak plus Na. TBDMS in the Examples mectin B1 derivatives (mixtures of avermectin B1a and B1b represents the radical —Si(CH) (tert-butyl). Mixing ratios derivative) is described. The B1b derivative generally repre of solvents are given in parts by volume. “Ether is under sents about only from 5 to 10% by weight of the mixtures and, stood to mean diethyl ether. US 2010/0210574 A1 Aug. 19, 2010

Example P.1 4"-O-benzyloxymethyl-Avermectin B 014.6

0147 Step A: To a solution of 0.5g of 5-OTBDMS-Aver (consisting of 25 g 70% HF-Pyridin, 27.5 ml tetrahydrofuran mectin B and 0.26 g of N,N-diisopropylethylamine in 10 ml and 12.5 ml pyridine), and the mixture is stirred at room dichloromethane at 0°C. is added 276 mg of benzyloxym temperature for 12 hours, poured into water, extracted with ethyl chloride. The mixture is stirred at 35° C. for 12 hours. ethyl acetate; the organic phase is washed with Saturated The reaction mixture is cooled to room temperature, poured Sodium bicarbonate, dried over Sodium Sulfate, and concen into water, extracted with ethyl acetate, dried over NaSO, trated in vacuo. The residue is purified by preparative HPLC and concentrated in vacuo, providing crude 5-OTBDMS-4"- to afford 4'-O-benzyloxymethyl-Avermectin B. LCMS: O-benzyloxymethyl-Avermectin B which was used directly B: t: 12.16 min., 1015 (M--Na). as follows: Example P2 0148 Step B: To a solution of 5-OTBDMS-4"-O-benzy loxymethyl-Avermectin B (obtained in step A) in 10 ml 4"-epi-O-(2-methoxyethoxymethyl)-Avermectin B tetrahydrofuran is added 2.2 ml of a HF-pyridine solution 0149 1.

N O 1N10 N1 O

, O O, US 2010/0210574 A1 Aug. 19, 2010

0150 Step A: To a solution of 0.3 g of 5-OTBDMS-4"- epi-Avermectin B and 0.31 g of N,N-diisopropylethylamine in 5 ml dichloromethane at 0°C. is added 0.21 ml of 2-meth oxy-ethoxymethyl chloride. The mixture is stirred at reflux for 6 hours. The reaction mixture is cooled to room tempera ture poured into water, extracted with ethyl acetate, dried over Na2SO4, and concentrated in vacuo, providing crude 5-OT BDMS-4'-epi-O-(2-methoxy-ethoxymethyl)-Avermectin B which is used directly as follows: 0151. Step B: To a solution of 5-OTBDMS-4"-epi-O-(2- methoxyethoxymethyl)-Avermectin B in 10 ml tetrahydro furan is added 3.5 ml of a HF-pyridine solution (consisting of 25g 70% HF-Pyridin, 27.5 ml tetrahydrofuran and 12.5 ml pyridine), and the mixture is stirred at 50° C. for 2.5 hours, poured into water, extracted with ethyl acetate; the organic phase is washed with saturated sodium bicarbonate, dried over sodium sulfate, and concentrated in vacuo. The residue is purified by flash-chromatography (silica gel hexane/ethyl acetate 1/1), to afford 4"-epi-O-(2-methoxyethoxymethyl)- Avermectin B. LCMS: B: t: 9.37 min. 983.5 (M--Na), 961.6 (M+H); B: t: 8.65 min.,969.5 (M+Na). Example P.3 4'-O-Butoxymethyl-Avermectin B monosaccharide 0152

N-1N1'N-1'.

0153 Step A: To a solution of 5-OTBDMS-Avermectin B methanol (5 ml) at 0°C. is added methanesulphonic acid monosaccharide (420 mg) and N,N-diisopropylethylamine (0.02 ml). The reaction mixture is stirred for 1 hour and (0.4 ml) in dichloromethane (5 ml) at room temperature is poured into Saturated sodium bicarbonate, extracted with added chloromethyl n-butyl ether (220 mg). The mixture is ethyl acetate, dried over MgSO4, and concentrated in vacuo. stirred at 35° C. for 24 hours. The reaction mixture is poured into brine, extracted with ethyl acetate, dried over NaSO, Flash chromatography (silica gel, hexane/ethyl acetate 3/0) and concentrated in vacuo. The residue is purified by flash affords 4'-O-butoxymethyl-avermectin B monosaccharide. chromatography (silica gel, hexane/ethyl acetate 4/1) provid 0155 4'-O-Butoxymethyl-Avermectin B monosaccha ing 5-OTBDMS-4'-O-butoxymethyl-avermectin B ride: B, CHO, MW: 814.5. LCMS: t: 11.4 minutes, monosaccharide which is characterized by its mass and NMR 837.3 (M+Na); 1H NMR (300 MHz, CDC1) selected data, spectra. ÖH (ppm): 3.15 (t, J=8.5 Hz, 1H, CH-4), 3.28 (m. 1H, CH-2), 0154 Step B: To a solution of 5-OTBDMS-4'-O-bu 3.44 (s, 3H, OCH). B. CHO, MW: 800.5. LCMS: toxymethyl-avermectin B monosaccharide (200 mg) in t: 10.6 823.5 (M+Na); US 2010/0210574 A1 Aug. 19, 2010

Example P4 4'-O-(1-Acetoxy-ethoxy)methyl-Avermectin B monosaccharide 0156

O o1 us1N-N-1'.O O.,

0157 Step A: To a solution of 5-OTBDMS-Avermectin B for 18 hours at room temperature, poured into aqueous monosaccharide (422 mg) and N,N-diisopropylethylamine NaHCO (50%), extracted with ethyl acetate, dried over (0.9 ml) in dichloromethane (5 ml) at room temperature is MgSO, and concentrated in vacuo. Flash chromatography added 1-acetoxy-2-chloromethoxyethane (610 mg). The (silica gel, hexane/ethyl acetate 1/1) affords 4'-O-(1-acetoxy ethoxy)methyl-avermectin B monosaccharide which is char mixture is stirred at 45° C. for 32 hours. The reaction mixture acterized by its mass and NMR spectra. is poured into brine, extracted with ethyl acetate, dried over I0159 4'-O-(1-Acetoxy-ethoxy)methyl-avermectin B MgSO and concentrated in vacuo. The residue is purified by monosaccharide: B, CHO, MW: 844.5. LCMS: t: flash chromatography (silica gel, hexane/ethyl acetate 4/1) 8.49 minutes, 867.5 (M+Na); B, CHO, MW: 830.5. providing 5-OTBDMS-4'-O-(1-acetoxy-ethoxy)methyl LCMS: t: 7.82 minutes, 853.5 (M+Na). avermectin B monosaccharide which is characterized by its mass and NMR spectra. Example P5 0158 Step B: To a solution of 5-0TBDMS-4'-0-(1-ac etoxy-ethoxy)methyl-avermectin B monosaccharide (384 4'-O-(1-hydroxy-ethoxy)methyl-Avermectin B mg) in Tetrahydrofuran (5 ml) is added pyridine (0.2 ml) and monosaccharide 0.2 ml of a 70% HF-pyridine solution. The mixture is stirred (0160

1.

1S-1'N-1'.O O US 2010/0210574 A1 Aug. 19, 2010

0161 Step A: To a methanolic solution (10 ml) of 5-OT BDMS-4'-O-(1-acetoxy-ethoxy)methyl-avermectin B monosaccharide (410 mg) cooled to 0°C. is added ammo nium hydroxide (2 ml, 25% in HO). The mixture is stirred at room temperature for 4 hours at room temperature and then concentrated in vacuo. Flash chromatography (silica gel, hex ane/ethyl acetate 1/1) affords 4'-O-(1-hydroxy-ethoxy)me thyl-avermectin B monosaccharide which is characterized by its mass and NMR spectra. (0162 Step B: To a solution of 5-OTBDMS-4'-O-(1-hy droxy-ethoxy)methyl-avermectin B monosaccharide (140 mg) in Tetrahydrofuran (2 ml) is added pyridine (80 pl) and 70% HF-pyridine solution (80 ul). The mixture is stirred for 5 dat room temperature, poured into aqueous NaHCO (50%), extracted with ethyl acetate, dried over MgSO, and concen trated in vacuo. Flash chromatography (silica gel, hexane/ ethyl acetate 3/7) affords 4'-O-(1-hydroxy-ethoxy)methyl avermectin B monosaccharide which is characterized by its mass and NMR spectra. 0163 4'-O-(1-hydroxy-ethoxy)methyl-avermectin B monosaccharide: B, CHOs, MW: 802.5. LCMS: t: 6.99 minutes, 825.4 (M+Na); B, CHO, MW: 788.4. LCMS: t: 6.35 minutes, 811.4 (M+Na). Example P6 4'-O-(1-Methoxymethoxy-ethoxy)methyl-Avermec tin B mono-saccharide (0164

N-1-

(0165 Step A: To a solution 5-OTBDMS-4'-O-(1-hy ride (100 mg) in Tetrahydrofuran (1.5 ml) is added pyridine droxy-ethoxy)methyl-avermectin B mono-saccharide (138 (50 ul) and 70% HF-pyridine solution (50 ul). The mixture is mg) and N,N-diisopropylethylamine (90 ul) in dichlo romethane (5 ml) at room temperature is added chloromethyl stirred for 48 hours at room temperature, poured into satu methyl ether (29 ul). The mixture is stirred at 35° C. for 20 rated aqueous NaHCO, extracted with ethyl acetate, dried hours. The reaction mixture is poured into water, extracted over MgSO and concentrated in vacuo. Flash chromatogra with dichloromethane, dried over MgSO and concentrated in phy (silica gel, hexane/ethyl acetate 1/1) affords 4'-O-(1- vacuo. The residue is purified by flash chromatography (silica methoxymethoxy-ethoxy)methyl-avermectin B mono-sac gel, hexane/ethyl acetate 7/3) providing 5-OTBDMS-4'-O- (1-methoxymethoxyethoxy)methyl-Avermectin B charide which is characterized by its mass and NMR spectra. monosaccharide, which is characterized by its mass and 0.167 4'-O-(1-Methoxymethoxy-ethoxy)methyl-aver NMR spectra. mectin B monosaccharide: B, C.H.O. MW: 846.5. (0166 Step B: To a solution of 5-OTBDMS-4'-O-(1-meth LCMS: t: 8.73 minutes, 869.4 (M+Na); B, CHO, oxymethoxy-ethoxy)methyl-avermectin B mono-saccha MW: 832.5. LCMS: t: 7.89 minutes, 855.4 (M+Na). US 2010/0210574 A1 Aug. 19, 2010 17

Example P.7 4'-O-(1-azido-ethoxy)methyl-Avermectin B monosaccharide (0168 1 N1-1 O N1 O, N 2N. O

(0169 Step A: To a solution 5-OTBDMS-4'-O-(1-hy HF-pyridine solution (50 ul). The mixture is stirred for 48 droxy-ethoxy)methyl-avermectin B monosaccharide (642 hours at room temperature, poured into Saturated aqueous mg) in N,N-dimethylacetamide (7 ml) cooled to 0°C. room NaHCO, extracted with ethyl acetate, dried over MgSO and temperature is added triphenylphosphine (551 mg) and tetra concentrated in vacuo. Flash chromatography (silica gel, hex bromomethane (696 mg). The mixture is stirred for 0.5 hours ane/ethyl acetate 1/1) affords 4'-O-(1-azido-ethoxy)methyl after which time sodium azide (228 mg) is added. The reac avermectin B monosaccharide which is characterized by its tion mixture is stirred at 40° C. for 1 hours and then poured mass and NMR spectra. into water, extracted with ethyl acetate, dried over MgSO 0171 4'-O-(1-Azido-ethoxy)methyl-avermectin B and concentrated in vacuo. The residue is purified by flash monosaccharide: B, CH5NO2, MW: 827.5. LCMS: chromatography (silica gel, hexane/ethyl acetate 5/1) provid t: 9.76 minutes, 850.5 (M--Na); B, CHNO, MW: ing 5-OTBDMS-4'-O-(1-azido-ethoxy)methyl-Avermectin 813.4 LCMS: t: 9.01 minutes, 836.4 (M+Na). B monosaccharide which is characterized by its mass and Example P8 NMR spectra. (0170 Step B: To a solution of 5-OTBDMS-4'-O-(1-azido 4'-O-(1-amino-ethoxy)methyl-Avermectin B ethoxy)methyl-Avermectin B monosaccharide (98 mg) in monosaccharide tetrahydrofuran (2.0 ml) is added pyridine (50 ul) and 70% 0172

1.

HN1 N1 O N1 O'... US 2010/0210574 A1 Aug. 19, 2010

0173 Step A: To a solution of 4'-O-(1-azido-ethoxy)me 0180 4'-O-(1-Bromomethyl-1-methoxy)methyl-Aver thyl-avermectin B monosaccharide is added trimethylphos mectin B monosaccharide: B, CHBrO2. MW: 864.4. phine (150 ul, 1.0 M in tetrahydrofuran) and water (30 ul). The reaction mixture is stirred at room temperature for 48 LCMS: isomer 1 to 10.56 min. 865.4 (M+H); isomer 2: to hours and then poured into water, extracted with ethylacetate, 10.35 min. 865.4 (M+Na). dried over MgSO and concentrated in vacuo. The residue is purified by flash chromatography (silica gel, hexane/ethyl Example P.10 acetate 5/1) providing 4'-O-(1-amino-ethoxy)methyl-Aver mectin B monosaccharide which is characterized by its mass 4'-epi-O-(Tetrahydro-pyran-2-yl)-avermectin B and NMR spectra. 0.174 4'-O-(1-Amino-ethoxy)methyl-avermectin B monosaccharide of the formula monosaccharide: BCH-NO, MW: 801.5. LCMS: t: 4.11 minutes, 802.5 (M--Na). 0181 Example P.9 4'-O-(1-bromomethyl-1-methoxy)methyl-Avermec tin B monosaccharide 0175

0182 Step A: A mixture of 5-OTBDMS-4-epi-avermectin B monosaccharide (500 mg), 3,4-Dihydro-2H-pyran (80.7 ul) and Pyridinium-(toluene-4-sulfonate) (14.9 mg) in 4 ml (0176 Step A: A mixture of 5-OTBDMS-Avermectin B CHCl is stirred for 6 hat room temperature. The reaction monosaccharide (1.0 g), mercury acetate (190 mg) and ethyl mixture is diluted with 20 ml diethyl ether and washed with vinyl ether (10 ml) is refluxed for 8 h. The reaction mixture is aqueous NaCl. Drying over Na2SO4, and concentration in poured into aqueous NaCO and extracted with ethyl acetate. vacuo provides the two possible isomers of 5-OTBDMS-4'- Drying over NaSO4, and concentration in vacuo provides 5-OTBDMS-4'-O-vinyl-avermectin B monosaccharide epi-O-(tetrahydro-pyran-2-yl)-avermectin B monosaccha which is characterized by its mass and NMR spectra. ride which can be separated by flashchromatography (hex (0177 Step B: To a solution of 5-OTBDMS-4'-O-vinyl ane-ethylacetate 4:1) and characterized by their mass and avermectin B monosaccharide (200 mg) in methanol is NMR spectra. added N-bromosuccinimide (46 mg). After stirring at room temperature for 24 h the solvent is removed in vacuo provid 0183 Step B': To a solution of the first isomer of 5-OTB ing 5-OTBDMS-4'-O-(1-bromomethyl-1-methoxy)methyl DMS-4'-epi-O-(Tetrahydro-pyran-2-yl)-avermectin B Avermectin B monosaccharide as a mixture of diastereoiso monosaccharide (148 mg) in THF (2.5 ml) is added pyridine mers which is characterized by its mass and NMR spectra. (244 ul) and 70% HF-pyridine solution (83 ul). The mixture is (0178 5-OTBDMS-4'-O-(1-bromomethyl-1-methoxy) stirred for 72 hat room temperature, poured into saturated methyl-Avermectin B monosaccharide: B aqueous NaHCO, extracted with ethyl acetate, dried over CsoH, BrO, Si, MW: 978.5. LCMS: isomer 1 : to 14.94 NaSO and concentrated in vacuo. Preparative HPLC min. 979.5 (M+H); isomer 2: to 14.64 min., 1001.4 affords the first isomer of 4'-epi-O-(Tetrahydro-pyran-2-yl)- (M+Na). avermectin B monosaccharide which is characterized by its (0179 Step C: To a solution of 5-OTBDMS-4'-O-(1-bro mass and NMR spectra. momethyl-1-methoxy)methyl-avermectin B monosaccha 0.184 4'-epi-O-(Tetrahydro-pyran-2-yl)-avermectin B ride (200 mg) in THF (2.0 ml) is added pyridine (50 ul) and 70% HF-pyridine solution (100 ul). The mixture is stirred for monosaccharide: CHO, MW: 812.5. LCMS: isomer 1 48 h at room temperature, poured into Saturated aqueous to 10.26 min. 813.5 (M+H): 835.5 (M+Na). NaHCO, extracted with ethylacetate, dried over MgSO and 0185. Step B". To a solution of the second isomer of 5-OT concentrated in vacuo. Flash chromatography (silica gel, hex BDMS-4'-epi-O-(tetrahydro-pyran-2-yl)-avermectin B ane/ethyl acetate 1/1) affords 4'-O-(1-bromomethyl-1-meth monosaccharide (46 mg) in THF (1 ml) is added pyridine (76 oxy)methyl-Avermectin B monosaccharide which is charac ul) and 70% HF-pyridine solution (26 ul). The mixture is terized by its mass and NMR spectra. stirred for 72 hat room temperature, poured into saturated US 2010/0210574 A1 Aug. 19, 2010

aqueous NaHCO, extracted with ethyl acetate, dried over diisopropylamine (8.1 ul) diluted with 30 ml CH2Cl and NaSO and concentrated in vacuo. Preparative HPLC washed with aqueous NaSO, aqueous NaHCO and aque affords the second isomer of 4'-epi-O-(Tetrahydro-pyran-2- ous NaCl. Drying over Na2SO4, and concentration in vacuo yl)-avermectin B monosaccharide which is characterized by provides 5-OTBDMS-4'-O-(1,4-Dioxan-2-yl)-avermectin its mass and NMR spectra. B monosaccharide which can be isolated by flashchro 0186 4'-epi-O-(Tetrahydro-pyran-2-yl)-avermectin B matography (hexane-ethylacetate 3:1) and characterized by monosaccharide: CHO, MW: 812.5. LCMS: isomer 2 to 11.03 min. 813.5 (M+H): 835.5 (M+Na). its mass and NMR spectra. (0189 Step B: To a solution of 5-OTBDMS-4'-O-(1,4) Example P.11 Dioxan-2-yl)-avermectin B monosaccharide (29 mg) in THF 4'-O-(1,4Dioxan-2-yl)-avermectin B monosaccha (0.7 ml) is added HF-pyridine solution (175ul). The mixture ride of the formula is stirred for 18h at room temperature, poured into saturated aqueous NaHCO, extracted with ethyl acetate, dried over 0187. NaSO and concentrated in vacuo. Flashchromatography (hexane-ethylacetate 1:1) affords 4'-O-(1,4-Dioxan-2-yl)- avermectin B monosaccharide which is characterized by its mass and NMR spectra. 0.190 4'-O-(1,4-Dioxan-2-yl)avermectin B monosac CSO charide: CHO, MW: 814.5. LCMS: to 10.07 min. 815.5 (M+H): 837.4 (M+Na): 832.5 (M+NH4).

Example P.12

4'-O-(dihydro-pyran-3-one)-avermectin B monosac charide of the formula

(0191)

O

O

0188 Step A: A mixture of 5-OTBDMS-4-avermectin B (0192 Step A: A solution of 5-OTBDMS-4-avermectin B monosaccharide (500 mg), 2-Phenyl-sulfanyl-1,4-dioxane monosaccharide (7100 mg), Carbonic acid allyl ester 6-phe nylsulfanyl-tetrahydro-pyran-3-yl ester (10240 mg and 2. (163 mg) and molecular sieves (3A) in 8ml CHCl is stirred 6-di-tertbutylpyridine (1890 ul) in 40.0 ml of N-methylpyr for 2 hat room temperature. The reaction mixture is cooled to rolidinone at room temperature is treated with N-iodosuccin 30° C. and N-Iodosuccinimide (267 mg) and Trifluo imide (7650 mg) in 40 min. The reaction is quenched with a romethansulfonic acid (5.1 ul) are added. After stirring for 75 mixture of aqueous NaSOs, aqueous KOC and water. The min at that temperature, the reaction is quenched with Ethyl aqueous phase is extracted with diethylether (3 times) and the US 2010/0210574 A1 Aug. 19, 2010 20 organic phase is washed with water and aqueous NaCl Suc added. The mixture is stirred for 10 additional minutes at cessively. Drying over NaSO4, and concentration in vacuo -75°C. then, the reaction mixture is allowed to come to 0°C. provides a mixture of three epimers of 4'-O-(3-allyloxycar The reaction is quenched with aqueous NaHCO and the bonyl-dihydro-pyran)-avermectin B monosaccharide which aqueous phase is extracted with diethyl ether (x3).The can be isolated by flash chromatography (hexane-diethyl organic phase is dried over Na2SO4 and concentrated in ether 1:0 to 0:1) and characterized by mass and NMR spectra. vacuo. Flash chromatography (hexane-ethyl acetate 1:3) In the alternative they are kept as a mixture for the following affords two of epimers of 4'-O-(dihydro-pyran-3-one)-aver step. mectin B monosaccharide which can be isolated and char 0193 Step B: A solution of a mixture of 4'-O-(3-allyloxy acterized by them mass and NMR spectra. carbonyl-dihydro-pyran)-avermectin B monosaccharide 0.195 Step D: To a solution of 4'-O-(dihydro-pyran-3- (54300 mg), tetrakis(triphenylphosphine)-Palladium (2870 one)-avermectin B monosaccharide (90 mg) in THF (2.5 ml) mg), triphenylphosphine (2580 mg), butylamine (7460 LL) is added HF-pyridine solution (500 ul). The mixture is stirred and formic acid in 50.0 ml of tetrahydrofuran is stirred at for 18h at room temperature, poured into Saturated aqueous room temperature for 4 h. The reaction is poured in a mixture NaHCO, extracted with ethyl acetate, dried over NaSO and of aqueous NaHCOs and ethyl acetate. The aqueous phase is concentrated in vacuo. Flash chromatography (hexane-ethyl extracted with ethyl acetate, dried over NaSO and concen acetate 1:2 to 0:1) affords 4'-O-(dihydro-pyran-3-one)-aver trated in vacuo. Flash chromatography (hexane-ethyl acetate mectin B monosaccharide which is characterized by its mass 3:2) affords a mixture of epimers of 4'-O-(dihydro-pyran-3- and NMR spectra. ol)-avermectin B monosaccharide which can be isolated by 0.196 4'-O-(dihydro-pyran-3-one)-avermectin B flash chromatography (hexane-diethyl ether 1:0 to 0:1) and monosaccharide : characterized by mass and NMR spectra. (0197) First epimer: B, CHO, MW: 826.5. LCMS: 0194 Step C: To a solution containing oxalyl chloride to 11.69 min. 827.5 (M+H); 849.3 (M+Na). (1010 LIL) in 30 mL of methylene chloride stirred at -75°C., 0198 Second epimer : B, CHO, MW: 826.5. is added DMSO (1390 uL) dissolved in 10 mL of methylene LCMS: to 10.94 min. 849.4 (M+Na); 844.5 (M+NH4). chloride during 10 min. Then a solution of mixture of 4'-O- (dihydro-pyran-3-ol)-avermectin B monosaccharide (7550 Example P.13 mg) dissolved in 20 mL of methylene chloride is added over 0199 The compounds listed in tables can also be prepared a period of 15 minutes at -75°C. The mixture is stirred at this analogously to the above Preparation Examples or by other temperature for 30 min and triethylamine (3560 u) was methods known to the person skilled in the art.

TABLE 1.

Compounds of formula

(Ia)

wherein R is sec-butyl (B1a) or isopropyl (B1b), A-B is -CHF CH- and Q is hydrogen:

Retention time (min

No. R2 R B1a. B1b

1.1 CH2C6Hs H 12.16 11.64 1.2 p-ClC6Hs H

US 2010/0210574 A1 Aug. 19, 2010 23

TABLE 1-continued

Compounds of formula

(Ia)

O

wherein R is sec-butyl (B1a) or isopropyl (B1b), A B is CHF CH- and Q is hydrogen:

Retention time (min) US 2010/0210574 A1 Aug. 19, 2010 24

TABLE 2

Compounds of formula (Ib)

O

wherein R is sec-butyl (B1a) or isopropyl (B1b), A-B is -CH=CH- and Q is hydrogen:

Retention time (min No. R B1a. B1b 2.1 2.2 2.3 2.4 2.5 7.14 2.6 9.65 8.91 2.7 2.8 9.39 8.69 2.9 9.84 2.10 2.11 2.12 2.13 11.20 2.14 1242 11.72 2.15 1243 11.84 2.16 8.85 8.11 2.17 9.98 9.23 2.18 11.52 2.19 6.09 2.20 2.21 2.22 2.23 2.24 2.25 2.26 2.27 2.28 2.29 2.30 2.31 2.32 2.33 2.34 2.35 2.36 2.37 2.38 2.39 2.40

US 2010/0210574 A1 Aug. 19, 2010 29

TABLE 4-continued

Compounds of formula

(Id) o1

R1

-O wherein R is sec-butyl (B1a) or isopropyl (B1b), A B is - CHFCH- and Q is hydrogen:

Retention time (min

No. R2 B1a. 4.43 4.44

TABLE A Compounds of the formula (I No. R2 A.1 A.2 A.3 A.4 AS A.6 A.7 A.8 A9 A.10 A.11 A.12 A.13 A.14 A15 A.16 A17 A.18 A19 A.20 A.21 MeOC COMe

CHCHCH- N2

A.22 n-Pr A23 n-Hexyl US 2010/0210574 A1 Aug. 19, 2010 30

TABLE A-continued Compounds of the formula (I US 2010/0210574 A1 Aug. 19, 2010 31

TABLE A-continued

Compounds of the formula (I

No. R2 A71

rN-1 O A72 ry 1 O)

A.73 rN-1 Nur A74

sé'so ryu-1 N

A.75

ryu-1 N

A76 C

N

A.77

-N-N-1S A78 CH2CH2CH2 A.79 CH2CH2CH2CH2

TABLE 5 TABLE 7

Compounds of the formula (Ia) wherein R is sec-butyl or Compounds of the formula (Ia) wherein R is sec-butyl or isopropyl, A-B is —CH=CH-, Q is TBDMS and the combination of isopropyl, A-B is —CH=CH-, Q is Hand the combination of the the Substituents R2 and R for each compound corresponds to Substituents R2 and R for each compound corresponds to a line a line A.1 to A.79 of table A. A.1 to A.79 of table A.

TABLE 6 TABLE 8 Compounds of the formula (Ia) wherein R is sec-butyl or Compounds of the formula (Ia) wherein R is sec-butyl or isopropyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of isopropyl, A-B is —CH2—CH2—, Q is Hand the combination of the the Substituents R-2 and R for each compound corresponds to a Substituents R2 and R for each compound corresponds to a line line A.1 to A.79 of table A. A.1 to A.79 of table A. US 2010/0210574 A1 Aug. 19, 2010 32

(0200 Retention time in HPLC analysis for derivative wherein R is sec-butyl: 13.83 min. TABLE 10 0201 Retention time in HPLC analysis for derivative Compounds of the formula (Ia) wherein R is cyclohexyl, A-B is wherein R is isopropyl: 13.40 min. —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 TABLE 9 of table A.

Compounds of the formula (Ia) wherein R is cyclohexyl, A-B is TABLE 11 —CH=CH-, Q is TBDMS and the combination of the substituents R and R for each compound corresponds to a line A.1 to A.79 of Compounds of the formula (Ia) wherein R is cyclohexyl, A-B is table A —CH=CH-, Q is Hand the combination of the substituents R- and R for each compound corresponds to a line A.1 to A.79 of table A.

0202 Retention time in HPLC analysis 12.43 min. US 2010/0210574 A1 Aug. 19, 2010

TABLE 12 TABLE 17 Compounds of the formula (Ia) wherein R is cyclohexyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and Compounds of the formula (Ia) wherein R is ethyl, A-B is R for each compound corresponds to a line A.1 to A.79 of table A. —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 13 Compounds of the formula (Ia) wherein R is 1-methyl-butyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of TABLE 1.8 table A. Compounds of the formula (Ia) wherein R is ethyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of the substituents TABLE 1.4 R2 and R for each compound corresponds to a line A.1 to A.79 Compounds of the formula (Ia) wherein R is 1-methyl-butyl, A-B of table A. is —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 19

TABLE 1.5 Compounds of the formula (Ia) wherein R is ethyl, A-B is Compounds of the formula (Ia) wherein R is 1-methyl-butyl, A-B —CH=CH-, Q is Hand the combination of the substituents R- and is —CH=CH-, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. R for each compound corresponds to a line A.1 to A.79 of table A.

0203 Retention time in HPLC analysis: 13.37 min. TABLE 20 TABLE 16 Compounds of the formula (Ia) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Ia) wherein R is ethyl, A-B is is —CH2—CH2—, Q is H and the combination of the Substituents R2 —CH2—CH2—, Q is Hand the combination of the Substituents R2 and and R for each compound corresponds to a line A.1 to A.79 of table A. R for each compound corresponds to a line A.1 to A.79 of table A. US 2010/0210574 A1 Aug. 19, 2010 34

TABLE 21 TABLE 29

Compounds of the formula (Ia) wherein R is methyl, A-B is Compounds of the formula (Ib) wherein R is sec-butyl or —CH=CH-, Q is TBDMS and the combination of the Substituents R2 isopropyl, A-B is —CH=CH-, Q is TBDMS and the combination of and R for each compound corresponds to a line A.1 to A.79 of the Substituents R2 and R for each compound corresponds to a table A. line A.1 to A.79 of table A.

TABLE 22 TABLE 30

Compounds of the formula (Ia) wherein R is methyl, A-B is Compounds of the formula (Ib) wherein R is sec-butyl or —CH2—CH2—, Q is TBDMS and the combination of the substituents isopropyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of R2 and R for each compound corresponds to a line A.1 to A.79 the Substituents R2 and R for each compound corresponds to a of table A. line A.1 to A.79 of table A.

is TABLE 23 TABLE 31 Compounds of the formula (Ia) wherein R is methyl, A-B is —CH=CH-, Q is Hand the combination of the substituents R2 and Compounds of the formula (Ib) wherein R is sec-butyl or R for each compound corresponds to a line A.1 to A.79 of table A. isopropyl, A-B is —CH=CH-, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 24

Compounds of the formula (Ia) wherein R is methyl, A-B is TABLE 32 —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. Compounds of the formula (Ib) wherein R is sec-butyl or isopropyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line TABLE 25 A.1 to A.79 of table A. Compounds of the formula (Ia) wherein R is i-propyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 33

Compounds of the formula (Ib) wherein R is cyclohexyl, A-B is TABLE 26 —CH=CH-, Q is Hand the combination of the substituents R2 and Compounds of the formula (Ia) wherein R is i-propyl, A-B is R for each compound corresponds to a line A.1 to A.79 of table A. —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 34

TABLE 27 Compounds of the formula (Ib) wherein R is cyclohexyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of the substituents Compounds of the formula (Ia) wherein R is i-propyl, A-B is R2 and R for each compound corresponds to a line A.1 to A.79 —CH=CH-, Q is Hand the combination of the substituents R2 and of table A. R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 35 TABLE 28 Compounds of the formula (Ib) wherein R is cyclohexyl, A-B is Compounds of the formula (Ia) wherein R is i-propyl, A-B is —CH=CH-, Q is Hand the combination of the substituents R- and —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of R for each compound corresponds to a line A.1 to A.79 of table A. table A. US 2010/0210574 A1 Aug. 19, 2010 35

0204 Retention time in HPLC analysis: 11.36 min. TABLE 38 TABLE 36 - Compounds of the formula (Ib) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Ib) wherein R is cyclohexyl, A-B is is —CH2—CH2—, Q is TBDMS and the combination of the substituents —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R2 and R for each compound corresponds to a line A.1 to A.79 of R for each compound corresponds to a line A.1 to A.79 of table A. table A.

TABLE 37 TABLE 39 Compounds of the formula (Ib) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Ib) wherein R is 1-methyl-butyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents is —CH=CH-, Q is Hand the combination of the substituents R R2 and R for each compound corresponds to a line A.1 to A.79 of and R for each compound corresponds to a line A.1 to A.79 of table A. table A. o1 O O -N- H O

(0205 Retention time in HPLC analysis: 12.59 min. US 2010/0210574 A1 Aug. 19, 2010 36

TABLE 40 TABLE 48

Compounds of the formula (Ib) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Ib) wherein R is methyl, A-B is is —CH2—CH2—, Q is H and the combination of the Substituents R2 —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of and R for each compound corresponds to a line A.1 to A.79 table A. of table A.

TABLE 41 TABLE 49

Compounds of the formula (Ib) wherein R is ethyl, A-B is Q is Compounds of the formula (Ib) wherein R is -propyl, A-B is TBDMS and the combination of the substituents R2 and R for each —CH=CH-, Q is H and the combination of the substituents R2 compound corresponds to a line A.1 to A.79 of table A. and R for each compound corresponds to a line A. 1 to A.79 of table A.

TABLE 42 TABLE 50 Compounds of the formula (Ib) wherein R is ethyl, A-B is Compounds of the formula (Ib) wherein R is -propyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of the substituents —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 R2 and R for each compound corresponds to a line A.1 to A.79 of table A. of table A.

TABLE 43 TABLE 51 Compounds of the formula (Ib) wherein R is ethyl, A-B is Compounds of the formula (Ib) wherein R is i-propyl, A-B is —CH=CH-, Q is H and the combination of the substituents R2 —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 and R for each compound corresponds to a line A.1 to A.79 of of table A. table A.

TABLE 44 TABLE 52 Compounds of the formula (Ib) wherein R is ethyl, A-B is Compounds of the formula (Ib) wherein R is i-propyl, A-B is —CH2—CH2—, Q is H and the combination of the Substituents R2 —CH2—CH2—, Q is H and the combination of the Substituents R. and R for each compound corresponds to a line A.1 to A.79 and R for each compound corresponds to a line A.1 to A.79 of of table A. table A.

TABLE 45 TABLE 53 Compounds of the formula (Ib) wherein R is ethyl, A-B is Compounds of the formula (Ic) wherein R is sec-butyl or —CH=CH-, Q is TBDMS and the combination of the Substituents isopropyl, A-B is —CH=CH-, Q is TBDMS and the combination of R2 and R for each compound corresponds to a line A.1 to A.79 the substituents R-2 and R for each compound corresponds to of table A. a line A.1 to A.79 of table A.

TABLE 46 TABLE 54 Compounds of the formula (Ib) wherein R is ethyl, A-B is Compounds of the formula (Ic) wherein R is sec-butyl or —CH2—CH2—, Q is TBDMS and the combination of the substituents isopropyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of R2 and R for each compound corresponds to a line A.1 to A.79 the Substituents R2 and R for each compound corresponds to a of table A. line A.1 to A.79 of table A.

TABLE 47 TABLE 55 Compounds of the formula (Ib) wherein R is methyl, A-B is Compounds of the formula (Ic) wherein R is sec-butyl or —CH=CH-, Q is TBDMS and the combination of the Substituents isopropyl, A-B is —CH=CH-, Q is Hand the combination of the R2 and R for each compound corresponds to a line A.1 to A.79 Substituents Rand Rfor each compound corresponds to a line of table A. A.1 to A.79 of table A. US 2010/0210574 A1 Aug. 19, 2010

TABLE 56 TABLE 62

Compounds of the formula (Ic) wherein R is sec-butyl Compounds of the formula (Ic) wherein R is 1-methyl-butyl, A-B or isopropyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds is —CH2—CH2—, Q is TBDMS and the combination of the substituents to a line A.1 to A.79 of table A. R2 and R for each compound corresponds to a line A.1 to A.79 of table A. Retention time (min)

Mn R2 R B1a. B1b TABLE 63 56.6 CH H 12.75 11.9S 56.7 CH(CH), H 13.87 13.07 Compounds of the formula (Ic) wherein R is 1-methyl 56.78 CH2CH2CH2 12.86, 12.21 12.11, 11.57 butyl, A-B is —CH=CH-, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 57 No. R2 R Retention time (min) 63.6 CH H 11.09 Compounds of the formula (Ic) wherein R1 is cyclohexyl, 63.7 CH(CH), H 12.27 A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents R-2 and R for each compound corresponds to a line A.1 to A.79 of table A. No. R2 R Retention time (min) TABLE 64 57.6 CH H 1542 Compounds of the formula (Ic) wherein R is 1-methyl-butyl, 57.7 CH(CH3)2 H 15.79 A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 58 Compounds of the formula (Ic) wherein R is cyclohexyl, A-B is TABLE 65 —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 of Compounds of the formula (Ic) wherein R is ethyl, A-B is table A. —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 59 Compounds of the formula (Ic) wherein R is sec-butyl TABLE 66 or isopropyl, A-B is —CH=CH-, Q is Hand the combination of the Substituents R2 and R for each compound corresponds Compounds of the formula (Ic) wherein R is ethyl, A-B is to a line A.1 to A.79 of table A. —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 No. R2 R Retention time (min) of table A. 59.6 CH H 11.31 59.7 CH(CH), H 12.56 TABLE 67 Compounds of the formula (Ic) wherein R is ethyl, A-B is TABLE 60 —CH=CH-, Q is I and the combination of the substituents R and R for each compound corresponds to a line A.1 to A.79 of table A. Compounds of the formula (Ic) wherein R is cyclohexyl, A-B is —CH2—CH2—, Q is H and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 68 Compounds of the formula (Ic) wherein R is ethyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 TABLE 61 and R for each compound corresponds to a line A.1 to A.79 of table A. Compounds of the formula (Ic) wherein R is 1-methyl butyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 69 No. R2 R Retention time (min) Compounds of the formula (Ic) wherein R is methyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents 61.6 CH H 15.36 R2 and R for each compound corresponds to a line A.1 to A.79 61.7 CH(CH3)2 H 15.79 of table A. US 2010/0210574 A1 Aug. 19, 2010

TABLE 70 TABLE 79 Compounds of the formula (Ic) wherein R is methyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of the substituents Compounds of the formula (Id) wherein R is sec-butyl or isopropyl, R2 and R for each compound corresponds to a line A.1 to A.79 of table A. A-B is —CH=CH-, Q is Hand the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 71 Compounds of the formula (Ic) wherein R is methyl, A-B is TABLE 8O —CH=CH-, Q is H and the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 Compounds of the formula (Id) wherein R is sec-butyl or isopropyl, of table A. A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 72 TABLE 81 Compounds of the formula (Ic) wherein R is methyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 Compounds of the formula (Id) wherein R is cyclohexyl, A-B is and R for each compound corresponds to a line A.1 to A.79 of —CH=CH-, Q is TBDMS and the combination of the substituents R table A. and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 73 TABLE 82 Compounds of the formula (Ic) wherein R is i-propyl, A-B is Compounds of the formula (Id) wherein R is cyclohexyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents —CH2—CH2—, Q is TBDMS and the combination of the substituents R2 R2 and R for each compound corresponds to a line A.1 to A.79 and R for each compound corresponds to a line A.1 to A.79 of table A. of table A.

TABLE 83 TABLE 74 Compounds of the formula (Id) wherein R is cyclohexyl, A-B is Compounds of the formula (Ic) wherein R is i-propyl, A-B is —CH=CH-, Q is Hand the combination of the substituents R2 and R. —CH2—CH2—, Q is TBDMS and the combination of the substituents for each compound corresponds to a line A.1 to A.79 of table A. R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 84 TABLE 75 Compounds of the formula (Id) wherein R is cyclohexyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and Compounds of the formula (Ic) wherein R is i-propyl, A-B is R for each compound corresponds to a line A.1 to A.79 of table A. —CH=CH-, Q is Hand the combination of the substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. TABLE 85 TABLE 76 Compounds of the formula (Id) wherein R is 1-methyl-butyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents R2 Compounds of the formula (Ic) wherein R is i-propyl, A-B is and R for each compound corresponds to a line A.1 to A.79 of —CH2—CH2—, Q is Hand the combination of the Substituents R2 and table A. R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 86 TABLE 77 Compounds of the formula (Id) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Id) wherein R is sec-butyl or is —CH2—CH2—, Q is TBDMS and the combination of the substituents isopropyl, A-B is —CH=CH-, Q is TBDMS and the combination of the R2 and R for each compound corresponds to a line A.1 to A.79 of Substituents R2 and R for each compound corresponds to a line table A. A.1 to A.79 of table A.

TABLE 87 TABLE 78 Compounds of the formula (Id) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Id) wherein R is sec-butyl or is —CH=CH-, Q is Hand the combination of the substituents R2 isopropyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of and R for each compound corresponds to a line A.1 to A.79 of the Substituents R2 and R for each compound corresponds to a table A. line A.1 to A.79 of table A. US 2010/0210574 A1 Aug. 19, 2010 39

TABLE 88 TABLE 97 Compounds of the formula (Id) wherein R is 1-methyl-butyl, A-B Compounds of the formula (Id) wherein R is i-propyl, A-B is is —CH2—CH2—, Q is H and the combination of the Substituents R2 —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 89 TABLE 98 Compounds of the formula (Id) wherein R is ethyl, A-B is —CH=CH-, Q is TBDMS and the combination of the Substituents R2 Compounds of the formula (Id) wherein R is i-propyl, A-B is and R for each compound corresponds to a line A.1 to A.79 of —CH2—CH2—, Q is TBDMS and the combination of the substituents table A. R2 and R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 90 TABLE 99 Compounds of the formula (Id) wherein R is ethyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of the substituents Compounds of the formula (Id) wherein R is i-propyl, A-B is R2 and R for each compound corresponds to a line A.1 to A.79 —CH=CH-, Q is Hand the combination of the substituents R2 and of table A. R for each compound corresponds to a line A.1 to A.79 of table A.

TABLE 91 TABLE 100 Compounds of the formula (Id) wherein R is ethyl, A-B is Compounds of the formula (Id) wherein R is i-propyl, A-B is —CH=CH-, Q is H and the combination of the substituents R2 —CH2—CH2—, Q is Hand the combination of the Substituents R2 and and R for each compound corresponds to a line A.1 to A.79 R for each compound corresponds to a line A. 1 to A.79 of table A. of table A. Formulation Examples for use in crop protection (% percent by weight) TABLE 92 Compounds of the formula (Id) wherein R is ethyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 a) b) c) of table A. active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5%. 8% 6% castor oil polyethylene glycol ether (36 mol EO) 5% - tributylphenol polyethylene glycol ether (30 mol - 12% 4% TABLE 93 EO) cyclohexanone 15%. 20% Compounds of the formula (Id) wherein R is methyl, A-B is Xylene mixture 65%. 25%. 20% —CH=CH-, Q is TBDMS and the combination of the Substituents R2 and R for each compound corresponds to a line A.1 to A.79 of table A. Example F1

TABLE 94. Emulsifiable Concentrates Compounds of the formula (Id) wherein R is methyl, A-B is —CH2—CH2—, Q is TBDMS and the combination of the substituents 0206 Mixing finely ground active ingredient and addi R2 and R for each compound corresponds to a line A.1 to A.79 tives gives an emulsifiable concentrate which yields emul of table A. sions of the desired concentration on dilution with water.

TABLE 95 Example F2 Compounds of the formula (Id) wherein R is methyl, A-B is Solutions —CH=CH-, Q is Hand the combination of the substituents R- and R for each compound corresponds to a line A.1 to A.79 of table A. 0207

TABLE 96 a) b) c) d) Compounds of the formula (Id) wherein R is methyl, A-B is —CH2—CH2—, Q is Hand the combination of the Substituents R2 and active ingredient 80%. 10%. 5% 95% R for each compound corresponds to a line A.1 to A.79 of table A. ethylene glycol monomethyl ether — 20% — US 2010/0210574 A1 Aug. 19, 2010 40

0212 Mixing finely ground active ingredient and addi -continued tives gives an emulsifiable concentrate which yields emul sions of the desired concentration on dilution with water. a) b) c) d) polyethylene glycol (MW 400) — 70% — Example F6 N-methylpyrrolid-2-one 20% - epoxidised coconut oil 190 59 Extruder Granules petroleum ether (boiling range: 160-190) - 94% 0213 Mixing finely ground active ingredient and additives gives a solution suitable for use in the form of microdrops. active ingredient 10% sodium lignoSulfonate 2% Example F3 carboxymethylcellulose 190 kaolin 87% Granules 0208 0214) Active ingredient and additives are mixed together, the mixture is ground, moistened with water, extruded and granulated and the granules are dried in a stream of air. a) b) c) d) Example F7 active ingredient 59% 10% 8% 21% Coated Granules kaolin 94% 79% S4% highly dispersed silicic acid 190 13% 79% attapulgite 90% 18% 0215

The active ingredient is dissolved in dichloromethane, the active ingredient 3% Solution is sprayed onto the carrier mixture and the solvent is polyethylene glycol (MW 200) 3% evaporated offin vacuo. kaolin 94%

Example F4 0216 Uniform application of the finely ground active Wettable Powders ingredient to the kaolin moistened with polyethylene glycol in a mixer yields non-dusty coated granules. 0209 Example F8 Suspension Concentrate a) b) c) 0217 active ingredient 25% 50% 75% Sodium lignoSulfonate 59% 5% - Sodium lauryl Sulfate 3% 59 Sodium diisobutylnaphthalenesulfonate 6%. 10% active ingredient 40% octylphenol polyethylene glycol ether (7-8 mol EO) 2% — ethylene glycol 10% highly dispersed silicic acid 5%. 10%. 10% nonylphenol polyethylene glycol ether (15 mol EO) 6% kaolin 62%. 27% Sodium lignoSulfonate 10% carboxymethylcellulose 196 aqueous formaldehyde solution (37%) O.2% 0210 Active ingredient and additives are mixed together aqueous silicone oil emulsion (75%) O.8% and the mixture is ground in a Suitable mill, yielding wettable Water 32% powders that can be diluted with water to form suspensions of the desired concentration. 0218 Mixing finely ground active ingredient and addi tives gives a suspension concentrate which yields Suspen Example F5 sions of the desired concentration on dilution with water. Emulsifiable Concentrate Biological Examples 0211 Example B1 Action Against Spodoptera littoralis active ingredient 10% 0219 Young soybean plants are sprayed with an aqueous octylphenol polyethylene glycol ether (4-5 mol EO) 3% emulsion spray mixture comprising 12.5 ppm of test com calcium dodecylbenzenesulfonate 3% pound and, after the spray-coating has dried, the plants are castor oil polyethylene glycol ether (36 mol EO) 4% cyclohexanone 30% populated with 10 caterpillars of Spodoptera littoralis in the Xylene mixture SO% first stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by US 2010/0210574 A1 Aug. 19, 2010 comparing the number of dead caterpillars and the feeding are populated with 10 caterpillars of Plutella xylostella in the damage on the treated plants with that on untreated plants. first stage and placed in a plastics container. Evaluation is 0220. The compounds of tables exhibit good activity in made 3 days later. The percentage reduction in population and this test. Especially the compounds 1.5, 1.6, 2.6, 3.2, 3.5, 3.6, the percentage reduction in feeding damage (% activity) are 3.8, 3.19, 4.8 and 4.18 exhibit an activity of over 80% in this determined by comparing the number of dead caterpillars and teSt. the feeding damage on the treated plants with that on the untreated plants. Example B2 0226. The compounds of tables exhibit good activity in Action Against Spodoptera littoralis, Systemic: this test. Especially the compounds 2.5, 2.8, 4.5, 4.6 and 4.8 exhibit an activity of over 80% in this test. 0221 Maize seedlings are placed in the test solution. 6 days later, the leaves are cut off, placed on moist filter paper Example B5 in a petridish and infested with 12 to 15 Spodoptera littoralis larvae in the L stage. 4 days later, the percentage reduction in Action Against Diabrotica balteata population (% activity) is determined by comparing the num 0227 Maize seedlings are sprayed with an aqueous emul ber of dead caterpillars on treated plants with that on sion spray mixture comprising 12.5 ppm of the test compound untreated plants. and, after the spray-coating has dried, the maize seedlings are 0222. The compounds of tables exhibit good activity in populated with 10 Diabrotica balteata larvae in the second this test. Especially the compounds 2.6, 3.6, 3.19. 4.8 and stage and then placed in a plastics container. 6 days later, the 4.18 exhibit an activity of over 80% in this test. percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants Example B3 with that on untreated plants. Action Against Heliothis virescens 0228. The compounds of tables exhibit good activity in this test. In particular, compounds 1.5, 1.6, 2.6 and 4.8 are 0223 30-35 eggs of Heliothis virescens, from 0 to 24 hours more than 80% effective. old, are placed on filter paper in a petri dish on a layer of artificial nutrient. 0.8 ml of the test solution is then pipetted Example B6 onto the filter paper. Evaluation is made 6 days later. The percentage reduction in population (% activity) is determined Action Against Tetranvchus urticae by comparing the number of dead eggs and larvae on treated 0229. Young bean plants are populated with a mixed popu plants with that on untreated plants. Especially the com lation of Tetranychus urticae and sprayed one day later with pounds 1.5, 1.6 and 4.8 exhibit an activity of over 80% in this an aqueous emulsion spray mixture comprising 12.5 ppm of teSt. test compound. The plants are incubated for 6 days at 25°C. 0224 The compounds of tables exhibit good activity in and Subsequently evaluated. The percentage reduction in this test. population (% activity) is determined by comparing the num ber of dead eggs, larvae and adults on the treated plants with Example B4 that on untreated plants. Action Against Plutella xylostella Caterpillars 0230. The compounds of tables exhibit good activity in 0225. Young cabbage plants are sprayed with an aqueous this test. In particular, compounds 1.5, 1.6, 2.6, 3.2, 3.5, 3.6, emulsion spray mixture comprising 12.5 ppm of test com 3.8, 3.19, 4.8 and 4.18 are more than 80% effective. pound. After the spray-coating has dried, the cabbage plants 1. A compound of formula

(I)

O O

O IOII. III Oil III I I II. p-( O O in a Ry R3 w US 2010/0210574 A1 Aug. 19, 2010 42

wherein from the group consisting of halogen, C-C-alkoxy, n is 0 or 1; C-C-haloalkyl, and C-C-haloalkoxy; Rs is H. C-Cs-alkyl, C-Cs-cycloalkyl, C-C-alkenyl, R is C-C2-alkyl, C-Cs-cycloalkyl or C-C2-alkenyl, C-C-alkynyl, benzyl or —C(=O)—C-C2-alkyl: R is methyl R is H. C-C-alkyl which is optionally substituted with R is H; C-C2-alkyl, or C-C2-alkyl which is substituted halogen, C-C-alkoxy, CN, C-C-alkenyl, C-Cs-ha with one to five substituents selected from the group consisting of OH, halogen, CN, - N - NO, C-C- loalkenyl, C-C-alkynyl, C-C-haloalkenyl, —X—C cycloalkyl which is optionally substituted with one to (=Y)—Ro. —X—C(=Y)—Z-Ro. —SC Ro, aryl, three C-C-alkyl groups, norbornylenyl, C-C-cy heterocyclyl, aryl-C-C2-alkyl, heterocyclyl-C-C- cloalkenyl which is optionally substituted with one to alkyl; or aryl; heterocyclyl: aryl-C-C2-alkyl; or het three methyl groups, C-Cs-halocycloalkyl, C-C- erocyclyl-C-C2-alkyl, wherein each of the aryl, het alkoxy, C-C-alkoxy-C-C-alkoxy, C-C8-cy erocyclyl, aryl-C-C-alkyl, or heterocyclyl-C-C- cloalkoxy, C-C-haloalkoxy, C-C2-alkylthio. alkyl are optionally substituted in the ring with one to C-Cs-cycloalkylthio, C-C-haloalkylthio, C-C- five Substituents selected from the group consisting of alkylsulfinyl, C-Cs-cycloalkylsulfinyl, C-C-ha halogen, C-C-alkoxy, C-C-haloalkyl, and or C-C- loalkylsulfinyl, C-Cs-halocycloalkylsulfinyl, C-C- haloalkoxy; or alkylsulfonyl, C-C-cycloalkylsulfonyl, C-C- Ra and R together are a three- to five membered alkylene haloalkylsulfonyl, C-Cs-halocycloalkylsulfonyl, bridge, wherein one of the methylene groups may be —NRR —X—C(=Y)—R —X C(=Y)—Z R - P(=O)(OC-C-alkyl), aryl, heterocyclyl, ary replaced by O, S, or SO; and loxy, arylthio, and heterocyclyloxy; R is H; C-C2-alkyl which is optionally substituted with wherein the aryl, heterocyclyl, aryloxy, arylthio and het one to five Substituents selected from the group consist erocyclyloxy groups are optionally substituted with one ing of halogen, hydroxy, C-C-alkoxy and CN; C-C- to five Substituents selected form the group consisting of alkenyl: C-Cs-alkinyl: aryl; heterocyclyl: aryl-C-C- OH, halogen, CN, NO, C-C2-alkyl, C-Cs-cy alkyl; heterocyclyl-C-C-alkyl; or aryl; heterocyclyl: cloalkyl, C-C-haloalkyl, C-C2-alkoxy, C-C-ha aryl-C-C2-alkyl; or heterocyclyl-C-C2-alkyl, loalkoxy, C-C2-alkylthio, C-C-haloalkylthio. wherein each of the aryl, heterocyclyl, aryl-C-C- C-C-alkoxy-C-C-alkyl, C-C-alkenyl, C-C-alki alkyl, or heterocyclyl-C-C2-alkyl are optionally Sub nyl, Si(C-C2-alkyl). —X—C(=Y)—R —X—C stituted in the ring with one to five substituents selected (—Y)—Z Ra, aryl, aryloxy, heterocyclyl, and hetero from the group consisting of halogen, C-C-alkoxy, cyclyloxy; or C-C-haloalkyl, and C-C-haloalkoxy; RandR together area three- to seven-membered alkylen or E/Z isomers in free form or in salt form, mixtures of E/Z or a four- to seven-membered alkenylenbridge, wherein isomers in free form or in salt form, or tautomers in free one or two CH2-groups are independently of each other form or in salt form. replaced by a group —C(=O)— —C(=S)—, O, S, 2-7. (canceled) - NRs - OC(=O) O, OC(=O)S —OC(=O) 8. A compound according to to claim 1 wherein R is H. N(Rs.) , —C(=O)C) , C(=O)S, C(=O)N 9. A compound according to claim 1 wherein R is C-C- (Rs.) , N(Rs)C(=O)S , N(Rs)C(=O)N(Rs.) , alkyl. and wherein the alkylene or alkenylenbridge may be independently of each other substituted with one or two 10. A compound according to claim 9 wherein R is Substituents selected from the group consisting of methyl. C-C-alkyl, C-C-alkoxy and C-Ca-halogenalkyl, or 11. A compound according to claim 1 wherein R and R RandR together area three- to seven-membered alkylen together area three- to seven-membered alkylen- or a four- to or a four- to seven-membered alkenylenbridge, wherein seven-membered alkenylenbridge, wherein one or two CH one or two CH2-groups may independently of each other groups are independently of each other replaced by a group be replaced by a group —C(=O)— —C(=S)—, O, S, - NRs –OC(=O)–O, OC(=O)S —OC(=O) N(Rs.) , —C(=O)C) , C(=O)S, C(=O)N (Rs)—, N(Rs)C(=O)S —N(Rs)C(=O)N(Rs)—, —N(Rs)C(=O)N(Rs)—, and wherein the alkylene or alk and wherein the alkylene or alkenylenbridge are inde enylenbridge may be independently of each other substituted pendently of each other substituted with one or two with one or two Substituents selected from the group consist Substituents selected from the group consisting of ing of C-C-alkyl, C-C-alkoxy, and C-C-halogenalkyl. C-C-alkyl, C-C-alkoxy and C-Ca-halogenalkyl, 12. A compound according to claim 1 wherein R and R X is O, NRs or a bond; together area three- to seven-membered alkylen- or a four- to Y is O or S; seven-membered alkenylenbridge, wherein one or two CH Z is O, S, or NRs: groups may independently of each other be replaced by a R is H; C-C2-alkyl which is optionally substituted with group —C(=O)— —C(=S)—, O, S, —NRs —OC one to five Substituents selected from the group consist (=O) O, OC(=O)S , OC(=O)N(R)-, -C(=O) ing of halogen, hydroxy, C-C-alkoxy and CN; C-C- O— —C(=O)S. —C(=O)N(Rs)— —N(Rs)C(=O)S alkenyl: C-C-alkynyl: aryl; heterocyclyl: aryl-C-C- or —N(Rs)C(=O)N(Rs)—, and wherein the alkylene or alk alkyl; heterocyclyl-C-C-alkyl; or aryl; heterocyclyl; enylenbridge are independently of each other substituted with aryl-C-C2-alkyl; or heterocyclyl-C-C2-alkyl; one or two Substituents selected from the group consisting of wherein each of the aryl, heterocyclyl, aryl-C-C- C-C-alkyl, C-C-alkoxy, and C-C-halogenalkyl. alkyl, or heterocyclyl-C-C2-alkyl are optionally Sub 13. A compound according to claim 1 wherein R is iso stituted in the ring with one to five substituents selected propyl or secbutyl. US 2010/0210574 A1 Aug. 19, 2010 43

14. A compound according to claim 8 wherein R is iso- 18. A compound according to claim 12 wherein R is iso propyl or secbutyl. propyl or secbutyl. 15. A compound according to claim 9 wherein R is iso- 19. A pesticide which contains at least one compound of propyl or secbutyl. the formula (I) as described in claim 1 as active compound and at least one auxiliary. 16. A compound according to claim 10 wherein R is iso 20. A method for controlling pests wherein a composition propyl or secbutyl. as described in claim 13 is applied to the pests or their habitat. 17. A compound according to claim 11 wherein R is iso propyl or secbutyl. ck