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.