1. STN Users Day Bologna, 11 Dicembre 2007 Indicizzazione in CA e brevetti elusivi

2. Un caso reale QUESITO: Libertà di attuazione di una FORMULAZIONE EW (Water Emulsion) a base di TEBUCONAZOLO (fungicida) COMPOSIZIONE a) TEBUCONAZOLE g/l b) TRIBUTYLCITRAT g/l c) SOLVENT1 g/l d) COSOLVENT1 g/l e) COSOLVENT2 g/l f) EMULSIFIER g/l

3. Un caso reale QUESITO: Libertà di attuazione di una FORMULAZIONE EW (Water Emulsion) a base di TEBUCONAZOLO (fungicida) COMPOSIZIONE a) TEBUCONAZOLE g/l b) TRIBUTYLCITRAT g/l c) SOLVENT1 g/l d) COSOLVENT1 g/l e) COSOLVENT2 g/l f) EMULSIFIER g/l

4. Considerazioni preliminari USE OF CITRIC ACID DERIVATIVES AS FUNGICIDAL ADJUVANTS Pubblicazione numero: EP1123002 B1 Data di pubblicazione: 2006-01-11 Inventore(i): BARDSLEY RICHARD ANDREW (GB); BICKERS UDO MATTHIAS (DE); BRIGGS GEOFFREY GOWER (GB); GREEN SHIRLEY ANN (GB); PATE ADRIENNE ELIZABETH (GB); SANWALD ERICH FRIEDRICH (DE); STOCK DAVID (GB) Richiedente(i): AVENTIS CROPSCIENCE SA (FR) Dati domanda: EP19990950920 19991022 Dati priorità: WO1999GB03430 19991022; GB19980023010 19981022 Riassunto The invention provides the use as a pesticidal adjuvant of at least one citric acid derivative and compositions containing the derivative, which has a log octanol-water coefficient (log P) of 2.6 to 11 and an equivalent hydrocarbon (EH) value of 29 to 47. The invention has been shown to enhance the efficacy of a range of pesticides. Estratto della Descrizione [0016] Particularly preferred compounds are tri-n-butyl citrate (log P = 4.3, EH = 32) and O-acetyl tri-n- butyl citrate (log P = 4.8, EH = 32). [0017] In a further aspect, the invention provides a fungicidal composition comprising at least one fungicidal compound and at least one citric acid derivative defined hereinabove. ………. [0020] A suitable fungicide is for example: (i) a conazole sterol Delta 14 -demethylase inhibitor, …… [0021] Conazoles are defined in ISO standard 257 as compounds based on imidazole or 1,2,4-triazole and containing a halogenated phenyl group. Examples include prochloraz (and its metal complexes - especially the zinc, manganese or copper complex), propiconazole, flusilazole, hexaconazole, tebuconazole,…..

6. REGISTRY TEBUCONAZOLO: => e tebuconazole/cn E13 1 TEBRON/CN E14 1 TEBROPHENE/CN E15 1 --> TEBUCONAZOLE/CN => s e15 L5 1 TEBUCONAZOLE/CN => d scan L5 1 ANSWERS REGISTRY COPYRIGHT 2007 ACS on STN IN 1H-1,2,4-Triazole-1-ethanol, -[2-(4-chlorophenyl)ethyl]- -(1,1-dimethylethyl)- MF C16 H22 Cl N3 O CI COM => sel l5 rn L6 SEL L5 1- RN : 1 TERM => s l6/crn L7 261 L6/CRN => s l7 not pms/ci 1190189 PMS/CI L8 261 L7 NOT PMS/CI

7. REGISTRY => s C16H22ClN3O L9 519 C16H22CLN3O => s l9 and 1H-1,2,4-Triazole-1-ethanol/hp 9554 1H-1,2,4-TRIAZOLE-1-ETHANOL/HP L12 156 L9 AND 1H-1,2,4-TRIAZOLE-1-ETHANOL/HP => s l12 and 2(w)4(w)chlorophenyl(w)ethyl L13 144 L12 AND 2(W)4(W)CHLOROPHENYL(W)ETHYL => s l13 and 1(w)1(w)dimethylethyl L14 143 L13 AND 1(W)1(W)DIMETHYLETHYL => s l14 not l7 L15 7 L14 NOT L7 => d scan

8. REGISTRY => s l14 and (w)2 and (w)1 L16 141 L14 AND (W)2 AND (W)1 => s l5 or l7 L21 262 L5 OR L7 => s l16 not l21 L22 4 L16 NOT L21 => sel l22 rn 1- L23 SEL L22 1- RN : 4 TERMS => s l23/crn L24 0 L23/CRN => s l21 or l16 L25 266 L21 OR L16 L25 TEBUCONAZOLO

9. REGISTRY TRIBUTILCITRATO: => s (tributyl(l)citrate) L26 7 (TRIBUTYL(L)CITRATE) => d scan L26 7 ANSWERS REGISTRY COPYRIGHT 2007 ACS on STN IN 1,2,3-Propanetricarboxylic acid, 2-(acetyloxy)-, 1,2,3-tributyl ester MF C20 H34 O8 CI COM L26 7 ANSWERS REGISTRY COPYRIGHT 2007 ACS on STN IN 1,2,3-Propanetricarboxylic acid, 2-hydroxy-, 1,2,3-tributyl ester MF C18 H32 O7 CI COM => S 1,2,3-Propanetricarboxylic acid/hp and (tributyl ester) L27 35 1,2,3-PROPANETRICARBOXYLIC ACID/HP AND (TRIBUTYL ESTER) => d scan

10. REGISTRY IN 1,2,3-Propanetricarboxylic acid, 2-amino-, tributyl ester IN 1,2,3-Propanetricarboxylic acid, 2-sulfo-, 1,2,3-tributyl ester, magnesium salt => S L27 and C H O/ELF L28 25 L27 AND C H O/ELF => S L28 not PMS/CI 1190189 PMS/CI L32 16 L28 NOT PMS/CI L32 TRIBUTILCITRATO

11. HCAPLUS L25 = TEBUCONAZOLO L32 = TRIBUTILCITRATO => s EP1123002/PN L1 1 S EP1123002/PN RN=77-92-9 => S L25 OR TEBUCONAZOL? L36 1717 L25 OR TEBUCONAZOL? => S L32 OR 77-92-9D L37 5345 L32 OR 77-92-9D => S L36 AND L37 L38 4 L36 AND L37 => S L38 AND P/DT L39 4 L38 AND P/DT => S L39 AND L1 L45 0 L39 AND L1 => S FUNGIC? AND L37 L46 97 FUNGIC? AND L37 => S L46 AND P/DT L47 93 L46 AND P/DT => S L47 AND L1 L48 0 L47 AND L1

12. HCAPLUS EP1123002 B1: USE OF CITRIC ACID DERIVATIVES AS FUNGICIDAL ADJUVANTS TITLE: Use of citric acid derivatives as pesticidal adjuvants ABSTRACT: The invention provides the use as a pesticidal adjuvant of at least one citric acid derivative which has a log octanol-water coefficient (log P) of 2.6 to 11 and an equivalent hydrocarbon (EH) value of 29 to 47. Examples are tri-Bu citrate and O-acetyltibutyl citrate. The invention has been shown to enhance the efficacy of a range of pesticides.

13. HCAPLUS SUPPL. TERM: citric acid deriv pesticide formulation adjuvant INDEX TERM: Pesticide formulations (citric acid derivs. as adjuvants in) INDEX TERM: 136426-54-5, Fluquinconazole ROLE: AGR (Agricultural use); BIOL (Biological study); USES (Uses) (Castellan; citric acid derivs. as adjuvants in formulations of) INDEX TERM: 77-90-7 77-92-9D, Citric acid, derivs. 77-94-1, Tributyl Citrate ROLE: MOA (Modifier or additive use); USES (Uses) (adjuvants in pesticide formulations) INDEX TERM: 115-29-7, Thiodan 23103-98-2, Pirimor 52918-63-5, Decis 74115-24-5, Clofentezine 81335-77-5, Pursuit 104206-82-8, Mesotrione 110488-70-5, Dimethomorph 111991-09-4, Milagro 120068-37-3, Fipronil 131475-57-5, Triaziflam 131860-33-8, Amistar 131983-72-7, Triticonazole 215657-11-7, Affinity ROLE: AGR (Agricultural use); BIOL (Biological study); USES (Uses) (citric acid derivs. as adjuvants in formulations of)

14. HCAPLUS Compounds indexed from Patents: Patent Examples (with supporting data) Tables in Disclosure (with supporting data) Patent Claims (unambiguously defined) Substances indexed in CAplus Estratto della Descrizione [0016] Particularly preferred compounds are tri-n-butyl citrate (log P = 4.3, EH = 32) and O-acetyl tri-n- butyl citrate (log P = 4.8, EH = 32). [0017] In a further aspect, the invention provides a fungicidal composition comprising at least one fungicidal compound and at least one citric acid derivative defined hereinabove. ………. [0020] A suitable fungicide is for example: (i) a conazole sterol Delta 14 -demethylase inhibitor, …… [0021] Conazoles are defined in ISO standard 257 as compounds based on imidazole or 1,2,4-triazole and containing a halogenated phenyl group. Examples include prochloraz (and its metal complexes - especially the zinc, manganese or copper complex), propiconazole, flusilazole, hexaconazole, tebuconazole,…..

15. RICERCA DEI BREVETTI ELUSIVI L32 = TRIBUTILCITRATO => s EP1123002/PN L1 1 S EP1123002/PN HCAPLUS RN=77-92-9 => S L37 AND P/DT 5982832 P/DT L49 3349 L37 AND P/DT => S L32 OR 77-92-9D L37 5345 L32 OR 77-92-9D => SEL L49 PN WITH "EP" L50 SEL L149 1- PN WITH "EP" : 1315 TERMS => SEL L49 PN WITH "US" L51 SEL L49 1- PN WITH "US" : 2492 TERMS

16. RICERCA DEI BREVETTI ELUSIVI EPFULL DE: Tebuconazol EN/FR: Tebuconazole => S L50 L52 1315 L50 => S L52 AND TEBUCONAZOL? L53 2 L52 AND TEBUCONAZOL? => S EP1123002/PN L54 1 EP1123002/PN => S L53 and L54 L55 1 L53 AND L54 => SEL L49 PN WITH "EP" L50 SEL L149 1- PN WITH "EP" : 1315 TERMS

17. RICERCA DEI BREVETTI ELUSIVI USPATFULL => SEL L49 PN WITH "US" L51 SEL L49 1- PN WITH "US" : 2492 TERMS => S L51 L56 2186 L51 => S US6551964/PN L57 1 US6551964/PN => S L56 AND TEBUCONAZOLE L58 7 L56 AND TEBUCONAZOLE => S L58 AND L57 L59 1 L58 AND L57 => S L32 OR 77-92-9D L60 597 L32 OR 77-92-9D => S L60 AND TEBUCONAZOL? L61 4 L60 AND TEBUCONAZOL? => S L61 AND L57 L62 1 S L61 AND L57

18. RICERCA DEI BREVETTI ELUSIVI PCTFULL DE: Tebuconazol EN/FR: Tebuconazole ….. PATDPAFULL, GBFULL, FRFULL

19. Marpat (Prev.) Registry Ifiudb USPat. (it,ti,st,clm,ab) Ifiref HCAPlus (PATIPC) RESULTS RNs keywords Structures RNs keywords RNs keywords keywords, NCL keywords RESULTS Uniterms, NCL NCL Wpindex (DCR) Others Wpids (FC-MC) keywords ICC Pn,Apps,keywords DUP. IDE. FSORT RESULTS Citations RESULTS FINAL RESULTS Patents search flow-sheet keywords ANs (subset) keywords (only subscribers) Un ringraziamento speciale al Dr Guglielmo Rucci per quanto ci ha saputo trasmettere in questi anni….. Alcuni di noi, grazie alle competenze costruite sulla base dei suoi insegnamenti, hanno avuto nuove opportunità professionali, spesso talmente innovative nel proprio ambito aziendale da imporre la necessità di nuovi profili professionali ………

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