TW311910B - - Google Patents

Description

3113111 V. Description of the invention (1 clear background f poems, first read the notes on the back and then fill out this page) 71 ^ Global economic damage and mite pest damage and rampant production in major agricultural crop production. Due to these pests, for example, the yield of 7-insect biochemical heart crops can be as high as 39% and 78% respectively. Pests and can lead to lower yields, lower crop quality, reduced consumption, increase = ease = failure, increased risk of disease, higher processing costs, higher shipping costs = and increased market prices. Therefore, novel and effective insect and mite control and crop protection methods are a continuous global demand. Λ Weekly, the object of the present invention is to provide an effective method for controlling harmful insects and mites. Another object of the present invention is to provide a method of protecting growing and harvested crops from harmful and harmful effects caused by insects and mites attacking and running. A further object of the present invention is to provide insecticide and acaricide compounds and compositions and methods for their preparation. SUMMARY OF THE INVENTION The present invention provides a method for controlling insect and mite pests, which includes contacting these insects or their food supply, habitat or breeding area with an insecticidally effective amount of a compound of formula I; consumption by employees of the Central Bureau of Standards of the Ministry of Economic Affairs Printed by cooperatives

-Rm— I I

Y N 2 A (I) -4- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) A7

SiiSl® B7 5. Description of the invention (2)

I (please read the precautions on the back before filling this page) where R, Y and Z include the electron evacuation group and no electron supply group, A is any group that can be enzymatically or hydrolytically cleaved and m is 1, 2, 3, Or an integer of 4. The present invention also provides a method for protecting growing crops from attack or rampage by insects and mites, which includes applying an insecticidally effective amount of a substituted vermicular compound of formula I to the leaf group of the plant, or the growth Soil or water. The present invention further describes compounds and compositions useful as insecticides and acaricides and methods for their preparation. Detailed description of the invention A variety of insects and mites cause large economic losses, by destroying or damaging agricultural crops and garden products and medical plants; by spreading and development of bacteria, molds and viruses that help produce plant diseases; , Other products and property prices. Insect and shout attacks and rampages have caused the biggest problems for some farmers around the world. The need for alternative and effective insect and mite control is a global consideration. It has been found that the substituted pyridine compounds of formula I are highly effective agents to control various insects and pests. 1 The indole compounds of formula I of the present invention include those with the formula: Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

This paper is applicable to the Chinese National Standard (CNS) A4 specifications (2 丨 X 297 mm) umQ V. Description of the invention (3 A7 B7 where Y and Z are hydrogen, halogen, cn, N02, 5 (0% ¾, Ci: -C6 halo-kinyl, Ci-Cg haloalkoxy, COR2, CSR3 or W, the restriction condition is only one of Y or z can be w and the further restriction condition is only one of Y or ζ Is argon; W is or

(Please read the precautions on the back before filling in this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, R is any combination of 1 to 4 halogens, CN, N02, S (0) nR7, haloalkyl or ( ： 1- 匸 6haloalkoxy; m is an integer of 1, 2, 3 or 4; η is an integer of 0, 1 or 2; L, M and Q are each hydrogen, halogen, N02, CN, C ^ -C ^ haloalkyl, C ^ -C ^ haloalkoxy, COR7 or S (0) nR8; * R1, R2, R3, ruler 7 and R8 are each C haloalkyl; X is 0 or S ;; R4, R5 and R6 are each hydrogen, halogen, N02 ", CN 's (0) nk9 or 115 and R6 can form a ring together with the atoms to which they are connected, wherein R5R6 is represented by the following formula 12 pcs 13 -c—c—c = c—-; -6 Private paper under-applicable to China National Standard (CNS) A4 specification (210X297mm) $ nm A7 B7 V. Description of invention (4) R10, K · 11. R12 and R13 are each hydrogen, halogen, CN, N02 or.: (Please read the notes on the back before filling this page) S (0) nR "; R 9 and R! 4 are C i -C 6 haloalkyl; A is r15, 〇r154cn:

R15 is hydrogen, COR16, c HR 17NH C 0 R 18, c H2s Q! 'O CHR 丨' Yang Man Mi, c ^ _ c 6 burning group, optionally substituted by the following: .1 to 3 halogen atoms, | A two (Ci-C # pit group.) Broken burned group, 1 group, 1 cyano group, 1 or 2 c 丨 -C 4 alkoxy groups, optionally substituted with 1 to 3 halogen atoms,. 1 C i-C 4 alkylthio, 1 phenyl, optionally with 1 to 3 halogen atoms, 1 to 3 C plant C 4 alkyl or 1 to 3 (: 1- (: 4 alkoxy substituted , 1 stupoxy group 'is optionally substituted with 1 to 3 halogen atoms, 1 to 3 C i -C 4 alkyl groups or 1 to 3 (: 1-(: 4 alkoxy substitution, Ministry of Economic Affairs Central Standards Bureau The employee consumer cooperative prints 1 benzyloxy group, with 1 to 1 halogen atom, 1 to; 3 〇1- (: 4 alkyl groups or 1. to 3 (: 1_ (: 4 alkoxy substitution _ 丨,-. 1 C 1-C 6 pitylcarbonyloxy, optionally substituted with 1 to 3 halogen atoms, -1 C 2-C 6 alkenylcarbonyloxy, optionally Substituted with 1 to 3 halogen atoms, 1 stupylcarbonyloxy group, 1 to 3 closed atoms, 1 to 3 C i-(: 4 alkyl groups or 1 to 3 (:: 1- ( : 4 alkoxy substitution, 1 C 1-C 6 alkoxy Carbonyl group, according to the situation, with 1 to 3 halogen atoms or 1 to 3 ^ Paper scale, applicable to the Chinese Su ^ Standard (CNS) A4 specification (21〇 297 Gong Dong 1 311910 A7 B7, Ministry of Economic Affairs, Central Bureau of Standards, Employee Consumer Cooperative Printed Five 3. Description of the invention (5) Substitutes of 匸 厂 匚 #alkoxy, or 1 benzylcarbonyloxy group with 1 to 3 _atoms' j to 3 Ci_C4 burned groups or 1 to 3 Ci-C4 pitoxy substitutions, C 3 -C 6 alkenyl's optionally substituted with 1 to 3 halogen atoms or 1 stupyl group, c 3-c 6 alkynyls, optionally 1 to 3 Atomic or 1 phenyl substituted, Rie is CrC: 6-gauge or Cg-C6 cycloalkenyl, substituting 1 to 3 halogen atoms, _ 1 hydroxyl, 1 cyano, 1 or 2 C i-C 4 alkoxy groups, optionally substituted with 1 to 3 halogen atoms, 1 〇1- (: 4 alkylthio, 1 phenyl group, optionally 1 to 3 halogen atoms' 1 Up to 3 〇 丨 _ c 4 burned group or 1 to 3 (: 1- <: 4 alkoxy substituted, 1 phenoxy, with 1 to 3 atoms, 1 to 3 c 丨 _ c 4 burned groups or 1 to 3 (: 1- (: 4 alkoxy substituted, 1 benzyloxy, optionally 1 to 3 C on the phenyl ring _ c 4 alkyl or! to 3 halogen atoms, 1 to 3 c alkoxy substitutions, 1 C 丨 -C 6 carbonyl carbonyloxy, optionally substituted with 1 to 3 remote self atoms: 1 CrC: 6 alkenylcarbonyloxy, optionally substituted with 1 to 3 as halogenogen>, 1 phenylcarbonyloxy, optionally 1 to 3 halogen atoms, 1 to 3 Cr-CU Burning group or 1 to 3 <: 1- <: 4 alkoxy substitution, 1 C 丨 -C g-regoxycarbonyl group, with 1 to 3 halogen atoms or 1 to 3 C as appropriate!- C 4 alkoxy substitution, or 1 narrow carbonyl group 'is applicable to the Chinese National Standards (CN77X ^ · 格 ㈤χ29⑽) with 1 to 3 self-atoms and 1 to this paper scale on the stupid ring (optionally read the back first Please pay attention to this page and fill out this page) -Order the Mu® A7 __ _B7 __ of the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (6) 3 alkyl groups or 1 to 3 (: 1- (: 4 alkoxy substitution, c 2-C 6 alkenyl, optionally substituted with 1 to 3 dentate atoms or 1 phenyl, c 3-C 6 block, optionally 1 to 3 halogen atoms or 1 Phenyl substitution, extraction group, optionally with 1 or more halogens, Ci_C4 entertainment group, Ci-C ^ alkoxy, phenoxy , CiC * alkylthio group, tri (c 丨-(: 4 alkyl) silane group, C1-C4 alkyl sulfonyl group, Ci-C ^ alkyl sulfone group, CN, > ^ 02 or 0? 3 Group substitution, phenoxy, optionally with 1 or more halogens, Ci-C ^ burned group, Cn-C4 troxygen nose, Ci-C4 entertainment • thio group, tris (C ^ -Cj) group stone Xi-yaki group, (^-匚 doukeng base shiite wind group, Ci-C ^ entertainment group Qi group, CN, N02 or CF3 group substitution, 1-or 2-tea group, 2-, 3-or 4-p ratio Bite group, optionally substituted with halogen, c 1-C 6 alkoxy, optionally substituted with halogen, or C 2 -C 6 alkenyloxy, optionally substituted with halogen;

Rl7 is hydrogen or Ci-C ^ alkyl; R18 is C1-C6 pit group, Cj-Cg halo-hsinyl group, (^-(^ alkyloxy, Ci-C 6 haloalkoxy, phenyl, as the case may be Substituted with halogen, CN, N02, Circ4 alkyl, Ci-G alkoxy or CF 3, > ..: 2-or 3 -ρ-thiophene, or-2-or · 3-squeezyl; 1 η1 介 1 介 1 NR · 27 Q i is C'R22, C-〇R23, C_NR24R25, P- (〇R26) 2, C-NR2gR29 ^ NRl8 〇 8 and 0, -9- This paper size is suitable for China National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling in this cornel)

atl9ΐβ A7

3. Description of the invention (

CN, c 1 C 6 alkyl, optionally substituted with halogen, c N or phenyl, meaning ... phenyl, optionally with 1 to more halogen, C ^ -C ^ alkyl, c yl_, CN, N02 , CF3 or nr33r34 substitution; Αι is Ο or S; Han 22 is c alkyl or phenyl; alkyl; R24 and R25 are each hydrogen, Ci-Cg alkyl, or may be together with the atoms * * Form a 5- to 7-membered ring; C1-C4 entertainment * group; Han 27 is hydrogen, CKC4 pit group or can be formed with R28 or R29-together with the atoms to which they are connected to form a 5_ to 7-membered ring, depending on In case of substitution with 1 or 2 C plants C alkyl ^ ;: »,: R28 and R29 are each hydrogen or alkyl; > ,,: & 3〇 is 01- 匚 4 alkyl group or when R · 27 When together with the atoms to which they are attached, 5- to 7-membered rings can be formed, optionally substituted with 1 or 2 c 〖-c 4 burned groups;

Rn and R32 are each hydrogen, Ci-Cj alkyl or when taken together, may form a ring, where R31R32 is represented by -CH = CH-CH = CH-; Ruler 33 and R34 are each hydrogen or c ^- c # alkyl;

f Please read the notes on the back first and then fill in 'write this page; I

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

311810

Description (8 A7 B7

RR CC 19 is rat or C1-C4 alkyl; 2〇 and R21 are each hydrogen; 1- C 6 alkyl, optionally substituted with halogen, 1 ′ c 6 alkoxy, optionally substituted with halogen ′ c 6 Alkylthio, optionally substituted with halogen, or stupid, optionally halogen, N Ο 2, c N, optionally substituted with halogen, C j-C 4 alkyl, or optionally substituted with pixels C 丨-C 4 alkoxy substitution- R20 and r21 together with the atoms to which they are attached may form a C3-C6 cycloalkynyl group, optionally with Ci-C4 alkyl, C2-C6 alkenyl or phenyl, or R Or Han 21 can form a 4-to 7-member miscellaneous 2 ring with R35 and the atoms to which it is connected (read the notes on the back and then fill in this page> x is 0, 1, 2, 3 or 4 An integer

Q2 is A2R35, p- (OR36) 2, Nr37r38, CR39R4〇, COR, or C 3-c 6 ring system, optionally with 1 or more c 1 -c 6 alkyl groups, c 2-c 6 n-cylene groups, Or stupid substitution 'substitute with halogen, Ν Ο 2, c N, CC 4 pit group', Ci-C4 haloalkyl, C ^ -Cj alkoxy or ^-^ haloalkoxy; -a2 Is 〇 or s (0); hr P is an integer of 0, 1 or 2; R35 is hydrogen, Ci-C6 alkyl, c2-c6 alkenyl, c2-c6 alkynyl; phenyl, optionally halogen, N Ο 2. CN, -11-This paper scale is applicable to the Chinese National Standard (CNS) A4 ^ · (210X297mm): Ordered. Printed by the Ministry of Economy Central Standards Bureau Employee Consumer Cooperatives 311910 A7 B7 V. Invention description (9) ('Ci-c 4 morphology substituted with halogen as appropriate, C i-C 4 alkoxy substituted with halogen as appropriate, C Ο R 4 2, the limiting condition is P is 〇, C Ο R 4 3, the restriction is that P is Ο, (CH2CH20) qR44, or

R35 can form a 4- to 7-membered heterocycle with any of R2Q or R21 and the atoms to which they are attached; A 3 is O or S; R42 and R44 are each C "C6 alkyl, c2-c6 alkenyl , C2-c6 alkynyl, or phenyl, optionally halogen, Ν 2, CN, optionally halogen substituted C 丨 -C 4 burned group, or, optionally halogen substituted C 丨 -C 4 Alkoxy substitution; q is an integer of 1, 2, or 3;: Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) R43 is OR47a〇N48N49; '' R47 is C 1_ 匚 6technical group or. 'Phenyl group, optionally substituted with halogen, Ν Ο 2, CN, optionally substituted with a C 丨 -C 4 gauge > group, or optionally substituted with an i element 丨-C 4 alkoxy substitution; R48 and R49 are respectively 氲 or Ci-Ci pit base; _- 12 -_ This paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Central Bureau of Standards of the Ministry of Economic Affairs Printed by the employee consumer cooperative 311910 A7 B7 -------__ V. Description of the invention (ΊΟ) R45 and R46 are each hydrogen or C / C4 burning groups' or can form a ring when starting from ~~, of which R45R46 Department by -CH = CH-CH = CH-representative; Ruler 36 is C plant (: 4 alkyl; R37 is 氲, Ci-C6 alkyl, c2-c6 alkyl, C2-C6 block, or phenyl, depending on the situation, halogen, Ν Ο 2, CN, C 丨 -C 4 alkyl substituted with halogen as the case may be, or C 丨 -C 4 alkoxy substituted with the _ element as the case may be, or R37 may be connected to any one of ruler 2〇 or ruler The atoms together form a 4 · to 7-_membered heterocycle; R38 is hydrogen, Ci-Cg alkyl, c2-c6 alkenyl, c2-c6 alkynyl, phenyl 'is optionally halogen, Ν Ο 2, CN, Depending on the situation, the C 丨 -C 4 alkyl group substituted by the autogenous element, or optionally substituted by the iCi-C * alkoxy group, Π4

pD, CN, s〇2r51 * cochr52nhr53; A 4 is 0 or S; R50 is OR54, CO2R55, NR56R57, c C 6 alkyl, optionally substituted with halogen, 丨 2_ 匸 6 alkenyl, C 2_ C 6 block or >:,. Phenyl, optionally substituted with halogen, Ν Ο 2, CN, optionally substituted with halogen C 丨 -C 4 alkyl, or optionally substituted with a self-substituted C [-C 4 alkoxy ; R 54 and R 5 5 are each C i-C 6 alkyl, respectively, substituted with a phenyl group, or -13- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ( Please read the precautions on the back before filling in this education) Clothing · Order A7 311910 B7 V. Description of the invention (11) Phenyl, with halogen, N 0 2, CN, and D, which is replaced with dentin as the case may be C 丨 -C 4 alkyl, or optionally substituted with pixel-substituted C 丨 -C 4 alkyloxy; R 5 6 and R 5 7 are respectively nitrogen or alkyl, R51 is NR58R59, Ci-C ^ alkyl, c2-c6 Alkenyl, c2-c6 monoblock, or phenyl, optionally halogen-based Ν Ο 2, CN 'optionally halogen-substituted C i-C 4 burned group, or may be substituted with dentin C i-C 4 alkoxy substitution; R 5 8 and R 5 9 are respectively star 1 or C] __ C4 pit group; R52 is hydrogen, Ci-C4 burned group, and optionally substituted by radical, sr60, conh2, nh2,. NHC (= NH) NH2, C02H, phenyl, depending on The case is substituted with hydroxy, 3-丨 p Duo group or 4-Mi Jun group; R > 60 is gas or burning • group, 8 14:

II Ruler 53 is CR61; > 1 R (5 1 is C i-C 6 burned group, optionally substituted with halogen,-

Ci-C ^ alkoxyalkyl group, Ci-Cs alkylthio group, 'phenyl group, optionally halogen, Ν Ο 2, CN, optionally substituted with southern element of C 丨 -C 4 burning group, or optionally Pixel substituted C!-C 4 alkoxy substituted, __- 14 -_ This paper size applies to China National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page) . A7 B7 311910 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (12) OR54, C02R55 or NR56R57; Ruler 39 and R40 are each hydrogen 'C 丨 -c 6 burned groups, and halogen substituted as appropriate 'c J-C 6 alkoxy, optionally substituted with halogen' C 1-C 6 thiothio '' optionally substituted with halogen 'stupid group, optionally halogen, CN, N 0 2, optionally substituted with halogen C 1-C 4 burned group, or-optionally substituted with halogen substituted with halogen-pentyl alkoxy group 'or when Ruler 39 and R4〇 together with the atoms to which they are attached' may form a C3_C6 ring Hyun * ring ' Depending on the situation, C 1 _ C 4 alkyl group, C 2 -C 6 dilute group or private group substitution Κ · 41 is 〇Κ · 62, NR58R59, C1-C4 alkyl group or phenyl group, as the case may be Halogen, c Ν, Ν Ο 2. C 1-C 4 plate bases optionally substituted with autogenous elements or ci-c 4 alkoxy groups substituted with halogens as appropriate; R 6 2 is C i-C 4 • radical or phenyl, optionally halogen, C Ν, Ν Ο 2, optionally substituted by halogen C i-c 4 alkyl, or; optionally substituted by iS element C 丨 -c 4 alkoxy :. ; The term 鍣 1 素 used within the scope of this specification and patent application means chlorine, fluorine, bromine or iodine. The term haloalkyl means alkyl c nH 2n + i, which contains from 1 i atom to 2n + 1 halogen atoms, wherein the halogen atoms may be the same or different. It is expected that A may be any group capable of being enzymatically or hydrolytically cleaved and γ, z and R may be any combination of 2 to 6 electron withdrawing groups, which is also lipophilic. Suitable electronic withdrawal bases include halogen, nitro, cyano, and trifluoromethyl sulfonyl _: __-15- This paper size is applicable to China National Stack Standard (CNS) A4 specification (210X297 meal) (please read first (Notes on the back and then fill out this page) Clothing, ιτ Du consumption printed by the Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation

8U9P A7 B7 Fifth, the description of the invention (13)., ·, Trifluoroethyl and its analogs. The preferred compounds of the present invention are those of formula I, wherein γ and Z are each hydrogen, halogen, CN, N02, Cl-C6 haloalkyl or CrC6 haloalkoxy, and the limiting condition is only γ or One of Z is hydrogen; ^ is 3 or 4 and η is 1 or 2. Also preferred are those compounds, wherein γ is hydrogen, CN, N0 2, S (〇) nRi, haloalkyl or 匸! -^ Halogenoxy or Cj-Cg haloalkyl and Z are phenyl, optionally substituted with L, M and Q. A more preferred compound is the compound of formula I, wherein γ is CN, Ci-C 6 functional group or S 0 2 R 1 and B is Ci-Cg from Fe group, S 0 2 R 1 or phenyl group , Replace with L, M, Q as appropriate. The compound of formula I, wherein Υ or 2 is (: 1-(: 6 haloalkyl, can be prepared by literature procedures, as described by Y. Kobayashi et al. In Organic Chemistry Monthly, 1836 (1974), or by The appropriate halogen precursor of formula 11 (where halogen is I) is reacted with C i-C 6 from an alkyl carboxylate or ester and a copper (I) halide, as shown in Scheme I, where Ci-C is halogen The alkyl carboxylate is sodium trifluoroacetate. "Flowchart I; Please read the notes on the back before filling this page." Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

R

Cul

N i A (II) CF3C〇2Na _I 4

NIA CF, the compound of formula I, where Y or Z is CN, can be prepared from the above-mentioned halo-16- This paper is under-applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Μ Β7 14) < The base intermediate is reacted with chloroisocyanate (CSI) in the presence of acetonitrile and dimethylformamide (DMF), as shown in Scheme 11. Flowchart 11

CSI

R • CF,

R

• CN

N I A

CH3CN DMF

I CF, A (Please read the precautions on the back before filling in this page) The compound of formula I, where Z is S (0) nRz, can be derived from the appropriate subsulfide precursor of formula III and the appropriate autogenization Extend the burning group such as gas trifluoroethylene, react in the presence of base to prepare the product of formula I, where η is 0. This haloalkylthio compound can then be oxidized in a general manner to produce Qi and Yabin analogs, as shown in Figure 111. Flowchart 111 Printed by the Employee Consumer Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs

: CFC1

R

R

I I base [〇]

R • S0oCF, CHFCl

-I -SCFXHFC1. N 'Η [〇] ν -S0CFXHFC1 The standard of paper music is applicable to China National Standard (CNS) A4 specification (210 X 29? Mm) -17- A7 B7 V. Description of invention (15 alternatives ^ The compound of the formula, wherein ¥ or 2 is s (〇㈣ " can be prepared by reacting the appropriate one with wood halide sulfoxide gas, and oxidizing haloalkylthio β-dole as shown above. Reaction series It is shown in the flowchart ...

Flowchart I V R.

RiSCl

Rm—- I 4 SR, [0] N I A [0]

SO R

Rm— I 4

SOR m. HI I- I HI I j----1 ″ Λ5 " ----- I --..., I-- ------------- I!- * «. I is the T mouth (please read the notes on the back before filling this page) The compound of formula I printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, where z is w, can be replaced by an appropriate base aryl hydrazone, Hydrazine and polyphosphoric acid (ppa) are cyclized for life. For example, in the case of phenyl, the glandular system of formula IV is cyclized or substituted for phenyl as shown in flow chart v. (CNS) A4 specification (210 X 297mm)

V. Description of the invention (16)

Flowchart V

-A compound of formula I, where A is not hydrogen, can be prepared by reacting NH indole precursor with a suitable i-brother or carbonyl halide in the presence of a base to obtain the product of formula I, as shown in Scheme VI . Flowchart VI

Y (please read the precautions on the back before filling in this page) Ai _ order R-

+ A-X domain N Η

(I) The -19-type ί product printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy, in which Υ or Z or R is halogen or Ν 0; can be obtained from standard halogenation and nitrification procedures known in the art. These and other methods for preparing the substituted throat derivatives of formula I will be changed from the examples described below to the bismuths. The substituted indoles of formula I and their N-substituted derivatives are effective in controlling insects and grasshoppers Pests and plants and crops that protect growing and harvesting are protected from attack and rampage by these pests. This paper scale is applicable to the Chinese National Standard (CNS) Μ specifications (21 〇 297 mm 31191 ° A7 B7 V. Description of the invention (17) In actual agricultural implementation, the compound of formula I is usually about 10ppm to 10,000 ppm, car Jiajiadi about 100 to 5,000 ppm is dispersed in the liquid body, when applied to the plant or the soil or water in which it grows, it is effective to protect the plant from attack and run by insects and snails. Applications, such as spray applications, are usually provided at a ratio of about 0.125 kg / ha to about 250 kg / ha, preferably about 10 kg / ha to 100 kg / ha of active ingredient Effective. Of course, it is expected that the higher or lower ratios of the substituted 4-indole derivatives may be based on prevailing environmental conditions such as ethnic density, rung, plant growth stage, soil conditions, climatic conditions and the like Advantageously, the compound of formula I can be used in combination with other biological and chemical control agents including other insecticides, nematicides, acaricides, molluscicides, fungicides and-fungicides such as nuclear hyperhidrosis virus, Eluo, aryl p than p each _Combined or combined use of acetoyl urea, pyrethroids, carbamates, phosphates and their analogues Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs m ^ l fm — ^ ϋ \ V * , Τ (Please read the precautions on the back before filling in this page) Formula I Mpod derivatives are suitable for typical formulations are granular compositions, flowable compositions, wetting agents, dust agents, microemulsions, Emulsified concentrates and their analogues. All compositions that can be used for soil, water and leaf application and provide effective plant protection are suitable. The composition k of the present invention includes the substituted pyridine derivative of formula I and inert solid Or a mixture of liquid body. When the composition of the present invention is administered in combination with other biological or chemical agents, the composition can be administered as a mixture of ingredients or can be administered in a series. When not required, it includes the compound of formula I and The combined composition of pesticides can also include other ingredients, such as fertilizers, inert formulation additives. For example, surfactants _-20-_ this paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm)

5. Description of the invention (π), etiquette, defoamer, dye, mixture and the like. In order to understand the present invention more clearly, its specific embodiments are described below. The invention described in and described in the scope of patent application does not limit the scope of these single illustrative embodiments. In fact, in addition to those exemplified and explained here, the different modifications of the present invention will make it clear to those skilled in the art from the following examples and prior explanations. Such modifications are also intended to fall within the scope of the accompanying patent application. 1Η, 13 c, and 1 9F N M R represent proton, carbon, and fluorine nuclear sulfur resonance spectroscopy, respectively. Ir means infrared spectroscopy and Gc knows TLC means gas chromatography and thin layer chromatography, respectively. -ί ^ η_ι_ methyl) indole preparation • > ^ 1— (please read the precautions on the back before filling this page)

,? Τ The Ministry of Economic Affairs, Central Standard Falcon Bureau Employee Consumer Cooperative printed a winter solution of 2.5 mol of n-butyl lithium in hexane (8.8 mL, 22 mmol) at room temperature, under N2, with N, N, N ,,, N, -raT * b ': ··· :: diamine (TMEDA) (3.3 ml, 22 mol) treatment, stirring at' Tang temperature # 〇 · 5 hours, with N-three Treatment with methylsilyl-0-toluidine (1.79 g, 10 comole), heating at reflux temperature for 6 hours, cooling to -7 8 ° C, using ethyl trifluoroacetate (1.4 ml, 12 mmol) Ear) treatment, stirring at -78 ° C for 0.2 5 hours, warmed to room temperature, diluted with water and extracted with ether. The combined extract is continuously washed with 1 equivalent concentration of HC 1 and saturated Na HC Ο 3, at -21-this paper scale is applicable to the Chinese National Standard Falcon (CNS) A4g (210X297mm) A7 B7 V. Description of the invention (19 ) Dehydrated in M g S 0 4 and concentrated under empty space to obtain residue. The residue was silica gel and 4: 1 hexane: ethyl acetate as the eluent. Chromatography gave the title product as a light yellow solid, mp 104. -106 ° C (document mp lOlt1), 0.81 g (47% yield), further identified by 1 foot, 1 «^ \ 111 and 19?> ^ 1 ^ 11 analysis.

Kobayashi, I. Kumadaki, Y. Hirose, and Y. Hanazawa, organic 4 d school month f'J, ^ _, 1836 (1974). Example 2 Preparation of Ndimethyl-2-(trifluoromethyl) indole f Please read the precautions on the back before filling this page) -Cloth ·

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 1-Methyl-2-iodine 5 indole (4.40 g, 17.3 mmol), sodium trifluoroacetate (24,0 g, 176.5 mmol) ) And copper iodide (1) (17.1 grams, 89.8 millimoles) in a mixture of N-methylpyrrolidone heated at 160X for 6 hours; " cooled to room temperature, diluted with water and self-crushing diatomaceous earth After removing ginger copper salt. .Tears are extracted with ether. The extracts were combined, washed with water, dehydrated in Mgs04 and concentrated in the air to obtain a residue. The residue used silica gel and 4: Shuji ^: ethyl acetate as the eluent, chromatography to obtain the title product as a pale yellow oil, which crystallized on standing '119 g (37% yield)' mp 28-32 ° C, identified by IR, hNMR and 19FNMR analysis. -22- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 5. Description of the invention (2〇) Example 3 Preparation of 5-gas-2 -iodo-1 -methyl ⑼indole

5-Gas-1-methylpyridine (10.0 g, 60.4 mmol) and n-butyllithium (29 mL of 2.5 mol solution in hexane, 72.5 mmol) in ether The solution was heated at reflux temperature for 3 hours, cooled to 0 ° C, treated with iodine (18.4 g, 72.5 mmol), stirred for 1 hour at 0 ° C, warmed to room temperature, stirred for 1 hour Salt treatment. After the liquid layer was separated, the organic layer was dehydrated in MgS0 4 and concentrated under empty space to obtain the title product as brown oil, which solidified on standing, 16.5 g (93.7% yield). The title product is used in Example 4. Example 4, Preparation of 5-Gas-1-methyl-2- (trifluoromethyl) indole ^^^ 1 mV — ^ n ml ^^^^ 1 ^^^^ 1 n ^ i ^^^ ^ 1 \ J,, I, Fang, v 'mouth (please read the notes on the back before filling out this page) Printed by Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs

I a N rg 〇 c 3 F c +

3 FC _: _- 23.- This paper wave scale is applicable to the Chinese National Standard (CNS) A4 specification (2 ~ 0 '2929? Each centimeter) Α7 Β7 V. Description of the invention (21 5 gas obtained from Example 3- 2-Iodine · 1-methyl indigo (i 6 5 g, 56.6 mmol), sodium trifluoroacetate (76.2 g, 56.0 mmol) and copper iodide (1) (10.6 g, 56.0 mmol) ) The mixture of n-methylpyrrolidone is heated at 16X: for about 8 hours, cooled to room temperature, diluted with water and filtered from diatomaceous earth. The filtrate is extracted with ether. The extracts are combined and washed with water , Dehydrated in MgS〇4 and concentrated under a narrow space to obtain a black oil residue. ^ Every use silica gel and 15: 1 hexane: ethyl acetate chromatography to obtain a yellow oil. The oil was rechromatographed using the same eluent and silica gel The second time, the title product was obtained as a yellow oil, 2.92 g (22% total yield from 5-gas-1-methylindole), which was identified by analysis of [r, WNMR, 13CNMR and 19FNMR. Examples 5 (Please read the precautions on the back before filling in the main text). Preparation of Ya • 3_Daiji-1_methyl_2_ (trifluoromethyl) g nozzle

Du Printing Co., Ltd. of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People ’s Republic of China Co., Ltd. Cooled a solution of 5-gas-1-methyl-2- (trifluoromethyl) indole (1 丨? 9 g., 77 mmol) in acetonitrile to 0X :, treated with gas-based isocyanate (CS1) (10 mL 11.5 mmol), stirred until the starting pyridine cannot be observed by thin layer chromatography, with 5¾ liter of dimethylformamide (DMF) Dispose, mix for $ 0 hours and dilute with ether and water. Separate the liquid layer. The organic layer was washed with water, dehydrated in Ma 2 SO 4 and concentrated under empty space. The generated residue uses silicone nn

Α7 Α7 Printed B7 by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (22) 4: 1 Hexane: ethyl acetate is used as the eluent chromatography to obtain the title product as a white solid, 0.99 g (49.7% yield) ), Mp 166. -167.5 ° C, identified by IR, iHNMR '13CNMR, 19FNMR and mass spectrometry analysis. Example 6 6-Preparation of gas < indole OCH ^ nmi

4-Gas-2-nitrotoluene (34 g, 0.2 mol), dimethylformamide dimethyl dimethyl (28 ml, 0.2 mol) and pylol (25 ml, 0.3 (Mole) in a mixture of dimethyl formamide (DMF) was heated at 100 ° C for 72 hours, cooled to room temperature and concentrated under empty space to obtain a dark red diurnal. Dianna is dissolved in methanol / tetrahydrofuran (1: 1), treated with about 2 ml of Raney nickel slurry and deuterated under normal pressure. The reaction was monitored by G C, T L C and H 2 uptake. After 2 hours, the hydrogenation was continued at 20 psi-40 psi to 24 hours of total hydrogenated pheasant. The resulting reaction mixture was filtered from crushed soil. ; ^ Cake with 1 Rustic nail: Wash and the combined filtrate is successively washed with 1 equivalent concentration of H C 1 and saturated Na H C O 3 ′, dehydrated in M g S Ο 4 and concentrated under empty space to obtain brown oil residue. The residue was crystallized from hexane to obtain the title product as a brown solid, 22 g (72.6% yield), which was identified by IR, 1HNMR, 13CNMR and mass spectrometry analysis. • ___- 25-, this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ^^^ 1 ^^^ 1 n ^ — — ^ n ί ί ί — ^ 1 n mu I., < " i (Please read the notes on the back before filling this page)

A7 B7 V. Description of the invention (23) Example 7 Preparation of 6-gas-1-methylpyridine

A mixture of 6-gas indole (22.0 g, 0.145 mol) and potassium tributoxide (Κ Ο t-B u) (2 0.0 g, 0 _ 1 7 9 mol in tetrahydrofuran at room temperature to Methyl iodide (1 1.2 ml, 0.17 mol) was treated in a stepwise manner, allowed to stir at room temperature for about 1 hour and diluted with a mixture of petroleum ether and water. Separate the liquid layers. The organic layer is divided into 1 Equivalent concentration HC 1 and water were washed, dehydrated in Ma 2 S Ο 4 and concentrated to a brown oil '. After chromatography (silica gel / 4: 1 hexane: ethyl acetate), the oil was obtained as a colorless after steaming The title product of oil, 16.25 g (67% yield), bp 1 1 0 °-1 15 ° C / 4 mmHg, identified by IR, 1 H NMR, 13 C NMR, mass spectrometry and microanalysis., Example 8; ... ·: Preparation of 6-gas-2 -iodo-1 -methyl 4-indole '"'

-26- This paper scale applies the Chinese National Standard (CNS) Α4 specification (210X 297 gong) ^^ 1 ^^^ 1----1 — ^ ϋ am-HI In mn · 11 n-VI · {^ Ί (Please read the precautions on the back before filling out this page) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7 5. Description of the invention (24) The 6-gas-1-methyl 4 bumu (0.83g ' 5.0 mmol) solution in ether with 1.7 mol concentration of the second butyl bell in hexane (35 ml, 6.0 mmol) at 0 ° C, stirred at room temperature for 0.25 hours, to 2 (1 52 g, 6.0 mmol) treatment 'was stirred at room temperature until the reaction was completed by tlc analysis, treated with aqueous sodium sulfite and extracted with ether. The combined ether extracts were dehydrated in M g S Ο * and concentrated in vacuo to obtain the title product as a brown solid, 1.52 g (containing ether). The product is used in Example 9. Example 9 Preparation of m-methyl-2-((trifluoromethyl) indole -------- ^ ---- "1. Policy-- (Please read the precautions on the back and fill in this booklet )

CF ^ CO.Na

Cul

Cl NI CH- The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printing -27- will be obtained in Example 8 6-gas-2-iodine-1-methyl < indole (1.5 g (9 6 , · 7% purity), 5.0 millimoles), sodium trifluoroacetate (6.8 g, 50 engine moles) and copper iodide (I) (0.9 5 g, 5.0 millimoles> in N- The mixture of methylpyrrolidone was heated at about 160 ° C for 2 hours and at i9.0 ° 'for 1 hour, cooled to room temperature, diluted with water and filtered from diatomaceous earth. The filtrate was extracted with ether. Combined The extract was washed with water, dehydrated in M g S Ο 4 and concentrated under empty space to obtain a residue. The residue was chromatographed (silica gel 4: 1 hexane: ethyl acetate) to obtain the title product as a yellow crystalline solid, 0.5 1 G (46% yield) 'mp 75 ° -78 ° C, by IR, hNMR, 13CNMR, 19FNMR, quality paper standards apply China National Standards (CNS) A4 specifications. (2 丨 0X297 public daughter) 311θ1〇A7 * B7 5. Description of the invention (25) Spectral and micro-analysis identification Example 1 0 Preparation of 6-gas-1-methyl-2- (trifluoromethyl) indole-3-carbonylnitrile

Using essentially the same procedure as described in Example 5, after chromatography, the title compound was obtained as a white solid in 8 0.4% yield, mp 1 4 2 · 5 °-145 T, by IR, iHNMR, 13CNMR, 19FNMR And identification by mass spectrometry. Example 1 Preparation of 6-chloro-1- (ethoxymethyl) -2- (trifluoromethyl) pyridine-3-carbonylnitrile 1) S〇2C12->

2) Na, C2H5〇H

Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs_

^^^ 1 ^^^^ 1 n ^ i ^ i ^ i— One I, I 1 I is the T port (please read the precautions on the back before filling in this page). 6-chloro-3-cyano-1 -Methyl- 2- (trifluoromethyl) indole (1.08 g, 4.2 mmol) and thiophene gas (0.68 mL, 8.4 mmol) are heated at reflux temperature in a mixture of four gases 8 hours, cool to room temperature and under the air. _-28- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 81191 ° A7 5. Description of invention (26) The shrinkage is 1 8 hours, Remove all volatiles. The residue was dissolved in ethanol and treated with a solution of sodium metal (0.38 g, i6 mmol) in ethanol, stirred at room temperature for 0 ‘5 hours and diluted with ether. The diluted reaction mixture was washed with water, dehydrated in Ma2S04 and concentrated under empty space to obtain a residue. The residue was chromatographed (silica gel / 4: 1 hexane. Ethyl acetate) to give the title product as a white solid, 0.66 g (52% yield), 1111) 83. -86.0: 'Identified by 111, 1 ^, 13CNMR, 19FNMR and mass spectrometry analysis. Example 1 2 Preparation of gas-3 -nitro-1 dimethyl-2 (trifluoromethyl) indole (please read the precautions on the back before filling this page) ί ^ Γ Cl Ν CF I ur3 CH ,

Cu (N〇3) 2

Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, 6-gas-1-.methyl-2- (trifluoromethyl) 4-pio (ι · l6 g, 5.0 mmol) in acetic anhydride solution Treated with Cu (N03) 2.3H2O (1.20 g, 5.0 halomol), at 0. Stir for 3 hours at -25 ° C and mix with water and ether. The machine layer was washed with water and saturated MaHC03. In M, a2S 04, k water and concentrated under empty space to obtain residue. The residue was chromatographed (silica gel / 4: 1. hexane: ethyl acetate) to give the title product as white leaflets, 0.87 g (62.41% yield), mpl57. -159 · 9 ° C, identified by I_R, 1HNMR, 13 C N M R, 1 9 F N M R and mass spectrometry analysis. -29- This paper scale is applicable to the Chinese National Standard (CNS) Α4 · Cash (210X297). 5. Description of the invention (27 Example 1 A7 B7 5 -Bromo-2-(trifluoromethyl) 4indole-3- Preparation of carbonyl nitrile

CN A. + Br9 N ~ CF 2 Η. -ΧλΙ Μ

CN • CF, place 3-cyano-2- (trifluoromethyl) pyridine (1.05 g, 5_0 mmol) in acetic acid solution with Br 2 (0.6 mL, 6.0 mmol) in Work at room temperature and stir until the reaction is complete by TLC analysis. The reaction mixture was carried out as described in Example 22, and after chromatography (silica gel and 4: 1 hexane: ethyl acetate) and crystallization, the title product was obtained as a white solid, 0.95 g (6 5 % Yield) mp 188 ° -191.5 ° C, identified by IR, iHNMR, 19FNMR and mass spectrometry analysis. Example 1 Preparation of 4, 5,6- and 6,7-digas-3 -cyano-1-methyl-2- (trifluoromethyl) pyridone II ln ^ i — —λ ^ ϋ nn nn tn ml m 1 I \ I '(Please read the precautions on the back before filling out this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ·

The 6-gas-3-cyano-2- (trifluoromethyl) indole (0.51 g, 2.0 mmol) paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -30-, A7 B7 V. Description of the invention (28) Ear) A suspension of 2 ml of H 2 S 0 4 and 6 ml of water is treated with acetic acid to achieve dissociation; the solution is in increments of Na〇Cl (2.8 ml, 2.0 mmol) Treat with H2S04 until the reaction is complete (4 parts total, 8.0 millimoles Na0C1). The resulting reaction mixture was poured into water and extracted with acetic acid. The organic layer was washed with NaHCO 3 until neutralized, dehydrated in MgSO 4 and concentrated under empty space to obtain a residue of the title product mixture. The mixture was separated by column chromatography (silica gel / 4: 1 hexane: ethyl acetate) to obtain: .-_ heart 5,6-digas-3-cyano-1-methyl-2- (trifluoromethyl Base) Meow voice, white. Solid, 0.077g (13% yield), 11 ^ 175. -18〇. (:, Identified by 1 foot, 1H NMR, 1 9 FNMR and mass spectrometry analysis, and 6,7-digas-3-cyano-1-methyl-2- (trifluoromethyl) 4-indole, white solid, 0.082 g (14% yield) 'mp 220. 223 ° C, identified by IR, hNMR, 19FNMR and mass spectrometry analysis. Example 1 5 dichloro-2- (trifluoromethyl) β pd and 5,6- II _ λ arginyl trifluoromethyl) Preparation of meow voice (please read the notes on the back before filling in this page) Printed by the Ministry of Economic Affairs, Central Cooperative Bureau, Consumer Cooperative Printed

Mix 4,5-digas-2-nitro-y5-trifluoromethyl styrene (55 g, 19.2 mmol) and triethyl phosphite (26 mL, 153 mmol) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs · A7 ----_ V. Description of the invention (29) — 'The liquid is heated at 160 ° C for 4.5 hours (monitored by GC, TLC and NMR) and cooled to room temperature Warm, concentrated under the sky to get residue. The residue was taken up in ether, washed successively with water and brine, dehydrated in MgS 〇4 and concentrated under empty space to obtain the title product mixture. The mixture was chromatographically separated (silica gel / ^ 〇: hexane: ethyl acetate) to give: 5,6 digas-2- (trifluoromethyl) indole, colorless leaflets, 0.82 g (17% yield) ), Mp 96. A 98Ό, * IR, 1HNMR '13CNMr and mass spectrometry analysis Zhong Ding, and once _-5,6-dichloro-1-ethoxy_2_ (trifluoromethyl) pyridine, yellow solid, 1.19 g (20.7 % Yield), 11 ^ 71. -73 5. (:, Identified by analysis of 1Han, 1H NMR, 1 9F NMR and mass spectrometry. Example 16 Color: 7. Digas-1- (ethoxymethan ~ 2-(Sanyu methyl) 丨 indole_ 3 _Carbononitrile preparation

Using the same procedure substantially described in Example 11, after chromatography (Shixi gum / 41 hexane: ethyl acetate), the title product was obtained in a yield of 44 〇 / 〇 as a white solid. 127C, identified by ir, Ihnmr, 19FNMR and mass spectrometry analysis. '-32- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210X297mm) f Please read the precautions on the back and then fill out this page JI Yi-order S11910 A7 5. Description of the invention (30) Width_Example 1 7 h6 -dichloro-2- (trifluoromethyl Shun-3-jin jg

. The flicking is substantially the same as the bed described in Example 5. ". ^ 7, after the prayer (dura / 8- :. 丨 hexane: ethyl acetate), 19.6% yield can be obtained as white The title product of the solid, mp> 260 ° C, was identified by IR, iHNMR, 19FNMR and rod spectrum analysis. Shell Example 1 8 Preparation of 5-nitro-2- (trifluoromethyl) Μ Buduo ^; one pack I. f Please read the notes on the back before filling this page j Η 'CF. 02N Cu (N〇3) 2 · 3H2〇

Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs; printed by the Industrial and Consumer Cooperatives. 2- (difluoromethyl)》 5 丨 throat (0.2 g '1.1¾ mol) in 11 hepatic acetate solution to 0.131 g (0.54 mmol) ) Cu (N03) 2 · 3H2〇 at (TC. 下 4 理 'at room temperature for 2 and 5 hours and diluted with water and ether. Separate the liquid layer: the organic layer was continuously washed with saturated NaHC〇3 and brine, After dehydration in MgS〇4 * and concentration under a void, a yellow solid residue was obtained. After extensive analysis (Shi Xijiao / 20% ethyl acetate in hexane), the title product was obtained as a yellow solid, -33- this paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male Fen) 31191 ° A7 B7 V. Description of the invention (31 0.073 g (29.4% yield), mpi90 ° -93 ° C, identified by IR, iHNMR, 19FNMR and mass spectrometry analysis Example 1 95 -Nitro_ 2-(trimethyl) 丨 indole and 3 · cyano_ 6 _nitro_ 2 _ (trifluoromethyl) 4 indo-3 -carbonitrile

Co

CN

〇, N

CN

Cu (n〇3) 2

N CF, 0oN

A § The Ministry of Economic Affairs, Central Bureau of Standards, Employees Consumer Cooperatives printed and used the same procedure as described in Example 18 and replaced it with 3-cyano-2- (trifluoromethyl) indole as the substrate. The title product mixture. The mixture was chromatographically separated (silica gel / 20% ethyl acetate in hexane) and recrystallized from ethyl acetate / hexane to obtain: 3-cyano-5-nitro-2- (trifluoromethyl) Indole, yellow-brown crystals, 41% yield, mp> 260. C, identified by IR, 1HNMR, 19FNMR and y spectrum analysis, and :; §_ · 3 -cyano-6 -nitro-2 _ (trifluoromethyl) indole 1, yellow solid color ', 6% Yield, mp> 230. C, determined by IR, 1HNMR, 19FNMR and-mass sulfon analysis. Example 2 Preparation of 0 2-(Trifluoromethyl X-dole-34- il ^^ in ^ i —fl ^ i BR ^^ im · ^ im HB— m BUI 1 _ 1. τ (Please read the back Please fill in this page for more details.) The standard of common national standard (CNS) M specifications (M7 male thin) 311910 A7 B7 V. Description of invention (32

0, N Ο, Ν

Cu (Ν〇3) 'CF,

Using substantially the same procedure as described in Example 18 and long-time substitution of 5- (2-fluoro (trifluoromethyl) indole with substrates, 16.7% Θ, can be obtained. Degree I (90% pure)-, as the title product as a yellow solid, mp 225 ° -228. (:, 1 BN M R, 1 9F N M R and mass spectrometry analysis and identification. Example 2 1! _, 6-and 5, 7-dinitro-2-(tris | methyl) ketole-3 outfit #

By IR ---;-. I ---- 一 蓈 丨 (Please read the notes on the back before filling this page)

CN Ο, Ν ΗΝΟ 3 N 、 CF +, Η-

CN Ο Μ

Ν CF, -The economy, which is printed by the Central Standards Bureau employee consumer cooperative, will be 3-cyano-5-nitro-2- (trifluoromethyl) pyridine (〇23g, 〇09〇mmol) A mixture of 7 ml of fuming nitric acid (90%) was stirred under nitrogen at 0. 5 hours under nitrogen and 19 hours at room temperature, poured into water and extracted with ethyl acetate. The combined extracts were washed successively with saturated Na H C O 3 and salt, and dehydrated in M g S O 4 and concentrated under empty space to obtain a brown solid residue. After chromatography and crystallization, the title product mixture was obtained as a yellow solid, '0.104 g (3.7% yield), mp> 230. C, determined by IR, 1HNMR and 19FNMR analysis. 35- Table paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm) 31191 ° V. Description of invention (33) A7 B7 Repeat Example 2 2 1 ·! · Oxy-2- (three Preparation of fluoromethyl) indole CH, 〇

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, tetramethylethylenediamine (TMEDA) (49 g '0.42 mol) and n-butyl lithium (168 ml 2.57 equivalent concentration in hexane, 042 mol) under nitrogen Treated at .0 ° C, stirred at room temperature for 0.5 hours, dropwise with N- (trimethylmonolyl) -4-methoxy-O-aniline (40.0 g, 0.19 mol) Treated, heated at reflux temperature for 4 hours, cooled to -78 ° C, diluted with anhydrous cyclohexane, and treated with ethyl trifluoroacetate (45g, 0.23mol) dropwise at -78. 〇 Next 0. 5 hours, warmed to room temperature and quenched with saturated NH 4 C 1 solution. The mixture was extracted with ether. The combined extracts were successively washed with saturated N H 4 C 1 and brine, dehydrated in Na 2 S Ο 4 and concentrated under empty space to obtain a brown oil residue. The oil was chromatographed (silica gel / 10% ethyl acetate in hexane) to give the title product as white needle winter, 5.0 g (12% yield), mp 6 0 ° C (after re-liquor from pentane) , Identified by IR, iHNMR, 13CNMR, 19F> lMR and mass spectrometry. .; Example 2 Preparation of 3 3 -cyano-5-methoxy-2- (trifluoromethyl) indole 36- This paper is applicable to China National Standard (CNS) A4 specification (210X297mm) (please Read the precautions on the back before filling in this page) 蠮. Order 5 311910 A7 B7 'Invention Description (34 CH, 0 • CF ch3cn, dhf C1S02NC0 CH3〇 \ v ^ r.

Place a solution of 5-methoxy-2- (trifluoromethyl) pyridine (3.0 g, 13-0 mmol) in acetonitrile with a gaseous isocyanate (2.02 g ′ 14.3 mmol) at 0 ° C. It was treated dropwise, stirred at room temperature for 2.5 hours, treated with dimethylformamide (CIMF) (2.1 g, 28.6 mmol), stirred at room temperature for 0,75 hours and poured into water. The resulting mixture was extracted with ether. The combined extracts were successively washed with water and brine, dehydrated in MgS04 and concentrated under empty space to obtain brown oil residue. The oil was crystallized from diethyl ether / hexane to give the title product as crystals which were colored, 0.78 g (25% yield), m p 189. -1 9 〇 X: 'Identified by IR, 1HNMR, 13CNMR and 19FNMR. Example 2 42-Preparation of (2 -Krypton-I 1,2-trifluoroethyl) thio 1 indole (please read the precautions on the back before filling this page) Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs .

K2C〇3 s CF2 = CFC1

SCF.CHFCl know 5,6-_ gas extension 4 ^ -2-thiodi (3_71 g, 17'〇 millimoles) and wear. Potassium acid (2.35 g, 17.0 millimoles) in a mixture of isopropyl alcohol Put in a pressure tube, with gas trifluoroethylene (2 · 18 grams, 18.7 millimoles). Handle, seal and 37- This paper scale is applicable to China National Standard (CNS) A4 specifications (210X297 mm) 311910 A7 B7 5. Description of the invention (35) Stir at room temperature for 16 hours. After breaking the seal, the reaction mixture was concentrated under empty space, diluted with ethyl acetate, washed successively with water and brine, dehydrated in MgS Ο 4 and concentrated again under empty space to obtain a dark residue. Flash column chromatography (silica gel / 1: 10 ethyl acetate title product, 3.4 g (56% yield), iHNMR and 19F NMR analysis and identification. Example 2 5 2 7. Substituted 2-thiocarbamate Preparation of compounds

Hexane) to obtain a mixed white solid mp 54 ° -60 ° C, from IR.R one

R

IIS — R, ^ ^ One binding (please read the precautions on the back before filling in this page) Use the same procedure as described in Example 2 4 and replace it with the appropriate 4 throat-2 -thione The following compounds in Table I are available for quality and desired properties. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -38- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public daughter) 311910 V. Description of invention (36) A7 B7

Table I

S — R number of examples 1m 1χ% production mp ° C 25 Η ch2 chf2 33 oil 26 Η CH2 CHFC1 54 oil 27 5-Br CH2 CHFC1 49 oil Example 2 8 ill (2-lL- U__l, 2 trifluoroethane ) Preparation of sulfur 1-pyridin-3-carbonyl nitrile j

CN I I I. I. I---^^ 1 · 11 I ^^ 1-Yi Qin J5 (please read the precautions on the back before filling in this page) ^^ \ n ^^ SCF0CHFC1 Η

CSI

SCF.CHFC1 The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printed. Will 2-[(2 _ gas-ii, 2 _ trifluoroethyl) sulfur] pyridine '(〇 · 6 4 g, 2 4 _ Mohr ) A solution of acetonitrile with gaseous isocyanate i: CS 1 y (0.85 g ·, 6 · 0.0 mmol) in acetonitrile solution at ice bath temperature, stirring at room temperature for 3 hours' Take dimethylformamide (〇88g, a millimolar) at 0. The next treatment is to stir at 4 / m for 1 hour, pour into ice water and extract with ethyl acetate. The combined extracts were washed with brine, dehydrated in Mg'sc > 4 and concentrated under 眞 i to obtain a residue. Flash chromatography (silicone / i: 4 ethyl acetate: hexane

a 7 B7 V. Description of the invention (37 entertainment) The title product was obtained as a white solid, 0.44 g (63% yield), m p 134 °-136 ° C, identified by IR, hNMR and 13CNMR. Example 2 9 Preparation of gas-1,1,2-trifluoroethyl) thio-1-pyridine-3-carbonylnitrile

Br

Br

CN 'SCF., CHFC1 CSI, DMF ch3cn' SCF.CHFCl (please read the precautions on the back before filling this page).

Using essentially the same procedure as described in Example 28 but applying 5-bromo-2 [(2 -chloro-1,1,2-trifluoroethyl) sulfur] 4, it can be obtained as a white solid The title product, mp 187. -192. (:, Identified by IR, WNMR and 13CNMR. Example 3 0 Preparation of 2- (trifluoromethyl) _3- 丨 (trifluoromethyl) thio 1 pyridine

I I cf3sci Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs N CF Η

Op SCF. N CF. ^ H '· A mixture of 2- (trifluoromethyl) pyridine (1.85 g, 0.01 mol) and 3 drops of trifluoromethanesulfonic acid in difluoroethane at 65 ° C Heat for 7 2 hours in a sealed pressure tube, seal, concentrate under empty space, dilute with ethyl acetate, successively wash with saturated NaHC03 and brine, dehydrate in NaS04 and re-40 under empty space-This paper size is subject to the Chinese National Standard (CNS ) A4 specification (210X297mm) 311910 A7

B7 V. Description of the invention (38) Concentrate to obtain residue. Flash column chromatography (silica gel / 丨: 10 ethyl acetate: hexane) gave the title product as a yellow oil, 2.03 g (71% yield), by IR, iHNMR, i3CNMH, 19FNMR and Mass spectrometry identification. Example 3 Preparation of 1, 2, 6-dibromo-3-[(trifluoromethyl) thiol pyridinium

SCF combines 3-[(trifluoromethyl) thio] indole (0.776 g, 3.57 mmol), 1.0 g of crushed gum, and N-bromobromine (NBS) (1.27 g, 71.9 mmol) The mixture of methane gas was stirred at room temperature for 2 hours and the residue was concentrated under empty space. Flash column chromatography (silica gel / 15:85 ethyl acetate: hexane) residue to obtain the title product as a brown slurry, 0.4 1 g (30.6% yield), by IR, iHNMR, 13CNMR, 19FNMR He quality analysis and identification. Example 3 Preparation of 2 5 -bromo-2-[(2 -gas 1, 1,1,2-trifluoroethyl) sulfur 14 丨 p 朵 -3 _carbonyl wax I ai mt am ”I ml 1 ^ 1 ^ 1 ^^^ 1 ^^^ 1 — * J..-F is i (please read the precautions on the back before filling this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

CN

Br,

Br

N SCF CHFC1 H UCl ...

CH3COOH

N SCF.CHFC1 H will be 2 [(2-gas-1,1,2-trifluoroethyl) sulfur] indole (〇 · 75 g, 2.58 milli-41. The paper size is applicable to China National Standard (CNS) Α4 specifications (210Χ297mm) V. Description of the invention (39) A7 B7 mol) The solution in acetic acid was treated with bromine (〇45g, 2.84 mmol), stirred at room temperature for 16 hours, poured into water and filtered. The white solid filter cake was dissolved in ethyl acetate, washed with brine, dehydrated in Mg S〇4 and concentrated under empty space to obtain a residue. The residue was chromatographed (silica gel / 1: 4 ethyl acetate: hexane) to give the title product as a white solid, 0.28 g (29% yield) 'mp 187. _ 192 ° C, identified by ir, iHNMr, 13CNMR, 19FNMR and mass spectrometry analysis. Example 3 3-Preparation of Μ fish substitution _3-Γ triglucide. A certain indole compound SCF, SCF,

Br.

R

N H — ^ ϋ m m 1--I— ^^ 1 In i ^ i I-.. ~ ^ T. (Please read the precautions on the back before filling in this page) Use the same procedure as described in Example 3 2 to replace and apply 1 or 2 equivalents of B r 2 with appropriate substitution of chitosan substrate. The following compounds listed in Table III are obtained. Table 111 ’:;:’ Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs.

R -I Η SCF, -42- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male thin) A7 -___ Β7 5. Description of the invention (4〇) Number of examples Z mp ° C 33 5-Br cf3 76 -78 34 5,6-diBr cf3 slurry 35 5-Br CN 172-175 36 6-Br CN 153-156 Example 3 7 LlL trifluoromethane. 碁 _.) Di 3-[(trifluoromethyl) Preparation of sinoyl 1 bendol SCF3 I H2 ° 2 N CF Η

SOCF. —— ^ II into CF3 Η (please read the precautions on the back before filling out this page) 袈 · order the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative to print 2-(trifluoromethyl) -3-[(三Fluoromethyl) sulfur] pyridine (0.96 g, 33.6 mmol) and 30% hydrogen peroxide (Jj 5 mL, 1.0 mmol) in a mixture of acetic acid in Heat at 50 ° C for 16 hours, cool to room temperature, pour into water and filter. The filter cake was air-dried to obtain the title product as a colorless solid, 0.5 3 5 g (50% yield), mp 183 °-185 ° C, identified by IR, 1 H N M R.:, 13CNMR, 19FNMR and mass spectrometry analysis. ) 1 ′ 'Example 3 8-4 1; Preparation of indole compound by taking Ron-3-((alkyl) salicylidene 1

-43- This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 gong) aiisio A7 B7 5. Description of the invention (41) Use the same procedures and applications that are substantially described in Example 3 7 as appropriate 3- [(Trifluoromethyl) sulfur] < Indo-substrate, the compounds shown in Table IV are available

Table IV n I ------ ''------ ------ I: \ τ. W ~ 倷 二 呑 (Please read the precautions on the back before filling out this page) .SOCF,

Rm-

II Η Z Number of examples Rm Z mp ° C 38 5-Br cf3 210-212. 39 Η CN 154-156 40 Η conh2 185 (decompose) 41 6-Br Br 95-97 Example 4 2 2 ((2 -Gas-1,1,2-trifluoroethyl) Qi group 1 4 丨. Duo-3-Preparation of carbonyl nitrile

CN

CN Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

-I

N H * SCF0CHFC1 H2〇2

I I ch3c〇2h -►

NH * S0.CFoCHFCl will be 2 [(2 -chloro-1, 1,2-trifluoroethyl) sulfur] pyridine-3-carbonyl nitrile (2.3 9 grams of this paper scale applies China National Standards (CNS) A4 specifications ( 210X297mm) -44 311910 at B7 5. Description of the invention (42), 8_22 millimoles) and 30% hydrogen peroxide (2.80 grams, 24.7 millimoles) in a mixture of B heated at 60 C. 1 6 hours, cool to room temperature, pour into water and filter. The filter cake was air-dried to give the title product as a white solid, 2.37 g (89% yield), 111 ° 164. 167. Ma, identified by IR, hNMR, 1 3 C N M R and 1 9F N M R analysis. Example 4 3-4 8 Preparation of Substituted Chiral Noise Compounds Υ

R

SR Η2 ° 2 Υ

R Ν Η Ν 'Η nnf— -1— II II— 111'-'> ^ mi- -------I-. 1 ^ 1 \ — > (Please read the notes on the back before filling in (This page) Using the same procedure substantially described in Example 4 2 and applying the appropriate one) Thiazolidine substrate and heating to about 60-90 ° C, the compounds shown in Table ν can be obtained.

Table V Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs.

45 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 311910 at B7 5. Description of the invention (43) Number of examples Δα. Ζ Y mp ° C 43 5,6-diCl S〇2 CF2 CHFC1 CN 178-180 44 5-Br S〇2 CF2 CHFC1 CN 220-223 45 Η HS〇2 cf3 115-118 46 Η cf3 so2 cf3 104-107 47 Η CN so2 cf3 152-154 48 5-Βγ CN so2 cf3 > 230 Example 4 9 3 -Bromo-5,6-digas-2- "(2-gas-1,1,2-trifluoroethyl) syl 1 indole (please read the notes on the back before filling in This page) Printed and prepared by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

I I Rr II

Cl- \ ^ N S0, CF, CHFC1->-Cl N S09CF, CHFC1

H CH3C〇2H H will be 5,6-digas-2-[(2-chloro-1,1,2-trifluoroethyl) satyl] 4 Rong (0.84 g, 2.29 mmol) and sodium acetate (0.211 g, 2'.52 mmol) The mixture of acetic acid was treated with bromine (0.40 g, 2.5 2 mmol), stirred at room temperature for 0.5 hours, poured into water and filtered. The filter cake was air-dried to obtain the title product as a white solid, 093 g (91% yield), mp 200 ° 205 ° C, identified by IR, WNMR and 19FNMR quality analysis. -46- This paper is again applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) A7 B7 5. Description of the invention (44) Example 5 0 gilllJt-1,1,2-trifluoroethyl U-based〗 Preparation of -1-(ethoxymethyl) indole-3 -carbonylnitrile

CN N Η 'S07CF, CHFC1 I cich2oc2h5

CN KOt-Bu

NI CH, OC, H S0, CF ,, CHFC1 Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs will be 2-[(2 -Gas-1,1,2-Trifluoroethyl) Saxo] Dindo-3- Carbonyl nitrile (χ 0 g '3.1 mmol), gas methyl ethyl ether (〇35 g, 372 mmol) and 95% potassium tributoxide (〇44 g, 3 72 mmol) in tetrahydrofuran The mixed solution was stirred at room temperature for 16 hours, treated with 1.55 millimoles of additional gas methyl ethyl ether and potassium tributoxide, stirred at room temperature for another 16 hours, and concentrated under empty space , Diluted with ethyl acetate, washed successively with water and brine, dehydrated in M g S Ο 4 and concentrated under a void to obtain an oil residue. In flash column chromatography (silica gel / 1: 4 ethyl acetate: hexane, the title product was obtained as a white solid, 0.32 g (28% yield), 1111) 97. -100. (:, Identified by 111 and 1HN MR analysis.:;; Example 5 1-6 1 1 ‘Lightly substituted -1- (ethoxymethyl) indole compound preparation

Y

C1CH20C2H5 KOt-Bu, R

Y

II 1 ^ 1 1 ^ 1 In ^^ 1 1 1-Τ »-* | Teeth,-mouth (please read the precautions on the back before filling this page) 47 This paper size is applicable to China National Standard (CNS) A4 specification ( 210X297 mm) 3: Ι§10 A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (45) Use the same procedures described in Example 5 0 and apply appropriate substitutes Indole, the compounds listed in Table VI.

Table VI

Y

R

Ν '' ZI CH, 〇C, Hc package number Rm ZZ Y mp ° C 51 5-Br S02 CF2 CHFC1 CN 146-147 52 Η cf3 SOCF3 99-102 53 Η Η S02 cf3 97-98 54 Η cf3 scf3 58 -60 55 Η Η scf3 60-62 56 5-Br cf3 scf3 oil 57 Η CN H 50-52 58 Η CN S〇0F3 '101-103 59 Η CN S02 cf3 124-126 60 Η cf3 so2 cf3 93-94 61 6-Βγ Br scf3 oil 48 The paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297mm) ^^^ 1 ^^^^ 1 * mn ^ l mV nm -— ^ n 11-IB—I Bnn One V * I One Ί (Please read the precautions on the back before filling in this page) Five 311S10 A7 B7 Description of the invention (46) Example 6 2 _3 ', 5'-two gas Ben Yi You Tong, (3, 5-- Ratatouille) Preparation of lunar stay

NHNH

C1 Combine 2,4-difluorophenylhydrazine (4.25 g, 0.025 mol), 3> ethyl ketone (4.5 g '0.024 mol) and io ml HC1 in ethanol. The temperature is heated for 1 hour 'cooling and filtering. ; The cake was dried by air to obtain the title product as a white solid, 6.2 g (74% yield), 1111) 11 (). 1 1 1 ° C, identified by IR and 1HNMR analysis. . Example 6 3 Preparation of 5,7-digas-2- (3,5-digasphenyl) 4-indole I n Hi I--: i I — ^ ― ite ^ HI m---1 -I -I ---.--I-. I 爻 τα (Please read the precautions on the back before filling out this page) Central Bureau of Standards of the Ministry of Economic Affairs β: Printed by the Industrial and Consumer Cooperative

PPA

Will), 5_-Ranben Yijiu I, (3,5-digasoyl) Teng (52 g 〇_〇15 mol) and 20 ml of polyphosphoric acid (PPA) at Ϊ75 °,] 8λ. Guang ’1 0 υ L down force mouth Heat for 2 hours, cool, treat with ice and allow to stand still at room temperature. Generated -49- This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm). Nnu A7 -------. B7 5. Description of the invention (47) The mixed solution is extracted with ether. The combined extracts were dehydrated in anhydrous K2CO3 and concentrated under empty space to obtain the title product as a brown solid, 4.35 g (87.8% yield), mp 189. -190. (:, From the analysis of ... and ~ ruler Zhong Ding. Example 6 4 Preparation of difluoro-2 -m -difluoroi group) 3-(trifluoromethylcarbonyl X indole 〇

(CF3CO) 20 ^^ 1 »^^ 1 mm ^ nn HI nn am · HI-J., * W (please read the precautions on the back before filling in this page) 5,5-dichloro-2_ (3, 5-Difluorophenyl) indole (2.0 g, 6.0 mmol) in a solution of dimethylformamide in 1 () ml of trifluoroacetic anhydride in 0. _5 ° C treatment, stirring for 1 hour, at 50. Heat at 60 torr for 1 hour, stir at room temperature for 7 to 2 hours, pour into ice and extract with ether. The combined extracted ginseng was continuously washed with water and brine, printed in M 2 water in anhydrous K 2 c 〇3 and under the sky. It was printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy to obtain the title product as a mixed white solid, 丨6g ^ 6 2. / 〇 'yield), m p 2 1 4 ° — 2 1 6 ° C, identified by IR and 1 H N M R analysis. , Example 6 5 Preparation of 5,7-digas-2-(3.5 -digasphenyl) -3 -nitro 4 Shuo_-50- This paper scale is applicable to China National Standard (CNS) Α4 specifications (2 丨 0X297mm) 311910 A7 B7 V. Description of the invention (48)

Mix a mixture of 5,7-digas-2- (3,5-dichlorophenyl) 4 indole (1_25 g, 3_8 mmol) in acetic acid with 3 mL of concentrated HN 〇3 at 90 ° C Drop treatment, heating at 90 ° C for 1 hour, cooling and filtering. The filter cake was air-dried and recrystallized from methanol / water to obtain the title product as a yellow solid, 0.60 g, (42% yield), mp 272. -273 ° C, silver, IR, iHNMR and elemental analysis. Example 6 6 5, 7 -Dixian-2 "3.5 -difluorophenyl) -3-" (trifluoromethyl) satyl 1 indole Evening preparation

-^^ 1 I- I!-—II 1 1 y1 * ^ n ^ i-I -1-1--ί 一 W 、 一 = t > fPlease read the notes on the back before filling this page j Ministry of Economic Affairs Printed by the Central Standards Bureau employee consumer cooperatives (CF3S〇2).

Know 5,7-Diqi-2- (3, 5--milk private) p5 丨 p stay (2.0 g '6_0' millimoles) in a solution of dimethylformamide with 1 ml of trifluoromethyl Said acid anhydride is treated at 0 ° -5 ° C, stirred at normal temperature for 0-5 hours at 50. -60. (Heated for 1 hour at 3 times, stirred at room temperature for 7 2 hours, poured into ice and filtered. The cake was air-dried to obtain the title product as a white solid, 165 g (5 9 〇 / 0 yield) 51 copies Paper; Applicable to China National Standard (CNS) A4 (21 () < 297 Gong Ning) A7 B7

Cl + S〇2〇l2 311910 V. Description of the invention (49), mp 300 ° -302 ° C, (decomposition), identified by IR and 1HNMR and elemental analysis. Example 6 Preparation of 7 3,5,7 -trifluoro-2 _ (p-gas phenyl) pyridine

Cl Dissolve a solution of 5, 7-digas-2-(p-gas phenyl) indole in tetrahydrofuran with 1.0 mL thiosulfate gas, stir at room temperature for 16 hours, pour into ice and filter . The filter cake was air dried to give the title product as a yellow solid, 0.85 g (76% yield), 111.148. -14 9 ° (:, by 111, 111 ^^: \ 411 and elemental analysis and identification. Example 6 8 8 5 (please read the notes on the back before filling this page) Printed by Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs 2-Preparation of (substituted phenyl) pyridine compounds

R

L

L

Q

R Υ

Μ 52 This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297). S11310 A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Fifth, the description of the invention (50) 1 1 is used in Example 6 2 To the same procedures and applications as described in Chapter 6 7 as suitable reagents, the compounds shown in Table VII can be obtained. Please refer to Table 1 VII. Read the notes on the winter 1 I / YL 1 1 1 I < Η Q • Fill in this page 1 Pack 1 1 Number of examples YLMQ mp ° C 1 1 I 68 4,6-diCl H 3- C1 H 5-C1 210-212 1 1 69 4,7-diCl H 3-C1 H 5-C1 202-203 Order 1 • 70 5,7-diCl HH 4-C1 H 165-166 1 1 71 4,7 -diCl no2 3-C1 H 5-C1 115-117 1 I 72 4,6-diCl N〇2 3-C1 H 5-C1 258-260 _ 丄 73 (4,6-diCl N〇2 H 4-C1 H 248-250; 1 74 5,7-diCl no2 H 4-C1 .H 290-291; 1 75 4,7-diCl COCF3 3-C1 H) M 5-C1 '198-199 1 Ί 76 4,6 -diCl COCF3 3-C1 H 5-Cl 165-166 '1 | 77 5,7-diCl COCF3 H 4-C1 H 112-113 1 I 78 4,7-diCl so2 cf3 3-C1 H. 5-Cl 212 -213 1 1 f 79 4,6-diCl so2 cf3 3-C1 H 5-Cl 304-306 1 1 80 4,7-diCl Br 3-C1 H 5-Cl-1 1 1 -53- i 1 1 book The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) 311910 A7

1 Example 8 1 Insecticidal and antiviral compounds of the compound The test solution was prepared by dissolving the test compound in 35% acetone in a water mixture to obtain a concentration of 10,000 ppm. Subsequent dilution is made with water when needed. It is infested with blight, 3rd instar larvae, southern armyworm (saw) Sieva (Sieva) Lima beans and leaves spread to 7-8 cm long. Immerse in test solution and shake It takes 3 seconds and is allowed to dry in the evacuation chamber. The bean leaves were then placed on the bottom with wet filter paper and 10 * 3rd instar caterpillars. After 5 days, observe any disturbances in mortality, reduced feeding-feeding, or normal tax coverage. Melon leaf melon, 3rd-instar southern corn reported λμγτμ 1¾ liter fine talc was placed in a 30 ml wide-mouth screw cap glass bottle. 1 ml of appropriate winter acetone suspension was pipetted onto talc to provide i 25 and 0.2 mg of active ingredient per bottle. The bottle is allowed to stand under a gentle air flow until the acetone evaporates. Loosen the dried talc, add 1mm corn seeds as insect food and add 25¾ litres of wet soil to each bottle. The bottle is capped and the contents are removed and mixed in the v〇rtex mixer. After this, 10 3rd instar rootworms were added to each tile and the bottle was loosely capped to allow air exchange of the larvae. The management group maintains 6 days before making the death rate. The lost larvae are presumed to be dead, because ‘they decompose quickly and cannot be found. The concentrations used in this test are relative to about 50 and 10 kg / ha, respectively. Cotton leaf snail (Ο P -resistant species), 2 spot field spider worm (τ S Μ) The first leaves of the Siwalai horse bean plant are expanded to 7-8 cm. Selected and cut to one plant per pot. Small pieces of infected leaves taken from the main community are cut and placed in the test ————————————— ______-54 -__ This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 male seam) _ f Please read the precautions on the back and then fill out this page) Outfitting--Ordered by the Ministry of Economic Affairs Zhongshang Standards Bureau Consumer Labor Cooperative Printed 311910 A7 B7 Fifth, the invention description (52) on each leaf of the plant. This is done about 2 hours before the treatment to allow the worms to move to the test plant to lay eggs. The size of the cut and infected leaves is different to obtain about 100 insects per leaf. At the time of the test treatment, the leaves used to remove snails were removed. New mite-infected plants are immersed in the test solution for 3 seconds under shaking and placed in the evacuation chamber until dry. After 2 days' take the next leaf and calculate the mortality rate. After 5 days, remove the other leaf and observe the mortality of eggs and / or new neck bugs. Fish jF potato microleafhopper, adult worm, western potato leafhopper (LH) Western frog Lima bean about 5 cm is immersed in the test solution under shaking and placed in an air-chamber to dry. This leaf was placed in a 100 mm x 10 mm petri dish containing wet filter paper at the bottom. Approximately 10% of leafhoppers were added to each dish and the treatment was maintained for 3 days before the mortality rate was established. American tobacco budworm, third-instar tobacco toothworm (T B W). Immerse cotton cotyledons in the test solution and allow to dry in the evacuation chamber. When dry ’Cut into 4 pieces each and place 10 knots individually into a 30¾ litre plastic medicinal ring containing 5 to 7 mm long sections of wet floss. Add a 3rd instar caterpillar to each cup and place the cardboard lid on the cup. The treatment group was maintained for 3 days before making an estimate of the mortality rate and the reduction in feeding loss. Maize root leafworm, 3rd instar Western corn rootworm (WCR ,; printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Place 1 ml of fine talc in a 30 ml wide mouth spinner Cover glass ▲ bottle. Pipette the appropriate acetone test solution onto the talc with a straw to provide 25 mg of each legal ingredient. The bottle is allowed to stand under a gentle air flow until the acetone evaporates. Loosen the dried talc, Add 丨 mm corn seeds as food for insects and add 25 liters of wet soil to each bottle. The bottle is capped and the contents are removed and mixed in the v 0 rte X mixer. After this, add 3rd instar rootworms to each bottle Bottles and bottle pine ____- 55-This paper scale is in accordance with the Chinese National Standard (CNS) from the specifications (21 (rx297mm) A7 B7 5. Invention description (53) Cap to allow air exchange of larvae. The treatment group keeps 5 The number of deaths is recorded at the time. The lost larvae are presumed to be dead because they decompose quickly and cannot be found. The concentration used in this test is relative to about 50 kg / ha. The test is based on the scale shown below Number and income The data is shown in Tables VIII and IX. When more than one test is conducted, the results are averaged. Γ; _ binding (please read the notes on the back before filling in this page) the amount of printing system of the employee consumer cooperative of the Central Bureau of Standards Scale ratio% mortality rate% mortality 0 no effect 5 56-65 1 10-25 6 66-75 2 26-35 7 76-85 3 36-45 8 86-99 4 46-55 9 100 untested-56 -This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (2 丨 Ο X 297mm) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (54)

Table VIII Pesticidal and acaricidal evaluation of substituted indole compounds% Mortality compound SAM SCR TSM LH TBW (number of examples) (1000 ppm) (300 ppm) (50 ppm) (300 ppm) (300 ppm) (100 ppm) 2 0-0 8 0 0 4 0-9 0--5 9-0 0-9 -9-0-0 0--10 9-9 0--11-9-9-9 12--- 0--13-9 0 8 7 9 • 14A disgrace 9 7 8 9 9 14B-9 9 6 9 9 15A-3 4 8 1 0 15B 8 9 9 0 2 1 16-9 9 8 9-. 17-9 9 8 9 9 18-2 0 0 ι 0 · 0, 19A-9 0 0 3 5. 19B.-0 0 0 0 0 20-7 0 0 0 0 21-8 9 5 3 3 22-0 0 3 0 1 23 _ 0 0 3 0 1 (Please read the precautions on the back before filling out this page) Binding · Order -57- This paper scale is applicable to China National Standards (CNS) A4 specifications (210X297 mm) A7 Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperatives 311910 B7 V. Description of invention (55)

Table IX Pesticidal and acaricidal evaluation of substituted β-indole compounds% Mortality compound SAM WCR TSM LH TBW (number of examples) (1000 ppm) (300 ppm) (50 ppm) (300 ppm) (100 ppm) (100 ppm) 24 9-2 8--25 0-3 7--26 0-2 5---27 7-0 9--28 2-0 0--29 9 9 0 0--30 0-0 0 --31 9 4 0 4 0 0 * 33 9 9 5 4 9 0 34 9-9 9--35 9-0 8--37 9 9 0 0--38 8 9 0 0--, 39 9-2 3, '--40 0-3 〇1! I -1 '41 9-2 0--1 42. 9-6 0 8 4 44 9-0 9--45 0-0 0--46 9 9 9 4 9 8 47 9 _ 0 9--^ 1. ^ 1 tt ^ tt Bv ^^ i ^^^^ 1 — ^^^^ 1 ^ 1 ^ 1 ^^^^ 1 ^^^^ 1 a ^ m 1. T, I-^ ¾ i (please read the precautions on the back before filling in this page) -58- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 311910 A7 B7 V. Description of invention (56 ) Table IX, (cont.) Evaluation of insecticidal and acaricidal substitution of substituted pyridyl compounds Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperatives% mortality compound SAM WCR TSM LH TBW (number of examples) (1000 ppm) (300 ppm ) (50 ppm) (300 pp m) (100 ppm) (100 ppm) 50 8 3 3 4--51 2-0 9--52 9 9 6 7 8 0 * 53 0-4 0--54 0-7 0--55 0-9 0--56 9 9 8 7 9 0 57 4-2 0--'58 9-9 3--59 9-8 0--60 9-9 5--62 2-0 0--63 5-0 0--; 64 9-8 8 ·;--65 9-9 ϊ 0: j-66 0-0 0---68 7-2 0--69 7-0 0--71 9-7 0- -75 9-0 0--78 0 0 0 _-(Please read the precautions on the back before filling in this page) Binding · Order_-59- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm )

Claims (1)

4 1 ϋ 8 7 2 Patent broken patent. Tfj A8 B8 C8 D8 ίPatent yttrium siege Method, which includes contacting these pests or their food supply, habitat or breeding grounds with a pesticidal effective formula I compound Y Rm Ν ζ wherein Υ and Z are hydrogen, halogen, CN, Ν02, SCCOnRj, C! -C6 haloalkyl, COR2 or W, the restriction condition is that only one of γ or z may be W, and the further restriction condition is that only one of γ or ζ may be hydrogen; w is phenyl or functional phenyl; R Is Η, Ν02, halogen or ^-(: 4 alkoxy; m is an integer of 1, 2, 3 or 4; η is an integer of 0, 1 or 2; R 丨 and R 2 are each C 丨 -C 6 Halogen group; Α is Η, CrC4 alkyl, (^-(: 4 alkoxy or CrC4 alkoxyalkyl. 2 • According to the method of patent application item 1, wherein γ and ζ are each hydrogen ' Halogen, CN, N02, S (0) nRl or C1-C6 haloalkyl, the limiting condition is that only one of Y or Z is hydrogen .; R is halogen or (^-(: 4 alkoxy; '·- m is an integer of 3 or 4 and -11 is an integer of 1 or 2. 3 • According to the method of claim 1 of the patent application, where A is hydrogen or c ^ -c ^ -------- installed ------ ordered ----- call line (please read the back first Please pay attention to this page and then fill out this page.) This paper is suitable for foreigners (CNS) (210X297mm). 311S10 A8 B8 C8 D8 Patent application alkyl group According to the method of patent application in item 1, wherein Y is hydrogen, CN, NC > 2 'S (〇) nRi or C1-C6_ alkyl and Z is w. According to the method of item i of the scope of patent application' where z is phenyl or halophenyl. 6 ·: According to the scope of patent application The method of item 1 is to protect growing plants from attack or rampage by insects or mites. It includes a compound Y of formula Ϊ in an insecticidally effective amount (please read the precautions on the back before writing this page) K N Z 1 A is applied to the leaf group of the plant or the soil or water in which it grows, where Υ 'Z' A, R and m are according to item i of the scope of the patent application. According to the method of applying for item 6 of the patent scope, where a is hydrogen or c, _ base 0 printed by the C4 Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy 8. According to the method of applying for item 6 of the patent scope, where z is CN, cKc alkyl or. 9. The method according to item 6 of the patent application scope, wherein Z is phenyl or phenyl in the south. '·-10. The method according to item 7 of the patent application scope, wherein z is CN, c Pc6 is an alkyl group, or phenyl or halophenyl. Halogen -2- This paper is suitable for China National Standard Falcon (CNS) M specifications (210X297mm)