AU656227B2 - Insecticide compounds for agricultural and horticultural use - Google Patents

Description

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PCT

ANNOUNCEMENr OF THE LATER PUBUCATION OFINTERNATIONAL SEARCH

REPORT

0 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 International Publication Number: WO 93/03618 A01N 53/00, 41/02, 37/44 A3 A01N 37/38, 31/14 (43) International Publication Date: 4 March 1993 (04.03.93) (21) International Application Number: PCT/US92/07288 (74)Agents: THOMPSON, Raymond, D. et al.; Uniroyal Chemical Company, Inc., World Headquarters, Mid- (22) International Filing Date: 27 August 1992 (27.08.92) dlebury, CT 06749 (US).

Priority data: (81) Designated States: AU, BG, US, European patent (AT, 238,923 27 August 1991 (27.08.91) JP BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, 289,157 8 October 1991 (08.10.91) JP NL, SE).

(71) Applicant (for all designated States except US): UNIROYAL Published CHEMICAL COMPANY, INC. [US/US]; World Head- With international search report.

quarters, Middlebury, CT 06749 Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of (72) Inventors; and amendments.

Inventors/Applicants (for US only) KATAOKA, Masaaki [JP/JP]; NAKAMURA, Takehiko [JP/JP]; WAKAI, (88) Date of publication of the international search report: Akira [JP/JP]; Nippon Soda Co., Ltd., Haibara Agricul- 13 May 1993 (13.05.93) tural Research Station, 62-1 Sakbe, Haibara, Haibaragun, Shizuoka (JP).

(54) Title: INSECTICIDE COMPOUNDS FOR AGRICULTURAL AND HORTICULTUIAL USE (57) Abstract Compounds comprised of 2-(4-tert-butylphenoxy) cyclohexyl prop-2-ynyl sulfite and a synthetic pyrethroid exhibit synergistic pesticidal activity.

1__1 WO 93/03618 PCT/US92/07288 TNSECTTCTDE COMPOUNDS FOR AGRTCULTURAL AND HORTTCULTURAL USE BACKGROUND OF THE INVENTION 1. Field of the Invention This invention is directed to mixtures of propargite and synthetic pyrethroids, which exhibit synergistic activity as pesticides.

Thrips palmi is a transplanted insect from Southeast Asia which has caused serious damage to cucumber, watermelon, melon, eggplant and green pepper in recent years. It has no strong natural enemy, and is believed to cause more serious growth damage or fruit damage than any other known insect. Compounds such as sulbrophos, oxamil, carbosulphane, cypermethrin, pemfracalp, BMPC, DMTP, cyfulbenzron, etc. have been used in the past. However, none of them has had a sufficient protective effect.

SUIMARY OF THE INVENTION The compositions of the present invention contain an active ingredient comprising a mixture of A) propargite, and B) a synthetic pyrethroid. The present invention also comprises a method for controlling undesirable insects which comprises applying an effective amount of a composition according to the present invention to a locus to be protected.

SUBSTITUTE SHEET i i WO 93/03618 PCr/US92/07288 -2- DETAILED DESCRIPTION OF THE INVENTION The propargite portion of the active ingredient is a well known insecticide sold under the trademark OMITE (Uniroyal Chemical Company) and has the chemical name 2-(4-tert-butylphenoxy) cyclohexyl prop-2-ynyl sulfite.

Examples of the synthetic pyrethroid active ingredient are cyfluthrin, fenpropathrin, cyhalothrin, fulvalinate, tralomethrin, etofenprox, fulcytirinate, cypermethrin, permethrin, and fenvalelate.

In the insecticide compositions of the present invention, the propargite component may be present in the amount of from 3 to 1,000 ppm, or more preferably 100-400 ppm. The synthetic pyrethroide type component may be present in the amount of from 1 to 1,000 ppm, or more preferably 10-200 ppm.

Propargite, which is one of the effective components of the insecticide offered by the present invention, shows almost no effect against minami-kiiro-azamiuma (also known as Thrips palmi) by itself. In addition, synthetic pyrethroide type insecticides, which is also one of the effective components of the insecticide compounds offered by the present invention, does not show sufficient effect against minami-kiiro-azamiuma by itself even in the case of cypermethrin which has obtained the Agricultural Chemical Registration in Japan. The compositions offered by the present invention give superior effectiveness which cannot be obtained by each component WO 93/03618 PCT/US92/07288 -3alone.

As it is described in the application example, common forms of agricultural agents such as aqueous solutions, emulsions, dry-flowable, flowable, or smoke agent which contain the propargite and the synthetic pyrethroide type insecticides may be prepared.

Alternatevely, agents which contain the individual active ingredients are prepared and then mixed together later.

The present invention is explained in detail by reference to the following examples.

Example 1 Propargite 30 parts Tralomethrin 1 part White Carbon (Silica) 2 parts Diatmaceous Earth 58 parts Alkylbenzene sodium sulfonate 2 parts Lignin sodium sulfonate 7 parts The above components were uniformly mixed, and dissolved in water to obtain a 31% aqueous solution.

Example 2 Propargite 30 parts Tralomethrin 1 part Xylene 44 parts Dimethylformamide 15 parts Alkylbenzene calcium sulfonate 4 parts Polyoxyethylene-alkylphenylether 6 parts WO 93/03618 PCT/US92/07288 -4- The above components were mixed and melted to obtain a 31% emulsion.

Example 3 A mixed aqueous solution of propargite (BPPS) and synthetic pyrethroid type insecticides was diluted to the concentrations shown in Table 1, and sprayed on individually potted 20-30 cm tall greenhouse grown eggplants (kind: Kokuyo) which were severely infested by minami-kiiro-azamiuma by using a portable sprayer until the liquid started to drip from the leaves. The number of adult and larvae of minami-kiiro-azamiuma were counted before the spraying and a few days after the spraying, and its effectiveness compared with the effectiveness obtained by spraying them individually.

The results are shown in Table 1.

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TABLE 1 Number of Insects /4 leaves 1 Treatment 3 Number of Insects Concentration (ppm) o DAT2) A. L.

4 DAT A. L.

7 DAT A L.

11 DAT A L.

Control(No Treatment) Propargite(Pro.) Pro. Tralomethrin Tralomethrin Pro. Cypermethrin Cypermethrin Pro. Cyhalothrin Cyhalotliin Pro. Permethrin Permethrin Pro. Fluvalinate Fluvalinate Pro Fenpropathrin Fenpropathrin Pro. Etofenprox Etofenprox 59 79 48 80 93 136 152 183 176 212 104 626 106 546 400 130 400+10 28 10 31 400+60 80 60 17 400+25 42 25 26 400+100 25 100 42 400+50 12 50 45 400+100 27 100 22 400+200 18 200 33 179 108 138 169 160 132 188 138 206 91 259 86 0 153 12 118 10 196 15 180 0 123 0 57 0 185 16 183 2 224 9 130 10 244 1 44 6 49 12 39 41 ill 6 57 9 77 12 131 2 marked leaves pot DAT=Days after treatment Sprayed on May 27, 1991 Adults L.=Larvae TABLE 2 Number of Insects/4 leae 1 Treatment3) Concentration (ppm) 0 DAT2) A. L. 4) 4 DAT A. L.

7 DAT A. L.

11 DAT A L.

Control(No Treatment) Propargite(Pro.) Pro. +Tralomethrin Tralomethrin Pro. +Cypermethrin Cypermethrin Pro. +Cyhalothrin Cyha 10th rin 28 38 28 38 57 82 19 37 55 91 15 46 43 87 33 72 400 400+10 35 10 19 400+60 60 70 57 102 24 62 41 400+100 34 100 18 Pro. +Cyfluthrin Cyfluthrin Pro. +Fluvalinate Fluvalinate 4 00+2 5 25 0 104 400+50 50 43 2 marked leaves pot DAT=Days after treatment Sprayed on May 27, 1991 Adults L.=Larvae cll ~c~a m~ WO 93/03618 PCr/US92/07288 -7- Example 4 The effect of propargite (BPPS) and synthetic pyrethroid mixtures on minami-kiiro-azaiuma was studied in a manner similar to Example 3, except that the emulsion form of Example 2 was used. The results are shown in Table 2.

,_1

Claims (4)

1. An insecticidal composition comprising:

2-(4-tert-butylphenoxy) cyclohexyl prop-2-ynyl sulfite; and a synthetic pyrethroid selected from the group consisting of cyfluthrin, fenpropathrin, cyhalothrin, fulvalinate, tralomethrin, etofenprox, fulcytirinate, cypermethrin, permethrin, and fenvalelate. 2. A composition in accordance with claim 1 wherein component is present in an concentration from 3-1000 ppm and component is present in a concentration from 1-1000 ppm..

3. A process for controlling undesirable pests which comprises applying to a locus to be protected a pesticidally effective amount of a composition in accordance with claim 1. F C 1 International Application No Page 2 PCT/US 92/07288 III. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category 0 Citation of Document, with indication, where appropriate, of the relevant passages Relevant to Claim No. CHEMICAL ABSTRACTS, vol. 85, no. 19, 8 November 1976, Columbus, Ohio, US; abstract no. 138545t, C.B.RATHBURN ET AL. 'Tests of resmethrin with several synergists in a laboratory wind tunnel against caged adult mosquitoes' page 152 ;column 2; see abstract MOSQ. NEWS vol. 36, no. 2, 1976, pages 204 205 US,A,3463859 (R.A.COVEY ET AL.) 26 August 1969 see column 1, line 29 column 2, line 17 se. column 7, line 12 see column 8, line 15 li e 17 EP,A,0412937 (CIBA-GEIGY) 13 February 1991 see claim 6 CHEMICAL PATENTS INDEX, DOCUMENTATION ABSTRACTS JOURNAL Section Ch, Week 9049, 13 February 1991 Derwent Publications Ltd., London, GB; Class C, AN 90-365870/49 JP,A,2 264 702 (NIPPON SEIKA) 29 October 1990 see abstract 1-3 1-3 1-3 1-3 Form PCISII etaaet J-ay13jSeme niwpnw he Term PCTSA 210 extr rbeetj jJraxry 1995 See notes on accompanymez sheet I INTERNATIONAL SEARCH REPORT International Application No PCT/IIS cl2/fl728R I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all)b According to International Patent Classification (IPCI or to both National Classification and IPC A 01 N 53/00 A 01 N 41/02 A 01 N 37/44 A 01 N 37/38 A 01 N 31/14 II. FIELDS SEARCHED Minimum Documentation Searched" Classification System Classification Symbols A 01 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched 8 Ill. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category 'Citation of Document. 1 with indication, where appropriate, of the relevant passages 2 Relevant to Claim No. 13 A CHEMICAL PATENTS INDEX, DOCUMENTATION ABSTRACTS 1-3 JOURNAL Section Ch, Week 9032, 3 October 1990 Derwent Publications Ltd., London, GB; Class C, AN 90-241983/32 JP,A,2 167 207 (MITSUI TOATSU CHEM) 27 June 1990 see abstract PATENT ABSTRACTS OF JAPAN vol. 14, no. 431 (C-759)(4374) 17 September 1990 see abstract A CHEMICAL ABSTRACTS, vol. 95, no. 1, 6 July 1981, 1-3 Columbus, Ohio, US; abstract no. 1918d, SUMITOMO CHEMICAL 'Synergistic acaricide composition' page 205 ;column 2 see abstract JP,A,8 129 509 o Special categories of cited documents 0 'T later document published after the international filing date or priority date and not in conflict with the application but document defining the general state of the arn which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered no",l or cannot be considered to 'L document which may throw doubts on priority claim(s) or involve pa inventive step which is cited to establish the publication daie of another document ,f particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the inteaiional filing date but in the a r t later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 01-12-1992

20. 04. 93 International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE W. LAMERS Form PCTIISA/210 i econd beetl l Jaanry 19851 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 9207288 SA 64171 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 06/04/93 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date US-A- 3463859 26-08-69 BE-A- 648821 01-10-64 CH-A- 430314 DE-A- 1567205 23-11-72 FR-A- 1404674 GB-A- 1012496 LU-A- 46280 09-12-64 NL-A- 6406854 19-01-65 US-A- 3272854 EP-A- 0412937 13-02-91 AU-A- JP-A- US-A- 6085490 3083903 5093358 14-02-91 09-04-91 03-03-92 SFor more detaili aout this annex see Official Journal of the European Patent Office, No. 12/82 _I Internat. 1 applica!ion No. PCT/US 92/ 07288 INTERNATIONAL SEARCH REPORT Box I Observations where certain claims were found unsearchable (Contin' i of item I of first sheet) This international search report has not been established in respect of certain claims under Article 17(2)(a) for the following reasons: 1. D Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely: 2. Claims Nos.: because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3. O Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a). Box II Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows: 1. claims :1-3 (incomplete) 2. claims 1-3 (incomplete) 3. claims :1-3 (incomplete) 4. claims 1-3 (incomplete) see for futher information PCT/Form 206 (extra sheet). 1. D As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims. 2. As all searchable claims could be searches without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. D As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those claims for which fees were paid, specifically claims Nos.: 4. No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: 1. claims 1-3 (incomplete) Remark on Protest D The additional search fees were accompanied by the applicant's protest. SNo protest accompanied the payment of additional search fees. Form PCT/ISA/210 (continuation of first sheet (July 1992) I