TW382623B - Pesticide compounds, compositions and the preparation - Google Patents

Description

VvJ 5. The characteristics of the invention description (11) can be beneficial to change the early limited use, so it can be practically applied. The active substances of the general formula I can promote the following active ingredients of known arthropod insecticides: acetamidine derivatives, such as euchlorphenox (oxamyu (a pesticide trade name, the same below); phenylamidine gland Compounds; for example, flucycloxuron, hexafluffluron, teflubenzuro + n, triflumuron; phenylcarbazide-like IGR compounds; dipyridine Compounds: such as heptenophos; cross-linked biphenyl compounds: such as etofenprox, broraopropylate, m + ethoxycholor, temephos Tetradifon; carbamates; for example, aminocarb, aldicarb, aldoxycarb, asulam, bepdiocarb, 'Benfuracarb', carbol 1, carbetamide, carbo

I carbofuran, carbosulfan, fdiethofencarb, dioxacarb Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before (Fill in this page), ethiofencarb, fe η 〇bucarb}, fenok (fe η ο X ycarb), furathiocar (!)), Exterminator Isoprocarb, methomyl, ox.myl, pirimicarb (pirimor), propoxur, thiodicarb -13-Paper size Applicable to Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to alkynyl pesticide compounds of the general formula I, including the general formula I Active ingredient pesticide composition, pesticide synergist of general formula (I), synergistic pesticide composition with known pesticide active ingredients, and preparation method thereof:

Ar-(CRlR2) m-(YR3R4) n-X- (CR5r6) 〇-(CR7R8) p-c 5 c-E; (I) Within the general formula I, the meaning of the substituents is as follows:

Ar is an alicyclic, aromatic, or heterocyclic moiety containing one or more heteroatoms, and may be optionally substituted with one or more alkanoyl, methyldioxy, alkyl, halo, haloalkyl, or nitro groups Substituted and / or condensed with benzene ring; R1, R2 are hydrogen, alkyl, alkenyl, haloalkyl, phenyl, substituted phenyl, cycloalkyl, R3, R4 are hydrogen, alkyl, Alkenyl, haloalkyl, phenyl, substituted phenyl, cycloalkyl, or R3, R4 — together is oxygen; Y is C, P0 or R 9 YR 3 R 4 — together form -C = N- group X is -R9 is hydrogen, alkyl, phenyl, substituted phenyl;

Rw is hydrogen, alkyl; R5, R6, R7, R8 are each hydrogen, alkyl, alkenyl, haloalkyl, or

Ar-UR1 R2) m-(YR3) n -χ- together form a carboxyamidoimine group; E is hydrogen, tooth element, and methyl group; this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm)- -------- 丨 Install-(Please read the precautions on the back first 'for this page) Order

A7 __. '_B7 V. Description of the Invention (l2), thiofanox, xylylcarb; Derivatives of formazanyl formamidine: for example, alanyca.rb, Bujiaxin ( butocarboxim); Cyclodiene: for example, aldrin, chlordane, endosulfan, heptachlor; heavy carbohydrate: fipronil; : RH 5992, RH 5849, CGA 215'944; Nereistoxin with the same article: pi. Bensultap; nitro_base_sleeping house. Refers to amines: for example imidac .loprid); ./ Organic dish compounds: such as quinalphos, diazinon, phosalone, dimethoae, azonphos-methyl; organic Tin compounds: such as azocyc lot in, cyhexatini, fenbutationoxide SSI-12-12; phenoxy compounds: such as diafenttiiuron; batch miles: _ For example, white powder pine (P yr .a ζ ο ρ 〇s); Pyrethroid. Ester: For example, allethrin, biological yale_ning. (1) 1031161; 111 > 111) ( 6 8_ 1) 〇1), acridine B, quininathrin, fenvalerate, empenthrin, praiiethriiO, resnethri η, Μ TI -8 0 0, flufenprox, .permethrin, Zhifening _ 1 4-This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) --- --------- I 2 ---- ^-I Order -----. 1 #, (Please read the notes on the back before filling out this page) Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumption Printed by the cooperative A7 A7 Printed by the consumer ’s cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed B7 V. Description of the invention (2) m is 0, 1, 2; η is 0, 1; 〇 is 0, 1, 2; P is 〇, 1 , 2, Wei-bridge-(CR1 R 2) m-(CR 3 R 4)--X- (CR 5 R 6) 〇- (CR7R8) P The sum of the atoms or groups is 3, and -Csc-E skeleton Forms a straight chain with a bridge atom, containing 6 atoms, and the terminal is preferably a methyl group. Furthermore, for example, Ar represents a leaf group, Y means a sulfonic atom, X means a gas atom, and R3 and R4 cannot represent oxygen together. The present invention further comprises a salt of a compound of general formula (I) and an optically active isomer β. A narrower element of a compound of general formula (I) is represented by the general formula (IA >, (IB), (1C), (ID), ( IE) and (IF) indicate that the salts and optical isomers are the same as above, and the meanings of the substituents are also the same. "

Ar-(CRlR2) m · γ-〇 (CR5R6) 〇 _ (CR7R8) p-c s C-E Ο (ΙΑ)

Ar-(CRlR2) m-γ-N-(CR5r6) 〇. (CR7r8) p. C = C-EO Rl〇 (IB) -4-This paper size applies to China National Standard (CNS) A4 (210X297 mm) ) ------------ ir: \ (Please read the notes on the back and repeat this, write this page) Order%,

V. Description of the invention (I3 (tetramethrin), CyperBethrin >, and its isomers. • Structures and isomer compositions; (Please read the precautions on the back before filling in this tile) Class 阙: For example, pyridaben;. Guru derivatives:. For example, chlorpyriphos; '· · · · Pyramid derivatives: For example, pyrimiphenethyl (? 71 ^ 1111011〇8 -:, 'Λ · e: thy 1.), Lee'. Rice pound. Methyl (pyriraiphos-methyl) •-Pyrrole: For example 'such as AC 30 3-t, 6 3 0;, -... B Quizolidone: such as fenfenspira iifenazaquin); terpenes: dilute: conjugates. Derivatives. Raw materials: for example met. Hop re ne; •. ·, Tetrazines: for example ClofentezineK, Sz bu 121 Flufenzin; '…:. ·:-.:. Stele type: For example, bupr fenfen η; Blazolidines: Hexidol (P1. Hqxythiaz ο x); Triazoles: Pi. Isazophos, BH 7 988; Gasified tobacco: lindane; Macrolide ,; Defenpyra (TebufenpyradK; Fenpyroxymate; Sanchamar (Triazanate) (both pesticide products). The above-mentioned active ingredients printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs are listed in Pesticide Manual No. 8 and No. 10, and European Patent Application No. 0635499 (SZI-121), AG Cheu. Xinya Compound Review Vol. 11 (1993) and ACS Symposium 1 Series 504, page 272. Compounds of general formula I are best used for carbamate penetration (preferably, -15- X degree is applicable to Chinese National Standard (CNS) A4 ^ 格 ί 210X2.97 mm) A7 B7 V. Description of invention (3)

Ar- (CRlR2) m-(CR3R4) n-〇-(CR5r6) 〇-(CR7R8) p-C s C-E (IC)

-(CRlR2) m-(CR3R4) n-N-(CR5r6) 〇 · (cr7r8) C ξ C-E 、,,,,, 〆〆〆 * ---------- Rl〇 (ID )

Ar-(CRlR2) m-(CR3R4) n-N-(CR5R6) 〇-(Cr7R8) p-C Ξ C-E

Rio (IE) ---------- ^ II-.%. T (Please read the notes on the back first to write this page) * 11 R9

I

Ar-(CRlR2) m-C w 0-(CR5R6) 〇-(CR7R8) p-C is C, E

F 丨 Line ·% Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, with a typical example, the ether acetylene-butylated 2-I) * 7 {methyl-type acetylene naphthyl propyl II 1 2 methylene oxide II Acene-3 ester carboxylic acid

1 R 雠 3 benzene, radicals > Leythyl *])-D methyl-5 radicals propane ethoxy} alkyne > alkynyl butyl butane 2 oxygen 2-alkyne < alkyne- (but1- Ding-12-C 2-Ga ¢ 2-ί di 1-)-Phenylmethylformamide. Standards | Guoguo I;

AI centimeter 7 9. 2 X ο A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) 5-[(But-2-ynyl) methyl] -1,3-benzo Dioxo, 5- [2-methyl-bu (2-butynyloxy) propyl] -1,3-benzodioxo, 5-[(but-2-ynyloxy > phenyl Methyl] -1,3-benzodioxo, 2-[(2-butynyl) methyl] -1,4-benzodioxo, 2,3-dihydro_2,2- Dimethyl-7- (3-pentoxy) benzofuran. In terms of Ar, the aromatic group is preferably phenyl or phenyl, and when Ar is a heterocyclic moiety, it may contain one or more 一个 〇, S, H fluorene atoms represent benzodioxane, benzodioxane, 2-benzofuran, and 7-benzofuran moieties. The cycloaliphatic group is preferably condensed with a benzene ring. Indanyl or 1,2,3,4-tetraargonaphthyl. Carboximidoimide is preferably represented by phthalimidoimine. Aromatic, heterocyclic, and cycloaliphatic Ar groups may be selected as Ci -4 alkoxy, methanediyl, Ci-4 alkyl, halo, Ci-4 haloalkyl, or nitro substituted β The so-called synergist refers to a compound that is non-toxic or slightly toxic when used alone, but is related to agricultural chemicals Drugs, preferably arthropod insecticides, can significantly improve the effectiveness of the latter. These materials have several ways of action in principle, however, blocking the metabolism of the active substance can definitely give effect. Metabolism The effect can be carried out by oxidation, hydrolysis, conjugation and absorption reactions, and the way of change. At present, there are no clear examples of synergists that have an effect on the receptor level, and they have not played a major role in practice. In terms of pesticides The special emblem of synergistic efficacy is the so-called SR synergist ratio, which is defined as follows: LDso insecticide SR B0-LDso insecticide + synergist This paper applies the Chinese National Standard (CNS) A4 specification (210X297) (Centimeters) Please read the note of the first notice 意 Page ii A7 B7 V. Description of the invention (5) The greater the difference between SR 5 and 1, the greater the synergistic effect. The use of arthropod insecticide formulation increases The agents are very attractive because it is possible to realize new formulations that cover virtually all the representative examples in this category. Compared with the previous examples, these new formulations are cheaper, less toxic, more selective, less environmentally harmful, and can be suppressed. Arrive After showing the synergist and revealing its mode of action, from the mid-1960s to the late 1970s, extensive research and development operations were conducted to develop new However, this research has only reached a few molecules and can be truly applied (the number of currently registered pesticide synergists is below 10) ^ These compounds are of basic scientific importance in the study of resistance [K. F. Raffa and T. M. Priester, J. Agric. Entoa ο 1., 2 (1), 27-45, (1985)], however, only 2-3 molecules listed are in the pesticide manual Products, and only two materials (PBO, MGK264) are actually available in the market, and field applications are limited by many factors; it is not easy to find chemical tools that can be used selectively and safely, and their cost / benefit ratio is comparable to active ingredients. For economical use of synergists, they must be highly effective and must work in small amounts (not exceeding the original effective amount of the active ingredient). Based on the chemical structure, currently known arthropod insecticide synergistic compounds can be divided into the following groups: 1,3-dimethoxyphenyl (MDP) derivatives; 0-2-propynyl and propynyl are the same Phenols and their derivatives (ethers, oxime ethers, esters); N-alkyl derivatives; phosphorus esters; other derivatives, such as thiophosphonates, polyhalogen ethers, etc. This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the note on the back 'Sf Pack-write this page)-Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Printed by the Ministry of Economics, Central A7 B7 printed by the Consumer Cooperatives of the Bureau of Standards. —- V. Invention Description (6) Compounds can also be grouped according to their attack targets [κ · F. Raff a and T. M priester, J. Agric · Entomol ·, 2 (1 ), 2 7-4 5, (1 98 5 >), but this grouping is quite theoretical and low in accuracy, especially 0 is not fully understood in the process of interstitial metabolism. The metabolism of most compounds is used for gastric and gastric succession It can be carried out at the same time, following multiple mechanisms, so tlJ # has little information, even if the first step of step degradation is considered as a decisive step "_ For most arthropod insecticides, it is first attributed to The gas enzyme system. It is generally agreed in literature that this group of compounds is active, which basically uses the cytochrome P-4 50 enzyme that blocks the mitochondrial oxidation system [John E ·

Cassida, J. Agr, Food Chem., 1 8 (5), 7 5 3-7 7 2,., (1970), R · M · Sacher, RL Metcalf, and TR Fukuto; j. A gr. F ο od C hem., 16 (5), 7 7-7 8 6, (1 968)] 〇 Enzymes that form so-called heterozymes are structurally homologous and constitute the main part of the detoxification system of organic matter [〇 rtiz de Montellano, P · β., Ed ·· Two cytochromes ρ_450: Structural mechanism. System and biochemistry ", plenum, New York ~ about (1986)] ^ Detoxification by matrix single oxidation, resulting in more polar products, After further transformation, it may be eliminated by organic matter. This article degrades very different structures in the same way. Therefore, it can also be called mixed functional oxygenase (M F 0) and multi-matrix monooxygenase (P S M 0). Based on this, the surface of the enzyme is also expected to be a kind of synergist. On the contrary, it was optimistic to discover compounds. In order to isolate and test the cytochrome P-45Q of P. parasite, there are standard methods available [J. G. Scott and S. S. T. Lee; Arch Insect Biochemand Phys., 2 4, 1-1 9, (1 9 9 3)]. Various enzymes -3- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 fire 297 mm) (Please read the precautions on the back first 写 S write this page)-Binding · Order A7

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The description of the invention (7) shows that they are very similar, but are significantly different from each other. The synergists known in the literature and studied by the present inventors' belong to the 0-2_propynyl and propionyl homologues and their derivatives (ethers, oxime ethers, vinegars). As shown in the literature, it has different effects on different varieties, and the oxidative capacity of Italian loquat varieties varies to some extent. The reason is the high insect / mammalian selectivity and synergistic selectivity, the properties of this group of compounds. Such selectivity cannot be directly explained by the above-mentioned actions and modes, and is the basis for development and security applications. On the other hand 'is the reason why these compounds have not yet been released. All the compound groups made and evaluated so far generally have effects only on the propynyl side chain, which is substituted at the allyl position by various aryl rings, mainly through oxygen atoms. Known compounds can be grouped into the following groups: Phenylpropynyl ethers [Fellig et al., J. Agr. Food Chem., 1 8 (5), 7 8, (19 7 0)); benzyl propynyl ethers [Ciba Cargill, German Patent Publication No. 2 2 3 5 0 5 (1 9 7 2)]; Benzaldoxime propyne ethers [Ciba Cargill German Patent Publication 2 016 1 9 0 (1 9 7 0)]; propynyl naphthoate [Hoffman-La Roche Belgian patent 867 84Θ (1978)]; alkynyl phthalimide [FMC German patent 1 217 693 (1966)]; phenyl phosphonate Alkynyl esters [Technical Information Sheet NIA 1 6 8 2 4 (19 6 8)] of Niagara Chemical Department of FMC Company]. The first two groups are grouped because of the high diversity of aromatic groups and their substitutes. Therefore, it is known that this paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- -Sai-I ', (Please read the note on the back f: ¾ this 贳) " Quan-% A7 B7 V. Description of the invention (8) Leky propynyl ethers [Höffman-La Roche USA Patent No. 3 362 871 (19 &8); Ciba Cargill German Patent Publication No. 2 100 325 (1971 >); 4-Hydroxyphospholine propyne ethers [Alkaloida Hungarian patent 210 557 (1992); Methanedioxo Benzyl propynyl ethers [Sumitomo Corporation Japanese Patent 03 01177 (1973)]; Substituted methyldioxybenzyl propynyl ethers [Sumitomo Corporation Japanese Patents 6 1 2 4 5 8 5 and 6 1 2 4 5 8 6 (189 6)] * In the study of lylic propynyl ethers, it was concluded that butynyl ethers, especially 3-butynyl ethers are more effective than isopropylpropynyl and pentynyl ethers [RM Sacher et al. People, J. Agr. Food Chera., 16, 779-786 (1968)] β It is interesting that this work has not been entangled, and this patent has not yet been applied for. Detailed analysis and suggestions of literature The propionyl side chain cannot be replaced with the same I because the public # and patents are further related to propynyl derivatives. To clarify this contradiction, the inventors have made the compounds in question, and found that they are contrary to what is shown in the literature · BljJ-butynyl (terminally charged) is more effective than 3-butynyl derivatives; a-isomers are more effective than isoforms; and 3-pentynyl derivatives_fcb_2-butynyl derivatives Objects are more effective β ------------ " * ---- These materials fully conform to the theory of the inventors and others, and the materials provided in the literature may be the reason that no one follows in this direction In the same way, the activity of 4-pentynylphthalimide derivatives is also contradictory: although it has been proved to be an effective synergist for propylene pyrethroids, it is incompatible with pyrethroids [H. Jaffe , JL tieumeyer, J. Med. -1 0- This paper size applies to China National Standards (CNS) A4 specification (210X297 mm) Please read first Note: Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives, Printing, Central Standards Bureau, Ministry of Economics A7 B7 printed by the employee consumer cooperative V. Invention Description (9) Chern. 13, 901 (1970)]. In these structures, alkyne The end of the chain is a triple bond. A hybrid maltization of these structures, that is, N-alkylaminopropynylphthalimide, can also be made, and the triple bond is also at the terminal position [Sumitomo Dutch Patent No. 6 600 916 (1966 )] Β In short, the most active representative of this group has not been actually applied, although it shows excellent activity in some tests, and its synergist / active ingredient is outstanding [DJ Henessy: "Biochemical Toxicity of Pesticides" · Edited by R. D. O'Brian and I. Yamaiaoto, Academic Trading Agency, 10 5- 1 1 4 (19 7 0) «〕. There are a number of reasons: its activity is not as good as that of the derivative that was previously fully determined, and it only shows activity in a narrow range. Its effectiveness is highly variety-dependent, and most of the same variety depends on the different "strength J, so Failed to ensure its safe and wide application. The alkynyl compounds listed above are usually the derivatives of the best structure, but the authors do not know their falsity, and have not made the most active representative examples. Combine and improve these compounds. Advantage β The present inventors have experimentally tested, compared, and analyzed the known compounds and the biological effects of the new derivatives made by the inventors, showing that the structural elements are the cause of the effects β. In order to surpass the activity of earlier compounds, combining these properties can ensure the effect on more varieties and better than more known active ingredients.} The whole part of the present invention is to find that in the best compounds, the carrier has The third part of the alkynyl structure of the electron-rich Ar ring, the Ar part has been linked to a triple bond containing η m m. Ψ PL. The atom of the bridge is variable, and there may be substitutes, and the ring is also the same. In order to improve the activity Should introduce lipophilic and -11- Note that the first face I read in book

The size of the paper is applicable to Chinese National Standard (CNS) A4 (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (10) Electron-rich atoms and substitutes 0 Bridge atoms except master atoms The outer 9 may be a heteroatom such as oxygen N, sulfur, nitrogen, phosphorus, etc. These atoms may be connected to each other by a single bond or a double bond. 9 If necessary, there may be a substituent containing a hetero atom on top. Or derivatives substituted by 0 atoms can be replaced with each other 0-the first element of the bridge ^-the element can form a ring 9 with the substituent can be attached to the aromatic ring 9 and is part of the electron-rich back __- Molecules 0 can also be added with the above heteroatom 9 to be connected to the bridge 9 Note and further advance the effect by introducing alkoxy, halogen s, radical, alkyl, or nitro substitution 9 A A ring can be 5 -6- Section 7 »Can also be condensed with another __ ·% This ring 9 is constructed according to the above principle» The element that can be bridged--alkyne page '-^ acetylene% of the side bond of the compound when hydrogen is replaced by methyl » Shows that the activity is higher than that of the same strip with a bond at the end. Maintaining this principle allows new substitutions »According to the needs of the application (lipophilic interlaminarity, etc.), the persistence of the compound can be improved by 0 The 9 R (+) enantiomer is more effective than the s (-) enantiomer in the isomers of optically active compounds of a-methyl substituted benzyl derivatives. Poor activity between isomers »With the elimination Increased activity of the spin-mixed mixture to increase κκ 1 New compound developed by the present inventors »is characterized by outstanding * Tu milk / Kunmite > insect selectivity and high performance > Low dosage of active ingredient 0 Thanks to the outstanding height of the compounds of the invention Receptor affinity 0 In paired 1 experiments 9 The pseudo number of this compound far exceeds the synergist of the active ingredient previously known * Its metabolism is based on the oxidation of mitochondria. This highly active and selective 9 can be found in Field studies conducted in small areas have proved that the compound does not show toxicity. 9 Does not separate from the active ingredient »Its physical and chemical parameters and active ingredient are well coordinated. 〇 Through these doses / effects / cost value-1 2-this paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm)

VvJ 5. The characteristics of the invention description (11) can be beneficial to change the early limited use, so it can be practically applied. The active substances of the general formula I can promote the following active ingredients of known arthropod insecticides: acetamidine derivatives, such as euchlorphenox (oxamyu (a pesticide trade name, the same below); phenylamidine gland Compounds; for example, flucycloxuron, hexafluffluron, teflubenzuro + n, triflumuron; phenylcarbazide-like IGR compounds; dipyridine Compounds: such as heptenophos; cross-linked biphenyl compounds: such as etofenprox, broraopropylate, m + ethoxycholor, temephos Tetradifon; carbamates; for example, aminocarb, aldicarb, aldoxycarb, asulam, bepdiocarb, 'Benfuracarb', carbol 1, carbetamide, carbo

I carbofuran, carbosulfan, fdiethofencarb, dioxacarb Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before (Fill in this page), ethiofencarb, fe η 〇bucarb}, fenok (fe η ο X ycarb), furathiocar (!)), Exterminator Isoprocarb, methomyl, ox.myl, pirimicarb (pirimor), propoxur, thiodicarb -13-Paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm)

A7 __. '_B7 V. Description of the Invention (l2), thiofanox, xylylcarb; Derivatives of formazanyl formamidine: for example, alanyca.rb, Bujiaxin ( butocarboxim); Cyclodiene: for example, aldrin, chlordane, endosulfan, heptachlor; heavy carbohydrate: fipronil; : RH 5992, RH 5849, CGA 215'944; Nereistoxin with the same article: pi. Bensultap; nitro_base_sleeping house. Refers to amines: for example imidac .loprid); ./ Organic dish compounds: such as quinalphos, diazinon, phosalone, dimethoae, azonphos-methyl; organic Tin compounds: such as azocyc lot in, cyhexatini, fenbutationoxide SSI-12-12; phenoxy compounds: such as diafenttiiuron; batch miles: _ For example, white powder pine (P yr .a ζ ο ρ 〇s); Pyrethroid. Ester: For example, allethrin, biological yale_ning. (1) 1031161; 111 > 111) ( 6 8_ 1) 〇1), acridine B, quininathrin, fenvalerate, empenthrin, praiiethriiO, resnethri η, Μ TI -8 0 0, flufenprox, .permethrin, Zhifening _ 1 4-This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) --- --------- I 2 ---- ^-I Order -----. 1 #, (Please read the notes on the back before filling out this page) Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumption Printed by a cooperative

V. Description of the invention (I3 (tetramethrin), CyperBethrin >, and its isomers. • Structures and isomer compositions; (Please read the precautions on the back before filling in this tile) Class 阙: For example, pyridaben;. Guru derivatives:. For example, chlorpyriphos; '· · · · Pyramid derivatives: For example, pyrimiphenethyl (? 71 ^ 1111011〇8 -:, 'Λ · e: thy 1.), Lee'. Rice pound. Methyl (pyriraiphos-methyl) •-Pyrrole: For example 'such as AC 30 3-t, 6 3 0;, -... B Quizolidone: such as fenfenspira iifenazaquin); terpenes: dilute: conjugates. Derivatives. Raw materials: for example met. Hop re ne; •. ·, Tetrazines: for example ClofentezineK, Sz bu 121 Flufenzin; '…:. ·:-.:. Stele type: For example, bupr fenfen η; Blazolidines: Hexidol (P1. Hqxythiaz ο x); Triazoles: Pi. Isazophos, BH 7 988; Gasified tobacco: lindane; Macrolide ,; Defenpyra (TebufenpyradK; Fenpyroxymate; Sanchamar (Triazanate) (both pesticide products). The above-mentioned active ingredients printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs are listed in Pesticide Manual No. 8 and No. 10, and European Patent Application No. 0635499 (SZI-121), AG. Cheu. Xinya Compound Review Vol. 11 (1993) and ACS Symposium 1 Series 504, page 272. Compounds of general formula I are best used for carbamate penetration (preferably, -15- X degree is applicable to Chinese National Standard (CNS) A4 ^ 格 ί 210X2.97 mm) A7 B7 V. Description of Invention (M) Therefore, it can combat the electronic cross-barrier of the synergist, and the arthropod gasification strip with low potential The system cannot be gasified, which can remove complex molecules from the surface of the enzyme, causing paralysis of the system. This is the reason why the compound can be safely and selectively administered. In contrast to arthropods, the compound has high enzyme activity and fast enzyme binding. Over-average rapid degradation and excretion from mammals can ensure that these materials do not enhance the biotin effect seen or ingested by mammalian organisms, so it is safe and the invention proves its effect on various arthropod species β This compound is applied alone or as a synergist, and is active against insects, aphids, pupae, etc. In view of this, this fact also refers to the detoxification system of mammals with different qualities. The valuable advantage of the compound hibiscus of the present invention is that, for varieties that have evolved into resistance, the toxic dose can be reduced to the original dose of known active ingredients (measured for susceptible strains). This is not seen by other synergists »This allows the number of resistant groups to be managed safely and effectively, in compliance with regulatory rules. In addition to the above-mentioned expected advantages (which can be less expensive, less toxic to breastfeeding, selective, and inhibit resistance), the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs has printed many of these compounds with sufficient certainty. The active ingredient can be renewed, and its market has fallen behind in the past few years because it has evolved antagonism (Carbofuran, Quinalphos, Cartap, Methomyl). The compounds of the present invention create new uses and market possibilities, due to the enhancement of the effectiveness of less active materials (R e sm h t ri n, Bi oa 1 1 e t h r i n, Pi r i bi c a r b etc.) to the extent of the most active compounds, without increasing their toxicity. There are big deductions on the market; -1 6-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 5. Description of the invention (15) A7 B7 quantity but PB0 whose price rises due to the reduction of natural resources, its shortage Adhesion lies in the promotion effect of suspected tumors. The production of compounds of the general formula (I) by the compounds of the present invention can also be replaced by different compound groups, which can be carried out by chemical methods for producing special emblems of these groups. Therefore, (a) is the preparation of the compound of the general formula (IA), wherein Ar, R1, R2, Rs, R8, R7, R8, Y, E, m, 〇, p have the same meanings as above, and let the compound of the following general formula (II) :

Ar- (CRlR2) mYA 丨 丨 (II) reacts with a compound of the following general formula (m) B-(CR5R6) 0-(CR7r8) p-C = C-E (m) where Ar, R1, R2, Rs, R6, R7, R8, γ, E, B, 〇, P have the same meanings as above, A and B are groups suitable for forming an ester bond; (b) is a compound of the general formula (IB), wherein Ar, R1, R2 , R 5, R 6, R 7, R 8 Ri0, Y, E, b, ο, p have the same meanings as above, so that the following compounds of the general formula (IV): ---------- 装-. It -i., (please read ^ Notes on the back ^, " this page) Order-line-% Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Ar- (CRlR2) m-γ-c (iv 0 reacts with a compound of the following general formula (V) D-(CR5r6) 0-(CR7R8) p-C = C-E (v) where Ar, R1, R2, Rs , Re · r?, R8 · Y, E,, 〇-1 7- This paper size applies to China National Standard (CNS) A4 (210X2.97 mm) Printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 2. Description of the invention (16), P has the same meaning as above, and C and D represent groups suitable for forming an amidine bond; (c) It is a compound of the general formula (1C), wherein Ar, R1, R2, R5, R6 , R 7, R 8, E, in, η, ο, p have the same meanings as above. R 3 and R 4 refer to hydrogen, alkyl, alkenyl, haloalkyl, phenyl, and substituted phenyl, respectively. Let the following general formula ( VI) Compound: Ar-(CRlR2) m-(CR3R4) n-F (Vi) is reacted with a compound of the following general formula (vn, G-(CR5r6) 〇- (CR7R8) p-C is C-Ε (νι) where Ar, R1, R2, Rs, Re, R7, R8, Ε, η, ο, p have the same meanings as above, R3 and R4 refer to hydrogen, alkyl, alkenyl, haloalkyl, phenyl, substituted phenyl, F And G represent a group suitable for forming an ether bond; (d) is a compound of the above general formula (ID), wherein ArM CR1 R2) ra-(CR3R4) n -j-represents a carboxyamido group, β5, Re, R 7 f R 8, E, 0, p have the same meanings as above. Let the following general formula (VIII) carboximide: Ar ^-(CRlR2) m-(CR2R3) n. Nh (VIU) ~ —one-to-one— react with compounds of the following general formula (IX): Lg-(CR5r6) 〇- (CR7rB) p-C = C-E (ix) wherein R5, RS, R7, R8, E, 〇, p have the same meanings as above, and Lg represents a difficult residue; (e > is the production of the compound of the general formula (IE), wherein Ar, R1, R2, R3, R 4, R 5, R 6, R 7, R 8, R10, E, m, η, 〇, ρ have the same meanings as above, so that the following compounds of the general formula (X): _ 1 8-(Please read the note on the back first ^ (This page). Install-, νβ

This paper size applies to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (π) Ar- (CRlR2) m- (CR3R4) nH (χ) Reaction with the following compound of general formula (XI): I-(CR5R6) 〇- (CR7R8) p-C = c-E (XD where Ar, R1, R2, R3, R4, R5, R6, R7, R8, E, ffl, n, o, p have the same meanings as above, and H and I represent a group I R10 suitable for forming -N-, where R1Q has the same meaning as above; (f) is the production of the compound of general formula (IF) above, wherein Ar, R1, R2, Rs, 1ίθ, R7, R8, R9, E, m, 〇, p have the same meanings as above, so that the compound of the following general formula (XII) R9… I (XII) Ar- (CRlR2) m. C «N-OH Reaction of a compound of formula (IX), wherein Ar, R1, R2, R5, R6, R7, Ka, R9, E, η, η, ο, p have the same meanings as above, and Lg represents a hetero residue; and if Essentially, the compound of the general formula I can be converted into a salt or released from the salt, and the optical isomers can be separated if necessary. In order to produce the compound of the general formula (I), (a) the halide of the general formula (II) and An alkynyl alcohol of the general formula (ΠΙ), or a carboxylic acid of the general formula (II) and the general formula ( Π) an alkynyl halide, reacted in the presence of an acid binder, or a carboxylic acid of the general formula II and an alkynyl alcohol of the general formula (m), preferably diethyl azodicarboxylate and triphenylphosphine or a bicyclic ring Hexyl sulfonated diimide and other activators, as well as the reaction in the presence of acidic catalysts; -1 9- (Please read the note on the back of the original '1¾ this page)-Packing., 11-line paper standards applicable to Chinese national standards · (CNS) A4 specification (210X2.97 mm) A7 — ._B7_ _. V. Description of the invention (18) (b) Let the general formula (II) halogen halide and the general formula V-or secondary alkynamine, or general Carboximimine of the formula (IV) reacts with an alkynyl halide of the general formula (V), if necessary, in the presence of an acid binder; (0) make the alcohol of the general formula (VI) and an alkynyl halide of the general formula (W), or The general formula [π] halide and general formula (W > alkynol) in the presence of a base, or a general formula (milk) alcohol and general formula (W) Reacts with triphenylbenzene or dicyclohexyl sulfonium diimide and other activators, as well as in the presence of acidic catalysts; (d) Carboximidine of the general formula (VIII), in the presence of a base, reacts with the general formula < Ιχ ) Alkynyl halides, mesylate, methyl Sulfonate, trifluoroacetate, or (0 order a secondary amine of general formula (X) and an alkynyl dentate of general formula (XI), or a halide of general formula (X) and a secondary of general formula (XI) Amine, reacted in the presence of a base; (f) let the aldoxime or ketoxime of the general formula (XII), in the presence of hydrazone, and the general formula U) an alkynyl halide, mesylate, tosylate, three m Cool reaction. __ One by one ..... —- ·-....... ---------— _ ~ " 5 New compounds prepared and requested by the invention, not contained in the literature 》 '...-..............-........ The structure has been clarified after purification, and the purity is verified by TLC and GC methods. The molecular formula of the compound is proved by elemental analysis, and the structure can also be supported by IR, 1H and BC-NMR measurements. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back-1¾, and write this page)% The material can be formulated as an independent composition or with other known active ingredients of arthropod killer Mix, and according to the purpose of use, known carriers or other rib materials can be used. Therefore, by known methods, it can be prepared in concentrated solutions, microporous solutions, dusts, aerosols, vaporizers, tobacco tinctures, etc. [Rhone Poulenc-Geronazzo: Plant-protecting interface-active tincture and specialty products-20- Paper size applies Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 —1 — _-— .. —— ...... V. Description of Invention (19 ) Application Manual (1994), ICI: Handbook of Surfactant Application (1992)]. In the application process, the preparation containing the compound of the general formula I and the preparation containing the known active ingredient can be used before and after or made into a mixture. To prove the scope of the present invention, the following examples are provided, but the scope is not limited to the examples. The purity of the compound was verified by TLC and GC methods: (CP 9 0 0 0, CP-s I L-5 C B, 6O01X 0.5 3 > u n, 5 al / fflin N 2, FID, 2 2 0 * C). These methods show that the purity of all compounds exceeds 95U. The structure of the material is supported by I R, 1 Η, and C 1 3 -N M R measurements, and the molecular formula is proved by elemental analysis. 1. General procedure of alkynyl esters (A) Take appropriate alkynyl alcohol into anhydrous benzene, add pyridine, and cool the mixture to 0-5 ° C ^ Add thoron gas to this mixture at a rate such that the internal temperature does not exceed 5 ° Ce The mixture was stirred at room temperature overnight, and the precipitated pyrimidine hydrochloride was filtered off. The filtrate was neutralized with a hydrochloric acid solution, followed by washing with water and washing with saturated sodium gas solution, drying over MgS04 and evaporation of the beta product, and purification by chromatography. (B) Take 6 millimolar acid and dissolve it in 20 milliliters of dry THF, and add 1.Q g (6 millimoles) of diethyl azodicarboxylate (DEAD). The mixture was cooled on an ice-water bath, and 10 ml of THF was dissolved in 10 millimoles of alkynol and 1.6 g (6 millimoles) of triphenylene. DEAD's waiting orange faded. Search the solution at room temperature # --------- Μ 裂--s. ______ (Please read the note on the back, '. · Write this page) Order 1

-21- V. Description of the invention (20) A7 B7 overnight. Dilute with 50 ml of ethyl ethyl acetate and wash with saturated sodium hydroxide solution. Wash, dry and evaporate β. Add hexane-ethyl acetate mixture, remove from the residue Crystallize triphenylphosphonium oxide. The mash was purified by column chromatography. Compound Mp (C °) IR v (cm-1) IH-NMR δ (ppm)! 3C-NMR6 (ppm) 1.1 501 Propynyl 1,3-benzodioxo-5-carboxylic acid ester 69- 70 3270f 3010, 2922.2853, 2124. 1726, 1625, 1606, 1501, 1445, 1373, 1279, 1263, Π 57, Η 03, 1076, 1039,762. 2.51 (Hi. T, J = 2.4 Hz, sC-H ), 4.88 (2H, d, J = 2.4 Hz, OCH2-Cs), 6.03 (2H, s, 0CH20), 6.83 (1H, d, J = 8.2 Hz), 7.47 (! H, d, J = !. 6 Hz), 7.66 (1H, dd, J = 8.2, 1.6 Hz 52.34 (〇C * H2-tS). 74.92 (= CH), 77.81 (OCH2-C-) t 101.85 (OCH2〇). 107.99. 109.59 ( C-4, C-7X 123.29 (C-5), 125.71 (C 6), 147.74 (C-3a), 151.91 (C-7a), 165.07 (CO ester) 1.2 502 2-butynyl 1,3- Benzodioxo-5-carboxylic acid esters Ί 1 63-64 3016, 2959.2920, 2244, 1714, 1626, 1606, 1508, 1450, 1372, 1276, 1240, 1163, HI7, 1078, 1036, 970, 925, 758 . 1.86 (3H, t, J = 2.3 Hz, = C-CH3), 4.84 (2H, q, J = 2.3 Hz, OCH2-C =), 6.03 (2H, s, OCH2〇), 6.83 (1H (d , J = 8.2 Hz), 7.47 (IH, d, J = !. 6 Hz), 7.67 (lH, dd, J = 8_2, 1.6 Hz). 3.65 (= C-CH3) t 53.19 (OCH2-C = X 73.33 (OCH2-C-), 83.17 (sC-CH3), 101.81 (OCH2〇) 107.95, 109 .62 (C-4, C-7), 123.69 (C-5), 125.62 (C-6), 147.72 (C-3a), 151.78 (C-7a), 165.33 (COgS) ----.- ---. 1_, install II.. _C,. (Please read the precautions on the back before filling out this page) Order-T% Printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy Standard (CNS) Α4 ^ grid (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 __ B7_ V. Description of the invention (21) 2. General procedure for the block amidine solution Take the nitrogen solution and alkyneamine in pyridine In the presence, react at room temperature. The suspension was diluted, washed with water, dilute hydrochloric acid solution, sodium bisulfate solution, dried, evaporated, and purified by chromatography, and crystallized. Compound Mp (C °) IR v (cm-1) 1H-NMR 6 (ppm)! 3C-NMR6 (ppm) 2Λ N- (2-butynyl) 143-144 3334,3075,2918, 1641, 1.82 (3Hf t, J = 2.4 Hz, 3.54 (CHyC ^ l 30.37 523 3 , 4-methyldioxy 1620, 1605, 1546,1500, C // 3-C =), 3.16 (2H, m, (NH-CH2-Cs), 74.72 benzidine 1485, 1313, 1264, 1239, NH-C // 2-C =), 6.02 (2H, and 79.77 (C = C), 101.7 and 1042.s, (CH20) 2). 6.23 (NH), (OCH2〇), 107.72. 6.81 (1H , dd, J-0.6,7.8 108.02 (C-4, C-7X Ηζ, Η · 4), 7.28-7.34 (2Η, 121.70 (C-6), 128.26 (C- m, H-6, H -7) 5). 148.01 (C-3a). ≪ 150.49 (C-7a), 166.37 (CONH) 2.2 M2-butynyl) J33-I34 3295 (NH), 3055, 2922, 1'08 (3H , U = 2.1 Hz, 3.27 (CH3-C =), 29.11 (-535 2-naphthylamine 2913, 2850, 1641, 1629, CH3-C-), 3.38 (1H, s. CH2-G =), 76.77 ία 1602, 154 !, 1414, 1309, NH), 4.lO (2H, m, CH2- 78.07 (OC), 124.29 (C- 776,756 O), 7.60 (2H, m), 8.0 3) · 126. 90, 127.82 ((3H, m), 8.49 (11-1, s, H- three signals overlap), 1), 9.03 (IH, t. J = 5.3 128.08, 129.07. 131.51 i, two i-Hz ) (C-4a), 132.32 (C-2).-.! 'C 一 /, " Ό 134.37 (C-8a) t 166.07 (CO) -23- This paper standard applies to China National Standard (CNS > A4 size (210X297mm) (please read the notes on the back ',; «this page) 0. Wire-B7 V. Description of the invention (22) 23 N 5 * 11 1 " ^ 2-propynyl )-Lexamine-105-106 C- 3229 (NΗ), 3046, 2963, 2927, 2118 ,, 1635, 1618, 1590, 1576, 1531, 1415, 1301, 1245, 1033, 788,773, 759,519 2.27 (3Ht tf J-2.4 Hz, HO). 4.24 (2H, q, > 2Λ CH2-Ch), 6.52 〇H, width, Nil) 7.35 Oil, t, J = 8.l Hz), 7.50 (3H, m ), 7.84 (2H, ιη), 8.26 (lH, m) 29.62 (-CH2-C =), 71.80 (HC = C), 79.43 (H-Cs〇. 124.59, 125.19. 125.29, 126.41, 128.28, 130.06 ( C-8a), 130.85 (C-2 >, 133.?4(C·I), 133.59 (C-4a), 169.14 (CO) 2.4 h 542]-(2-butynyl)-Cai Lamine, V. ί., 120-122 u-c 3276 (NΗ), 3046, 3011, 2917, 2856, 1632, 1618, 1591, 1577, 15 22, 1444, 1432, 1287, 1258,783 1.83 (3ΗΛ J = 2.1 Hz, GH3-Ch), 4.25 (2H, q, J-2.1 Hz, CH2-C =), 6.25 (IH, s, NH ), 7.31-7.60 (3H, m), 7.85 (2H, m), 8.32 (1H, m) 3.50 (CH3-C =), 30.24 (-CH2-C-), 74.47 fQ 79.81 (CsC), 124.59, 125.19, 124.62, 125.09, 125.37, 126.39, 127.10. 128.26, 130.1 l (C-8a). 130.75 (C-2), 133.64 and 133.75 (0 * 1, CMa), 169.03 (CO) (read first read first read back Note from it. Meaning ^^ " ^ Write this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 3. General procedures for acetylenimines in anhydrous DM F solution containing phthalimide, plus 1 g A molecular equivalent of anhydrous potassium sulfonate is added dropwise to this suspension with a solution of 1 gram equivalent of alkynyl bromide in methylbenzene. The suspension was stirred at 80 ° C for 3 hours, then poured into ice water, and the crystals were collected and crystallized from 96X ethanol. -24- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A7B7 V. Description of the invention (23) Compound Mp {C °) IR v (cm " 4) lH-NMR6 (ppm) 13C-NMR6 (ppm) 31 537 8- (2-butynyl) ruimide 1 '\ c yy-'C- ^ 216-218 -L 3090, 3040 (HC aromatic), 2957, 2920 (CH aliphatic ), 2234 (Cs〇1768, 1718 (CO),! 609 (C = C Aromatic>, 1468, 1431, 1397, 1354, 1333, 1126, 1090,952, 775, 732,712, 629, 560, 532. I76 (3H, t, J-2.3 Hz, CH3.Cs), 4.32 (2H, q, J-2.3 Hz, N-CH2-C-), 7.86-7.91 (4H, m, aromatic) 3.12 (CH3-Ch ), 27.16 (N-CH2-Cs), 73.82 (CH3-C = X 79.06 (CH2-Cs), 123.48 (C-3.C-6), 131.64 (Cl, 02), 134.87 (C-4, C -5), 167.01 (CO) (Please read the note 1 on the back first --- VV write this page) 4 · (Arylalkyl) -Alkyl Fast Ethers 4.0 Manufacture 1-[(2-Butane Alkynyloxy) ethyl] -3,4-dimethylaminobenzene (compound 599) Prepare a 30 ml flask in a 50 ml flask equipped with a thermometer, magnetic stirrer, addition funnel, and connected to an inert gas system. Anhydrous THF and 1.5 g (0.03 mol) of NaH (about 90¾) Floating liquid. To the suspension, dropwise add 21 ml of anhydrous THF containing 4.0 g (0.021 mol) of the "_methyl resveratrol solution" mixture at room temperature under heating under reflux for 1 hour, cool to room temperature, add 4.1 g (0.0315 mol) of 1-bromo-2-butyne, followed by ore heating. The reaction was followed by TLC (eluent: hexane-EtOAc 4: 1). The reaction was completed in about 3-4 hours. 50 ml of the mixture was added to the cooled thick suspension and filtered on Celite plastic. The filtrate was washed with distilled water, dried over magnesium sulfate and evaporated. The residual oil was purified by column chromatography (eluent: hexane --25- This paper size applies to China National Standard (CNS) A4 (210X297 mm), -port-line-printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Consumer Standards of the Central Standards Bureau of the Ministry of Economic Affairs, printed by A7 B7 V. Description of the invention (24)

(EtOAc 4: 1, = 0.37). Yield: 2.3 g (9.8 millimolar), 46.9%. The purity of the product was determined by GC analysis (CP 9000, CP-SIL-5CB, 60 HX0.53 / U 1, 5ffll / nin N2 »FID, 250 eC) tR = 12.5 nin, > 99% 〇 Structure proof: Elemental analysis C14H17O3, 233 · 29; Calculated value: C% 72.08, H% 7. 35 Found value: C 3; 6 9 · 7 0, H% 7. 2 1 IR (CHCI3) v cm'1: 2976, 2855, 2837, 1605, 1595, 1514, 1465, 1419, 1371, 1353, 1311, 1260, 1164, 1141, 1086, 1027, 864 'H-NMR (200 MHz, CDCI3) δ: 1.46 (3H, d, J = 6.5Hz, 1.85 (3H, t, J = 2.3Hz, = C-CH3), 3.83 and 4.01 (2H, AI3Xj Jab = 15.0Hz, "αχ =" βχ = 2.3Ηζ, = C-CH! 0), 3.87 and 3.89 (cumulative 6H, s each OCHj) 4.55 (2H, q, J = 6.5 Hz, Ar-CHO), 6.80-6.89 (3H, m, aromatic). , JC-NMR (50 MHz, CDCI3) 5: 3.61 (sC-CH.!), 23.76 fCH-CHj), 55.87 (OCHi). 55.96 (= Ca-i2〇). 75.36 (sC-CH2), 76.40 ( Ar-ai-CH3), 81.91 (hC-CHj), 109.06 (C-2). 110.86 (C-5), 118.94 (C-6), 135.30 (Cl). 148.52 (C-3). 149.19 (C -4). In a similar manner as described in Example 4.0, the following compounds were prepared: -2 6- Standard (CNS) A4 specification (210X297 mm) ---------- Approved clothing II ..- > J (Please read the precautions on the back first. ≫ page) Order I line · V. Description of the invention (25 A7 B7 Consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed compounds Mp (C °) IR vCcm- *) IH-NMR δ (ppm) 13C-NMR6 (ppm) 4.1 1-naphthylmethyl Oil 3044, 3001,2945, 2920, 1.93 (3H, t, J * 2.3 Hz, 3.6 (CsC-CH3X 57.71 279 2-butynyl ether 2854, 1598, 1509, 1356, OC-f " 3), 4.22 (2H , q, (0-CH2-CC), 69.72 1166,1086,1067 J 2 2.1 Hz, 0-C // 2-CsC), C10H7.CH2-〇). 75.10 5.06 (2H, s, C10H7- (0 -CH2-C = C), 8176 C // 2-0), 7.45 (1H, t. (0-CH2-Cs〇t 124.03, J-8 Hz), 7.53 (3H, m). 125.10, 125.72, 126.19, 7.84 (1H, i J = 8.l Hz), 126.85, 128.43, 128.72, 7.88 (3H, m), 7.88 (IH, 131.79 (C-8a), 133.06.-D, J-7.7 Hz), 8.19 (1H, d, JS.2 Hz) 133.70 4.2 lU- (2-butane 3052,2977,2921,2856, 1.67 (3H, d, J-6.5 Hz, 3.64 (CsC-CH3). 22.96 292 acetylene Ethyl ethyl m 1596,1509,1444, 1371, 0 / 3-CH), 1.87 (3H, t, (CH3-CH), 56.37 (0-1095, 1078 J = 2.3 Hz, sC-CW3), CH2-CsCX 74.29 (CH3- 2.96 and 4. 丨 5 (cumulative CH >, 75.36 and 82.14 2H, ABX, JABH5.0 (CsC), 123.26 (C-8), Hz, JAX = JBX = 2 · 3 Ηζ · 123.52, 25.50, 125.85, OC // 2-CvC), 5.40 (IH, 127.92, 128.83. 130.78 0 ,, q,] = 6.5 Hz, C10H7- (C- 8a), 133.88 (C-4a). Π »1,: ': 〇 :: i- ~ 0- C CH-0 \ 7.51 (3H, m), 7.61 UH, d, J = 6.8 Hz), 7.79 ( 1H, dJ = 8.lHz), 7.89 (IH, ddJ-7.9, 1.8 Hz), 8.22 (IH, d, J = 8.l Hz) 138.42 (Cl) 4.3 Bu U- (2-butane 3058, 3048 , 3000, 2962, l.02 (3H, t, J = 7.4 Hz3.59 0.62 454 propargyloxypropyl W 2932,2923,2876, CHyC \ [2h 1.89 (3H, tv (C, H VCH2 > 30.27 2856 , 丨 598, 1509, J = 2.3 Hz, CsC-C // 3) ((CHrCH2), 56.54 (0- 1460 · 1105, 1062, 2 03 (2Htm.CHyC | / 2). CH2-C = * C ). 75 50 (O 3.95 and cumulative CH2-e * 〇, m). 1) 8 and 2H, ABX, Jab = I5, 0 81.96 (OCH-base HZ · JAX = JnX = 2-3 Hz, in o-ch2-co.! FREE 〇 OC «2-C * C), 5.I5 0H. 123.43 (C-8), 124.40. C-C " C- t, J = 6.4 1lz, C | 〇 HrC / f- 125.31, 125.36,1 25.73. 0 >, 7.53 (3H, ni), 7'59 127.91. 128.79. 131.19 (IH, d), 7_81 (lUd), (C-8a), 133.88 (C-4a). 7.89 (3H, m) , 8,27 (IH, d) 137.12 (01) Order I -3 > -27 Standards apply to China National Standards (cns) a4 specifications ⑺〇297297 mm> A7 B7 V. Description of the invention (26) Central standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 4.4 1- [2-methyl-1-oil 3051,2959,2922,2871, 0.87 and 丨 J6 (accumulative 3.57 (C ^ CH3), 19.87 472 t2-butyne gas plug) 1598, 1509, 1466, 1064. 6H. Each, J = 6Hz, ίΒ I8.77 (CH (CHj) 2). Propyl I Cai CH (C // 3) 2), 1.88 (3H. 34.20 (CH (CH3 > 2). L, y * 2.3 Hz, C = C- 56.71 (OCH2). 75.67 CH3l 2.31 (IHt (C = C-CH3), 81.77 C / ((CH3) 2 >, 3.89 and (CsC-CHj), 123.84 (C- 4.I4 (2H cumulative ABX3, 8), 125.15, 125.31. 15 Ηζ ^ αχ ^ 125.39. 125.60. 127.91 S'r: ~ -〇-; 'r C ^-' C ίτ, yBX = 2.3 Hz. OCH2). (C-4), 128.76 (C-5), ί_- 4.92 (IH, d, y-6Hz, 131.74 (C-8a), 133.87 • CH-O), 7.53 (4H, m) , 7.83 (m, d, J = 8Hz), 7.91 (IH, dd. ./ = 7.2 Hz)% 8.30 (IM, 7.6 Hz) (C-4a). 136.56 (C- l). 4.5 1-[(bumethyl (2 · oil 3306, 3049, 2990, 2935, 1.51 (3H, d. J = 6 Hz). 22.1, CHV 64.25 · OCH: 389 propynyl) methyl 2866,丨 599, 丨 510, 丨 447, CF / 3; 2.56 (IH% d, J-2 68.99, CM; 73.34, aryl- m. 1374, 1327, 丨 099, 1064 Hz), CM; 4.30 (H, qxd CH2; 83.71, CH-C: i-6.2 Η /) 〇 (Ή; 4.ι >) 124 11.C-8, I2VI7.C and 2; 125.74, C-3; I26.IH, = 15 Hz) OCH2: 7.46 C-6, 126.92. C-7; (IH, dd, J-7.8 Hz), 7.54 128.47, C-4; 128.75, C- (3H. M), 7.86 (2M, m). 5; 131.88, C-8a. 133.20, 0 8.18 (IH, mxd, J = 6 Hz) Aromatic C-4a; 133.77, Cl 4.6 256 1- [1- (2-Propanyl group > ethyl oil 3307, 3000,2979,2929, 2857, 1603,1505, 1442, (J = 6.5 Hz, C / vCHU2.44 (IH, t, 23.66 (CH3-CH), 55.55 (0-CH2 " C = C), 74.07 1 Ban 1373, 1311, 1270, 1215, household 2.4 Hz) CH, 3.92 and 76.8〇 (CH-0, 1087, 1055, 860, 821, (lH, dd, J = 2.4, 15.7 Hz) Ca〇, 79.98, (CCH ), 633 (OC / Za-CsG ^ .n (IH, 124.11, (C-6), 125.60 1 r :): j dd, J = 2.4, 15.7 Hz), (C-7), 125.90, 126.15. c; ^ QC ^ / 5-C = G > .8 4 (1H, 127.68, 丨 27.85, 128.5, q, J ~ 6.5 Hz. Cj〇H7 «133.16, 133.21. 139.75 1 C //-OX7.50 (3H, m), 7.77 (IH, si 7.85 (3H, m) (Cl)

M (Please read the notes on the back first and fill in this page) Equipment, tT-

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (27) 4.7 '293 2- [1- (2-butyne Oxy) ethyl 1Cai Ⅱ Oil L 3051,2977, 2920, 2854, 1602, 1444,1084 1.57 (3H, dJ = 6.5 Ηζ · C " 3-CH), l.87 (3H, t, J * 2.3 Hz, CHyC) t 3.90 and 4.08 (1-IH.ABX3, J-15, 2.3 Hz. 〇CHa b-CsC), 4.79 (lHt q, J = 6.5, Ci〇7-C //-0), 7.49 (3H, m), 7.77 (IH, bs, Hl), 7.85 (3H, m) 3.64 (C = C- ^ 3), 23.78 (CH3-CH), 56 23 (0-CH2-ChC), 75.28 ( OC-CH3), 76.72 (CH-CH3), 82.10 (CsC-CH3), l24.l4, (C-6) 125.42. 丨 25.78. 126.05 · 127.64, 127.80, I2S.40. 133.07 (C-4) , 133.19 (C-8),! 40.14 (C-2) 4.8 5-[(2-butyne gas oil 2997, 2946, 2921, 1.87 (3H, 1, J = 2.3 Hz, 3.52 (Me), 57.29 ( O-441) methyl) -1,3 2888,2376, 1609, Me), 4.10 (2H, q, J = 2.3 CW2-Ch), 7U5 (0 · -benzodioxo 1503.1491, 1445, Hz , 0-CW2-0 >, 4.47. C // 2-Ar). 82.54 1251.1099. 1070, (2H, s, 0-C // 2-Ar), C =), 100.9 02, 107.95, 1042,937 , 865,810 5.94 ( 2H, s, 0-C // 2 ·.), 108.71 (C-4,7) J 21.66 6.76 (! H, dJ-8 Hz, H- (C-6), 131.39, (C-5), 7), 6.8! (1H, dd, J = S.I5 147.15, 147.66 (C3a, Hz, H-6), 6.86 (IH, C-7a) J = l.5Hz, H-4) 4.9 5- [ 2-methyl-1-oil 2958, 2921,2874, 0.63 and 0.94 (cumulative 3.58 (CsC-ai3), IS.93 484 (2-butynyl) 1608,1502,1486, 6H, d! § · , 7 = 6.8 Hz, and 19.30 propyl] -1,3-benzene ΛΑ — n? 5 ϋ 1441, 1076, 1041,940 CH (CW3) 2), 1.76 (3H, ((CH (CH3) 2), 34.42 Sub-theta, 7 = 2.3 Hz, CsC- (CH (CH3) 2), 56.20 C // 3), 1.81 (1 H, m, (OCH2), 75.48 (CsC- C // (CH3) 2), 3.69 and CH3), 81.66 (C ^ C- 3 94 (cumulative: 2H, CH3), 86.25 (CH-O), ABX3, 7AB = 15.I Hz, 100.85 (0CH20), 'Ύ ,, :: '107.44, 107.63 (C-4,' -ν 0CH2), 3.86 (1H, d, J 7), 121.29 (C-6), t; 1 ί- -7.8 Hz, CH-O), 5.87 134.48 (05 ), 146.88 (2H, AB, OCH20), and '丨 47.63 (C-3a, 7a) 6.62 (IH.dd.J * 7.9, 1.6 Hz, 6-H), 6.68 (lH, • d, 7 = 7.9 Hz. 7-H), 6.71 (IH, d, 7 = 1.6 Hz, 4-H) --¾ -29-(Please read first Note the plane r '^. K Page' ^, τ

M This paper size applies to China National Standard (CNS) A4 specification (2i × 297mm) A7 B7

V. Description of the invention (28) ύ / -C 4.10 554 5-[(2-Butynyl) ring_S_ 碁 JP group] -1,3-Benzene oil 2920, 2877, 2851, 1610, 1502, 1485, 1441, 1357,1243, 1132, 1064, 1040, 942. 0.84-1.31 (6H, m), 1.50-1.77 (4H, m) 1.83 (3H, t, J »2.3Hz, sC-CH3), 2.08 (IH, m, H · 1,), 3.76 and -4.01 (ABX3, Jab = I5Hz1 JAX: JBX = 2.3 Ηζ · OCH2), 3.98 (HI, d, 1 = 8.3 Hz, CH-0), 5.97 (2H , s, 0CH20 >, 6.65-6.78 (3H, m). 3.64 (OC-CII3), 25.93 and 26.05 (Cm 26.52 (C-3), 29.25 ^ 29.86 (C-31. C-5), 43.97 (Cl ), 56.19 (OCH2), 75.57 (C = C-CH3 >, 8I .64 (ChC-CH3), 85.45 (CH-O). 100 * 88 (OCH2〇), 107.47 and 107,64 ((: · 4 , C-7), 121.31 (C-6), 134.48 (0-5), U6.9I and 147.69 (C-3a, C-7a). L · ——f ——.---- Ϊ '' (Please read the notes on the back first to fill in this page) / 4.11 555 5-[(2-Butyrocarbyl) phenylmethyl cap] -1,3-Benzodioxane 2993,2887, 2859, 1605, 1502, 1486, 1442, 1357, 1239, 1037, 937. 1.89 (3H, t, J = 2.3 Hz hC-CH3), 4.I2 (2H, q, J = 2.3 Hz, OCH2), 5.56 (1H, s, CH-0), 5.93 (2H, s, OCH2〇), 6.74-6.86 (3Hfm) f 7.25-7.39 (5 H (m) 3.69 (C ^ C-CHj): 56.34 (OCH2), 75.12 (ChC-CH3), 81.23 (C = C-CH3), 82.56 (CH-O), 100.99 (OCH2〇), 107.78 and 107.95 (C-4, C-7), 120.98 (C-6), 127.01 (C-2 \ C-6f), 127.50 (0 4), 128.36 (C-3 \ C-5). 135.54 (C-5 ), 141.62 (< M,), 147.05 and * 147.83 (C-3a, C-7a)

Ministry of Economic Affairs t Central Standard X Consumer Cooperative This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) A7 B7 V. Description of invention (29) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4.12 49J (2- Butynylmethyl) -3,4-dimethoxybenzene, / -K di ...,!. ::-Sleeve 3025, 3000, 2956, 2937. 2921,2855; 2839, ΙΟλ 1595. 1512 , 1466, 1443, 1420JI58, 1140, 1070, 1028 l.84 (3H, t, J-2.3 Hz, ChC-C // 3), 3.83 and 3.85 (cumulative 6H, * CH30), 4.08 (2H, q, J-2.3HZ, OCH ^ C = C-). 4.48 (2H, s, aryl-CH2), 6.77-6.88 (3H, m% aryl group) 3.45 (C = C-CH3), 55.67 and 55.71 57.31 (OCH2CeC -), 71.22 (aryl-CH ^), 75.0 (CsC-CHj). 82.42 (C ^ C ^ HjJJI0.76 (C-2), 111.23 (.C-5K I20.M (C-6X 130.05 (Cl) 148.58 (C-4), 148.S8 (C-3). 4.13 503 2.6-Digas + (2-butynyloxymethyl) benzene.-Emu Oil 2931,2918,2881,2849, 2241,1584 , 1563, 1473, 1356, 1198, 1157, 1091, 1073,787 / 769 1.87 (3H, t, J = 2.3 Hz, hC-CH3 >, 4.2I (2H, q, J = 2.3 Hz, OCH2-Cs) , 4.83 (2H, s, C6H4a2-0-CH2 \ 7.17 (IH, dd, J-9.1,6.7 Hz), 7,31 (2H, m) 3 .64 (SC-CH3X 58.68 (OCH2-Cs), 66.15 (C6H4arO-CH2), 74 force 4 (0CH2O), 82.81 (= C-CH3). 128.33 (C-3.C-5). 129.96 (0- 4), 133.17 (C-2, C-6), 136.97 (01) 4.14 498 1- (2-butynyl) -1,2,3,4-tetrahydrocaine… .g 〇- c ~ c = Oil 2998,2941,2860, 1604, 1489, 1440, 1070, 1044 1.84 (3H, t, J = 2.3 Hz, CsC-CW3U.83 and 3.85 (cumulative 6H, CH30), 4,08 (2Η q, J = 2.3 Hz, OCH2CsC-), 4.48 (2H, s, aryl-CH2), 6.77-6.88 (3H, m, aryl) 3.45 (CsC-CH3), 55.67 and 57.31 (OCH ^ sO X7I.22 (ar > l-CH2), 75.0 (OC-CH3), 82.42 (ChC-CH3), 110.76 (C-2) y 111.23 (C-5), 120.54 (C-6), 130.05 (0-1). 148.58 ( C-4). 143.88 (C-3) -31-This paper size applies to China National Standard (CNS) A4 (210X297 mm) A7B7 V. Description of invention (30) Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs H 4.15 479 '\ 1-(2-butynyl group) ¾ man / eij' / ik 3073, 3000, 2938, 2924, 2854, 2243, 1711, 1667, 1608, 1461, 1332, 1097, 1063, 1018 \ 1.91 (3H, t, J = 2.3 Hz, C3C-C // 3), 2.15 (I Η, dddd, J = 13.2,8.4,4.8, 3.8 Hz, 2 ^), 2.37 (1 ^ dddd, J- 15, 8Λ 6 .5, 6.5 Hz, 2-H), 2.83 (1H, ddd, J-15.8, 8Λ4. »Ha 3-H), 3.I2 (! H, ddd, J = I5,7.2,8.4,3-H ), 4.21 (2H, q, J = 2.3 Hz, OCH2), 5,14 (lH, ddt J = 6.5t3.7 Hz, IH), 7.23 7.28 (2H, m), 7.45 (1H, d, J = 7 Hz). 3.52 (ChOCH3). 30.H (C-2), 32.25 IC-3), 56.14 (OCH2), 75.45 (CsC-CH3). 8I.68 (ΟΙ), 82.15 (ChC-CH3 ), 124.80, 125.16 (C-5,6). 126.11, l2H.36 (C-4,7), 142.10, 144.14 (C-3a, 7a) · 4.16 2-[(2-butynyloxy, oil 2996, 2921,2858, l.87 (3H, t, J = 2.4Hz ,, 3.57 59.43 510 bases) sleepy bases] " (Ij 2222 · 1594 · 1 P J — 3.70 and 3.80 (2H, (0-CH2 -Cs), 65.58 • Benzodinoise ^ 1466. 1269. (〇97, 1043 ABX.iAB = IO.I Hz, (CM-ni2-0) .68.12lC- ^ Λχ ^ Βχ ^ ϋ Hz. CH- 3), 71.96 (C-2). 74.54 Difluorene / α / 2-〇λ 4.08 (IH, dd ((Cll2-Ca), 83.22 (H3C-;, hr 0 -CU ^ ^ J-7.6, 11.8 HZ .H-3P). 0 >, 117.12, 117.40 (C · I. · ^ 4.20 (2H, d, J = 2.3Hz, 5 and C-8 >. 121.37. OC // 2-C3X 4.28-4.41 121.56 ( C-6 and C-7), (2H, m, H-3a, H-2a). 143.07, 143.21 (C-4a, 6.81-6.92 (4H. M. C-8a) c6h4) 4.17 2- (2-butyne oxygen oil 3598, 3478 (wide), 2.65 (IHt t, J = 5.4 Hz, 31.18 (0-3), 64.77 539 methylmethyl 2,3- 3080,3040,2996, OH), 2.97 and 3.25 (CH2-OH), 83 02 (C-dihydrobenzofuran 2952, 2871, 1611, (cumulative 2H, ABX, 2), 109.3 ^ (0-7). 1598, 1481,1462 , JAB = 15.6Hz, JAX = 9.4 120.54 (05), 丨 24.97 1232, 1092,1050, Hz, Jbx = 7.5 Hz, H-3), (C-6), 126.48 (C-3a), 1012, 1004 , 954, 899, 3.79 (2H, m, C " 2_〇H), 127.95 (C-4X 159.08 Γ ': 〆, 865 4.90 6.79 (C-7a) (IH.d, J-8.0 Hz) f 6.87 (lH.td, J = 7.5,0.8Hz), 7.II (lH, d, J = 7.8Hz) 1-7.16 (td, J-7.2,0.5 Hz) -32----- ^ --- ^ ----- i clothing-(please read and read the notes on the back to write this page) The paper size of this book is applicable to China National Standard (CNS) A4 specification (210X2.97 mm) A7 B7 V. Description of the invention (31) -1 ^ 1 I · compound Mp (C0) IRicm · 1) [< 4.18 330 S-(-)-l- [1- (2-butane gas-based) -ethyl] -Rye, oil ah .'- cr like '1.2 292 ^ (-) 780 (c l. McOII) 〆1 4.19 331 R-(+)-l- [1- (2- butynyloxy) -ethyl] -Emu oil Like 4.2 292 (+) I 55 ° (cI. Ambient imitation) 4.20 456 ^ S-㈠ 伊 1- (2- but Huanoxy) -ethyl] -Liyou G1 :: like 4.7 293 Ό-(-) 190.8 ° (c = IO, Aminoform) 4.21 455 R-(+)-2- [1- (2- Butynyloxy) -ethyl] -naphthalene oil ig 4.7 293 (+) 199.0 ° (c = l · · 丨 7, azoform ) 4.22 474 S-(-)-2- [1- (2-propynyl) -ethyl] -naphthalene oil. $ 4.6 256 (-) 224.4 ° (c = l. 丨 8, azoform) '' 4.23 475 R-(+)-2- [l- (2-propanoxyl) _ethyl] -leaf 28-29 \% 4.6 256 (+) 228 ° (c = Kchloroform) (Please read the back first Please pay attention to this page before filling in this page) ---- Γ ----- binding. Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-33 · This paper size applies to China National Standard (CNS) A4 (210X297 mm) ) A7-. __ * _ B7_ V. Description of the invention (32) 5 · Aromatic alkylalkylalkynamine derivative General procedure: Take the amine into anhydrous benzene, add alkynyl bromide, and stir the mixture at room temperature. It was diluted with water and diethyl ether, and the phases were separated. The aqueous phase was extracted twice with diethyl ether. The combined organic phases were washed with water and dried over MgS04. (Please read the precautions on the back and write this page first) Printed by the Consumers 'Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 34 Compound Mp (C °) [R (cm-') IH-NMR6 (ppm) l3C-NMR5 (ppm 5.1 N -cr-dimethyl 51-53 3173,3053,2970, 2941, 1.455 (3H, d, CH-Me),-, 251 -N-2-propynyl 2837,2788, 1600, 2.271 (msCCH) -戌 -fluorenylmethylamine 1433, 1371, 2.360 (3H, s, NMe), 1334, 1295, 1227, 3.253-3.302 and 1123, _, 1011,969, 3.487-3.530 (2H, 952,935,900,863, CH2), 3.708-3.757 827,754,734,713, (m, m, CHMe), 557, 482 7.260-7.834 (7! Km, L Aromatic) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative, A7 B7___ V. Description of invention (33) 6. General procedure of aryl alkynyl ethers (A) Dissolve appropriate phenol in anhydrous DMF, add anhydrous K2 C03 and appropriate alkynyl halide to this solution " The reaction mixture was heated to 60 ° C and stirred at this temperature for 3-6 hours. DMF was distilled off in a vacuum, and the residue was extracted with a mixture of aeroform and distilled water. The phases were separated, and the water phase was Extracted twice by gas imitation, combined with organic phase, washed with water and saturated sodium hydroxide solution, dried on MgS04, and evaporated. The crude product was purified by chromatography. (B) Ph3 P was dissolved in water under inert atmosphere In benzene, add an appropriate alcohol to this solution, and then add phenol. The mixture is cooled to 0-10 ° C, and a small amount of DEAD (diethyl dicarboxylate) is gradually added in small portions. The temperature is maintained at 10 ° C and the β reaction mixture is stirred for 10 minutes. -2 4 hours. The precipitated Ph 3 PO is filtered off. The filtrate is washed with water, dried and evaporated. The residue is chromatographed. (C) Take 0.01 mol and dissolve it in 7 ml of anhydrous acetonitrile and cool to-in argon atmosphere. 4 ° 0: Add 1.968 g (0.0129 mol) of 0811 to this solution and keep the temperature below -4 ° C. Add 1.8 g of copper vaporized solution (π > Trifluoroacetate of the reactant. Take 0.0115 mole of alkynyl alcohol and dissolve it in 7 ml of acetonitrile. Cool the solution to -5 ° C under argon atmosphere. Add 1.98 g (0.012 9 mole) of this solution. DBU and keep the temperature below -5 ° C. To the mixture was added dropwise 1.6 g (01 15 Moore) of trifluoroacetic anhydride, keeping the temperature below 2 ° C. The resulting mixture -35- (Please read the notes on the back ¾, 舄 this page)-installed ·, tr .......- 一 " -.'-. Dllllulluiul · · this paper; Chinese National Standard (CNS) A4 specification (210X297 mm) 5. Description of the invention (34 A7 B7 compound was stirred in OeC for 30 minutes. The obtained trifluoroacetate solution was added dropwise to the first solution, keeping the temperature below 0 ° C The mixture was stirred at 0 ° C for 5 hours. After the reaction was followed by the end of the TLL reaction, the mixture of acetonitrile < > and 150 ml of benzene and 50 ml of water was distilled in a vacuum. The organic phase was shaken with 1N hydrochloric acid, 1N sodium hydroxide, water and saturated sodium nitride solution were washed, then the product was dried and evaporated to purify it by employment analysis. Compound Mp (C °) IRicm · 1) IH-NMR 6 (ppm) l3C-NMR6 (ppm) 6.1 547 Tris (3-butynyl) -4-nitrobenzene .- .: r 92-94 3287.3111,3085, 3075,2964,2947, 2920,1609,1596 Ι5ί0, 1466, 1344, 1333, 1263, 1179, 1110, 1019,856,846, 753,669,653. 2.07 (IH, t J = 2.6Hz, 2.73 (2H, td, J = 6.8, 2.6 Hz, C // 2CeC). 4! 8 (2H. T. J = 6.8 Hz, OCH2 \ 6.9 7 and 8. 丨 S (4H, dm, J = 9 Hz, C6H4> 19.37 (CeC-CH2). 66.60 (CsCH), 70.38 (OCH2), 79.62 (C = CH). Π4.5Ι (02. C -6), 125.89 (C-3.C-5). 141.73 (C-4), 163.40 (Cl) 6.2 540 1- (3-pentynyl) -4-nitrobenzene;-< · 77 -78 3067, 3048, 2963, 2917, 2886, 1923, 1607, 1594, 1512, 1467, 1403, 1339, 1260, 1178, 1110,866, 856, 75J, 694,648, 628, 522, 506. 1.78 (3H, t, J «2.3 Hz, OOC // 3), 2.66 (2H, m, CW2OC >, 4.12 (2H, t, J = 7.0 Hz, OC // 2), 6.95 and MS (cumulative 4H, dm. J- 9 Hz, C6H4) 3.57 (C = C-CH3), 19.61 (CsC-CH2), 67.26 (OCH2), 74.27 (CsC-CH3), 77.84 (C = C-CH3), " 4.49 (C-2, C · 6). 125.85 (C-3.C-5), 141.59 (C-4), 163.59 (Cl). 36-. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --- -, -----— Equipped!.. ____ (Please read Note V on the back to write this page) Order

A7 B7 V. Description of the invention (35) 6.3 377 2,3-Diargon-2,2-dimethyl-7- (3-butynyloxy) benzofuran: 'XV 78-80 3277,3071,3043 , 2970, 2923, 2889, 2858, 2119, 2022, 1874, 1795, 1714, 1656, 1624, 1611, 1591, 1492, 1470, 1440, 丨 492, 丨 396, 1385, 1371,1302, 1283, 1244, 1201 , 1172, U28, 1077,999, 972,946,887,838, 780. 753, 720, 682,663,635,600,546, 502,458 1.512 (6 ^ s (diMe), 2.033 (lH, t, CH >, 2.710 (2H, m.-CH2C), 3.027 (2H, s, CH2-ar), 4.206 (2ΗΛ 0-CH2), 6.739-6.815 (3H, m, aromatic) 19.12 (CH2-C), 27.88 (diMe), 42.93 (C-3), 66.79 (C-2), 69.61 (0-CH2), 79.96 (CCH), 87.06 (CC), 113.31 (C-6). 117.86 (C-5),! 19.99 (C-4), 12S36 (C-9 ), 142.62 (C-7), 147.52 (C-8) 6,4 2,3-dihydro-2,2- 58-59.5 2977, 2963,2942, 1.510 (6H, s, diMe), 3.471 (Me ), 19.63 413 dimethyl-7- (3- 2918, 2880, 2849, 1.800 (3H, t. Me), (CH2-C), 28.l8 (diMe), pentynyl) benzo 1621, 1591, 1492, 2.627-2.672 (2H, m,-43.26 (C-3), 67.54 (C-furan 1468, 1389, 1369, CH2Q, 3.023 (2H, s. 2), 74.82 (CC-Me), L 1329, 1305, 1286, CH2-ar), 4.I50 (2H. T. 77.32 (0-CH2). 87.26. 丨 1245, 1203,1174, 0-CH2). 6.751-6.784 (CC), 113.21 (C-6 ), 1135, 1115,1080, (3H, m, aromatic) 117.87 (C-5), 120.25 1065,966,947, 881, (C-4), 128.48 (C-9), 860, 841,779,751, 143.12 (C -7 >, 145.00 718, 634, 598,532, (C-8). 499. (Please read the legal notices on the back before filling this page): Pack-

Printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs. The paper is printed in accordance with the Chinese National Standard (CNS) A4 (2IOX297 mm). Printed by the Consumer ’s Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 _B7__ V. Description of Invention (36) 7. The general procedure of oxime ethers is to convert the oxime to an oxime ether in a traditional manner, that is, to make it react with the alkynyl bromide in dimethylformamide in the presence of potassium acetate (see Method A for the production of naphthyl ethers). The crude products were refined by column chromatography. Compound Mp (C °) iRCcm-1) 1H-NMR 〇 (ppm) 13C-NMR5 (ppm) 7.1 571 1-acenaphthoxime- (2-butynyl) ether oil 2990, 2919, 2853, 2230, 1604 , 1591, 1459, 1436, 1363, 1353, 1309, 1252, 1034, 1017, 1002,912 1.94 (3H, t, J = 2.3 Hz, CH3-0), 2.41 (3H, s, CH3-ON), 4.84 (2H, q, J = 2.3 Hz, 0-CH2), 7.46-7.57 (4H, m), 7.87 (2H, m), 8.15 (1H, m) 3.80 (CH3-Cs) f 17.51 (ai3- C = NX 62.25 (0-CH2), 75.33 (CH2-Ch), 82.75 (CH3-Cs), 125.15, 125.46 (C-6, C-7), 125.96 (C-3), 126.01 (C-3) , 126.49 (C-2), 128.40 (C-5), 129.10 (C-4), 130.85 (Cl), 133.86 (C-4a), 135.27 (C-89), 157.41 (CH3-C = N) 7.2 572 3,4-dimethoxyethenylphenoxy m- (2-butynyl) ® 85: 3080,3003,2963,2929, 2869,2840,2237, 1595, 1577, 1518, 1447, 1417, 1337, 1311,1278, 1249, 1234, 1176, H53, 1030, 937,879,804,768,634, 621 1.87 (3H, tJ-2.3 Ha CH3-0), 2.23 (3H, s, CH3-C = N), 3.88 and 3.90 (CH3O ), 4.75 (2H, q, J = 2.3 Hz. 0-CH2), 6.83 (IH, d, J-8.4 Hz), 7.15 (IH, dd, J = 8.4, 2 Hz), 7.29 (lH, d, J-2 Hz) 3,77 (CH3-Ch), 1176 (CH3-C-NX 55.86 (CH3 〇), 62.23 (0-CH2), 75.27 (CH2-O), 82.53 (CH3-C =). 108.8 (C-5), 110.51 (C-2), 119.28 (C-6), 129.18 (C- 1), 148.78 (C-3), 150.14 (C-4), 155.0 (CH3-C = N) Please read the 'Notes' on the back ^ & write this page)-I-. / _ \! --- Binding and binding ♦ The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (37) Activity result: g 觖 例 1 New research partner Mi (Mhsc? ≫ dnmostica) was effective after application. In two parallel experiments, 10 female houseflies born 2-4 days old were assisted by Hamilton MicroLab P micro-consumer on the ventral side of the chest. 2 > u 1 test solution treatment "In addition to a fixed synergist dose of lQOOng each, the other was treated with carbofuran at a dose of 20 ng each. As the solvent, fibrinolysin was used. Housefly selection and calculations were performed under the role of C02. After treatment, houseflies were kept in plastic cups and covered with tulle. 24 The lethality after 4 hours is expressed in%. The results are listed in the table below. I ---, ----- 1, installed II-,. \ (Please read the notice on the back page first) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Carbofuran + Synergist (per ng) M Division 20 + 0 20 + 1000 Lethality% alkynyl esters, aldehydes, amidines 501 3 53 502 0 47 523 0 17 535 3 27 541 0 46 542 0 42 Arylalkyl alkynyl ethers 279 0 72 256 0 32 441 1 97 484 0 63 493 1 100 599 10 100 503 0 95 292 0 72 293 0 45 -39 " The paper size of the book is applicable to China National Standards (CNS) A4 specifications (210X297 mm) V. Description of the invention (38) A7 B7 454 0 75 472 1 68 479 I 58 330 0 62 331 0 IX 455 0 70 456 0 47 389 2 27 554 0 58 555 0 90 539 0 48 474 0 50 510 2 75 498 5 70 475 0 47 Aromatic courtyards " Academic-fast amine derivatives 251 2 37 Aryl alkynyl ethers 547 0 47 540 0 60 377 0 57 418 0 63 Aralkylaldoximes, Ketooxime fast_class 571 0 53 572 0 55 ---------- install-`` f '· (Please read the notice on the back first ^^ this page) Staff of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative cooperative print window case example 2 Study on the monk-effect live pupa of cotton hex moth (Helicoverpa armigera) after using it in a similar manner as in Example 1, except that the cottonseed moth L2 stage The insects were treated experimentally. From the 24-hour dose, the probit analysis was used to determine the LD50 (ng per larvae) value. No synergist effect. -40-This paper is in accordance with China National Standard (CNS) A4 specifications. (210X297 mm) A7 B7 V. Description of the invention (39) A dose of 1000 ng per larva was applied. The LDS0 value of carbofuran administered separately was divided by the quotient of the synergist to calculate the synergist ratio. Repeat the experiment 2-4 times. The synergist ratio is listed in the table below. Materials' Synergist ratios are alkynyl esters, amidoamines 501,502,523,535,541,542,537 > 5 arylalkylalkyl alkynyl ethers 279,256,441,484,493,503,292,293,454,510,475,498,479,472,331,455, 456,389,474,555,555,539,555,539 5 Aromatic alkylalkylalkynamine derivatives 251 > 5 Arylalkyne successors 540,377,418 > 5 Alkyne oxime ethers 57 1 572 > 5 Plutonium neodymium spectrum preparation ----; ----- • — equipment-t, ^ (please read the notes on the back first 'V write this page) Order the invention printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Material 279 and 599 to various Synergistic activity of the ingredient, be determined using the method of Example 1 and processing 2 shown in FIG. The active ingredient uses the ISO common name (see Pesticide Manual 1994). The synergist obtained is as follows: 41 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 5. Description of the invention (40)

7 7 AB Active ingredients 279 599 Musca domestica cotton seed moth Musca domestica cotton moth synergist soil synergist t carbofuran > 20 > 10 > 40 > 20 bendiocarb > 20 > 10 > 40 > 20 isoprocarb > 40 > 40 > 20 fenobucarb > 10-> 20-aminocarb > 20-> 20-thiodicarb > 10-> 10-methomyl > 10-> 10-pirimicarb > 20- > 20-dioxacarb > 20-> 40 J > 20 propoxur > 20 > 10 > 40 > 20 imidacloprid > 5-> 5-lindan > 5 > 5--azinphosmethyl > 5 > 5--chlorpyriphos > 5 > 5--esbiol > 5-> 10-permethrin > 5 > 10 tetramethrin > 5 • (Please read the precautions on the back before filling this page) Order

______ »Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -42-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 V. Description of the invention (41) Case example 4 The hate cut hh uses the Hamilton MicroLab P drawdown depletor for the dysprosium neodymium and the living God's eve neodymium neodymium, and is processed as described in Example 1. In two parallel experiments, 10 female houseflies born 2-3 days old were treated with a 0.2 // 1 test solution in the chest and belly mistletoe. In addition to a fixed dose of 1000-400-200-80ng of each housefly, each housefly was treated with a certain 2flng carbofur_an dose. After the selection and counting of house flies under the action of (; 〇2), the house flies were stored in plastic cups and covered with tulle. After 24 hours, lethal percentages were recorded. Depending on the results, repeat experiment 2- 4 times. The results are listed in the table below. ---- ^ ------ 1 Race II, .. t. (Please read the notes on the back first, '->, .. write this page) Ministry of Economy Dosage of synergist for printed materials of consumer cooperatives of the Central Bureau of Standards (Housefly ng > 0 80 200 400 1000 2 4-hour lethality (%) 50 1 0 60 7 5 80 80 4 4 1 0 62 67 90 95 493 0 7 5 88 94 10 0 503 0 3 7 50 65 93 4 54 0 40 4 5 60 75 4 55 0 2 5 48 63 7 7 599 0 6 5 90 95 100 -43-The size of the paper used for the edition is in accordance with Chinese national standards ( CNS) A4 specification (2! 0'〆297mm) A7 B7 V. Description of the invention (42) Tube Example 5 Study on the neodymium-resistant birch which is inferior to the family's family in Hangzhou In terms of resistant housefly (INSEL, IX), the synergistic activity of various active ingredients was studied as described in Example 1, and the synergist was determined according to Example 2 |: | ^ --------- — 装--ί One (Please read the back Implications θ, this page) Order ill Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -44-Processing 1NSEL, a species of carbofuran + 279 LD50 | SR {per housefly ng) LD50 1 SR (each housefly ng) 15375 29 530 > 100000 94 4760 methomyl + 279 475 46 10 851 109 5 pirimicarb + 279 > 100000 696 145 > 100000 3562 115 aldicarb + 279 695 172 4 2104 507 4 bendiocarb + 279 100000 150 667 100000 746 134 isoprocarb ▲ 279 > 100000 983 102 > 100000 2145 47 esbiol + 279 10653 794 13--This paper size applies to China National Standard (CNS) A4 specifications (210 × 297 mm) A7 B7 V. Description of invention (43) The live strain of Rhodesiphum Padi was sown in a plastic cup of oat plants 5-8 cm tall and grown in different ways. Oat aphids of the same size were infected. Settled aphids were calculated before treatment, and then manually sprayed In addition to taking a fixed dose (30ppib) of the synergist, spray with 1 ml of spray. The compound No. 279 of the present invention was prepared into an emulsifiable concentrate having a concentration of 100 g / 1 by using a common preparation method, using a solvent and a surfactant. From this concentrated solution and a commercially available preparation, a spray solution was prepared by dilution. After 24 hours of treatment, the results of measuring the lethality β of aphids are as follows: Please read the note of φ. Load the lethality of treatment% carbofuran 1 ppm < 50 carbofuran 1 ppm + 279 > 9 5 pirimor 2 ppm < 30 piri bo r 2 ppm + 279 > 95 imidacloprid 0.1 ppm < 50 iaidacloprid 0.1 ppm + 279 > 95 Ordered by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to print a real mistletoe 7 Research on the family gate 銮 銮 neodymium _ new hatch 5 0 A group consisting of males and 50 female houseflies was fed with sugar nine including materials of the present invention 4 4 1 and 4 8 4 50 0 ρ ρ Β within 48 hours, and the number of eggs laid was increased within ten days. . The effect of hindering the insemination rate is expressed by the treatment of this paper size to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (44) and the housefly quotient of untreated groups. The experiment was repeated 4 times. Treatment Blocking effect on insemination rate 4 4 1 87% 484 90% Ning Lun Case 8

(Tetranvchus urt. Ioaf >) ^ M The effect of neodymium from the first pair of leaves of a 1-week-old bean plant, cut into round leaves H with a diameter of 22 5 sides, and immersed in a test consisting of a certain concentration of active ingredients and synergists Treatment 5 minutes "To prepare a stock solution of the desired concentration, 10 X acetone was used as a co-solvent, and QU Tween-80 was used as a cleaning agent. Dry leaf crickets were placed on a wet surface and each leaf was infected with 10 growing female lice. After 48 hours, use the display mirror and brush to record the fatality rate. The experiment was repeated 4 times. The average results are listed in the table below. (Please read the note on the back ^ J first write this page) Binding 'Order Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs · This paper size applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm>

B V. Description of the invention (45)

Treatment concentration of single active ingredient (PPB) 31 62 125 250 500 Lethality% 279 0 6 8 18 30 carbofuran 13 39 44 81 90 bromoropylate 18 28 90--Concentration (ppra) Combination active ingredient treatment 16 + 16 31 + 31 62 + 62 125 + 125 250 + 250 lethality% 279 + carbofuran 29 80 80 100 100 279 + bromopropylate 75 90 100--tube case 9 Μ M i \ f ^ Μ (1. ft ο t. Ί η 〇 〇. arsa decemlineata) ffl ^ M ---------- Tu Yi-_ *-~, (Please read the note on the back-write this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The test of neodymium and dysprosium uses a method commonly used in formulating practice to apply a solvent and a surfactant to prepare the compound No. 279 of the present invention into a 100 g / l emulsifiable concentrate. In a small area pastoral that was studying the resistance to Corolladus potato worms, a Chinufur 40 FW composition including 400 g / 1 carbofuran was applied together with a fixed dose of 2 liters per hectare of Compound 279. Apply 300 liters / ha of liquid for spraying with a motorized sprayer (Yuanshan brand). For the 2 5 nf area -47-one-to-one line · This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (46) The domain is repeatedly processed 4 times. The next day, live tapeworms were counted on the plants to evaluate the treatment effect. The results are shown in the table below: Treatment dosage (liters / acre) carbofuran: 279 than the number of potato bugs per plant before treatment Untreated after treatment- '-23.6 28.0 Chinufur 40 FW 0.1 1: 0 18.4 6.1 Chinufur 40 FW 0.2 1 : 0 32.0 6.8 Chinufur 40 FW + 279 〇.1 + 2.0 1: 5 21.3 0.4 59Q 諕 The same effect of the same effect 忡 I --------------- I-\ 1 /- '(Please read the precautions on this page, this page first) Example 糇 glM 0 Using the method described in Example 8, the synergistic activity of compound 59-9 and various specific pesticides on two-spotted spider lice was studied. The L C 50 and L C9i values calculated from the concentration and lethality thresholds are listed in the table below. -Order

-Line_ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -48-This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) A7

V. Description of the invention (47) Treatment of pesticides / sowing μ μ exposure LC50 LC95 synergistic fcb (mg / 〇SR ^ 〇SR »'Carboftjran 1: 0 24 163.9 799.9. · • Carbofuran + MB-599 1: 1 24 55.5 286.8 3.0 2.8 --- 1: 2 24 33.5 93.7 4.9 8.5 1: 4 24 27.5 67.0 6.0 Π.9 Fenazaquin 1: 0 3 > 1000---1: 0 24 41.9 801.3-Fenazaquin + PBO 1 : 1 3 326.7 > 1000 > 3 A --- " 1: 1 24 20.4 371.8 2.1 22 Fenazaquin + MB-599 1: 1 3 68. t 280.2 > 15 * 1: 1 24 31.3 174.8 1.3 4.6 Tebufenpyrad 1: 0 3 > 1000------ 1: 0 24 63.4 > 1000--Tcbufcnpyrad + PBO 1: 1 3 115.9 1081 > 9 __—- ^ 1: 1 24 35.7 118.0 1.8 > 8.5 Tcbufenpyrad + MB599 1: 1 3 61.8 658.7 > 16 a-^ > 7.0 1: 1 24 22,3 141.8 2.8 I (IΊ11 — IΊ equipment-(Please read the notes on the back first (this book)) Order the Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the People's Republic of China) Example 1 1 The field test of Agyrthosiphon piaun was tested in a small area (10 nf) in the field, and the compound No. 5 9 9 was tested as a potentiator of Bean @ Active '' using motorized spray (Yuanshan brand> 3ΰί per hectare spray) Liter capacity 丨 The average number of insects per leaf before and two days after treatment. The effect is expressed. (Henderson and Tilton: J. Econ. Entomol., 4 8: 1 5 7, 1 9 5 5). The results are shown in the following table. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). 5. Description of the invention (48) A7 B7 Treatment dose per hectare of active ingredient, efficiency (%) ) Pirimicarb 250 93.8 80 86.3 Pirimicarb + MB-599 80 + 80 95.5 Fipronil 240 94.6 Fipronii + MB-599 120 + 120 95.7 Carbofuran 160 99.1 110 98.0 Carboftiran + MB-599 i10 + 110 100.0 Triazamate 50 96.8 Triazamate + MB-599 33 +33 97.7 Imidacloprid 120 98.4 Imidac 丨 oprid + MB-599 120 + 120 100.0 Practical example 1 2 龃 R knows the reference 捎 f: h age study on homes treated with carbofuran and 1000ng known synergists For the fly, the LDso value of the reference compound was measured 4 times, and the SR50 ratio was calculated relative to the control carbofuran. These SR50 ratios were compared with the novel compounds prepared by the present invention. It shows that the compounds of the present invention are more active β (Please read the Caution Matters on the back side first. This page) • Packing. Order bit-line-Printed on paper standards of China National Standards (CNS) ) A4 size (210X297 mm)

7 B V. Description of the invention (49) 1. The alkynyl esters are known to be synergists of the present invention than 2-propynyl-1-naphthyl carboxylate 520 SR50.11.28 (arylalkyl) -alkylalkyne Ethers are known in the present invention as a synergist than (2.6-dichlorophenyl) methyl 2-propynyl ether 503 SR so 20.92 2 1.16 --------- 1 ^ .---〆 ' J ~ (Please read the note on the back for 'j to write this page) -9 It is known that the synergist of the present invention is 5-[(2-propynyl) methyl] -1,3-benzodioxo 44 1 SR 5〇10.60 25.70 -line. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs • 51. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm> A7 B7 V. Description of the invention (5) The synergist of the present invention is known to be biphenyl methyl 2-propynyl ether 279 SR 50.5.28 28.7 The synergist of the present invention is known to be 2-[(2-propynyloxy) methyl] -1,4-benzene Benzodioxo 510 SR so 5.58 18.32 Known in the present invention, please read the following precautions and install the synergist ratio (2-propynyloxymethyl 3,4-dimethylaminobenzene 493 SR 5). 6.58, 32.84 This paper size applies to Chinese National Standards (CNS> A4) Grid (210X297 mm) Ministry of Economic Affairs Bureau of Standards printed 52 employees consumer cooperatives

V. Description of the invention (si) 3. The aryl alkynyl ethers are known to the present invention (please read the notes on the back first; 'Printed by the Consumer Standards Cooperative of the Central Standards Bureau, Ministry of Economic Affairs, known naphthyl alkynyl ether enhancement ratio s R 50 1- Naphthyl 2 -propyne M 6.52 1-Zeidyl 3-butynyl ether 7.95 2- • Zeidyl 2-butynyl ether 7.72 2--Zeyl 3-pentynyl ether 9.97 -53- Pack- , This page) Order | line_ 丨 _ synergist ratio 2,3 -diazine ** 2,2-dimethyl-7- (2-propanyl) benzofuran 4 18 SR 5〇1.8 2 0.5 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)

7 7 AB V. Description of the invention (52) 4. Known alkynoxime ethers The synergist of the present invention is better than 1-acetamone oxime (2-propynyl) ether 57 1 SRso 2.79 10.02 Release example-commercially available auxiliary The name of the rib material is listed in parentheses, followed by the name of the manufacturer. 1. Manufacture powder (A) Mix 158 grams of fine-grained pearlite * 20 grams (3811 > 1) in a homogenizer, 2011 ^ 11 and 20 grams of compound No. 2-9, add 2 grams of fatty alcohol to this mixture Ethionase 3920, ICI), homogenize the mixture. The powder mixture was granulated in a jet mill, where 5 grams of cinnamopolyglycolic acid (E0 = 20) (Triton X-165, Rohm and Haas Company) and 2_ grams of succinyl dibutyrate were added. (Aeroso Bu 13, Gasamine Corporation). The resulting product was a wettable powder blend (WP). (B) The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed 10 grams of Compound No. 279 and 10 grams of carbofuran and diluted with 2 grams of ethanol. The solution was in a powder homogenizer with 5 g of calcium lignin sulfonate (801 ^ 68 卩 6360 &, 80-1 ^ 6 bar & company), 5 g of nonanol polyglycol (E0 = 20) (Arkopal N-200, Hearst Company) and 70 grams of calcium gallate 54 This paper size is applicable to Chinese national standards (CNS> A4 specification (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Explanation of the invention (53) The product obtained by mixing is granulated in an Alpine-100 mill. The average particle size is l-2> uffl. This composition can be used to make a complete suspension. (C) 3 g of D i azinon , 3 g of compound No. 441 and 0.3 g of fatty alcohol polyethylene glycol acid (G -3920, ICI), in a homogenizer device, for 1.0 g of synthetic oxalic acid (Aerosil 2 0 0> and 191 g Extraction of a mixture of talcum powder (dmax = 1 5 ~ 30 Μ twist), the pH of the latter is adjusted to P Η = 7.0 with osmium phosphate and sodium osmium in advance. Add 1 g of sulfobutane under stirring Dioctyl diacid (Α er 〇s ο 1 0 T B, cyanamide company), and 1 g of fatty alcohol polyglycol ether sulfonate (Genapol LR D, Hirst >, and finally granulate the mixture to an average particle size of 20. The product obtained is a free-flowing powder formulation. 2. Manufacturing an emulsion ring (A) Take a mixture of 5 grams of pirimicarb and 5 grams of compound 493 , Dissolved in a mixture of 20 grams of xylene and 40 grams of propanol. To this solution was added 4 grams of ethoxylated alkylphenol + straight alkyl alkyl aryl sulfonate calcium salt Ueronol FF / U 6 e ronazzo company ) And 6 g of ethoxylated amine + fatty acid + straight aryl aryl sulfonic acid age metal salt (Geronol MS, Geronazz 0 company). After completely dissolved, add 20 g of water to obtain a transparent solution, its characteristics are When diluted with water, an emulsion with a droplet diameter of 0.8-1.5 m was formed. (B) Take a mixture of 5 g of quinalphos and 10 g of compound No. 484, and 7 g of ethoxylated-(E0 = 13)- Propoxylated _ (P0 = 21) nonylphenol, 2 grams of linear dodecylbenzenesulfonic acid calcium salt and 12 grams of POE- (20) -sorbitan mono-55-I;-, ... · Ι -------- install! (Please read the cautions on the back page first) | Line | This paper size applies to China National Standard (CNS) A4 (21 〇X 297 mm) Order printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2. Description of the invention (.54) A mixture of oleate, dissolved in 28.6 ~ 28.6 ml of propylene glycol and pine fatty acid, and 23.8 ml of sunflower oil, 9.5 ml of hexanol and 95 ml of aliphatic hydrocarbon. In the mixture, the naphthenic constant 45丨. The resulting material is preferably used to make a demulsifier. (C) Take 0.02-0.02 parts by mass of the active ingredient and synergist mixture, dissolve in 10 parts by mass of propanol, add 99.96 parts by mass of odorless petroleum to the resulting solution, and stir the mixture to obtain a homogeneous solution. The resulting oily dispersant can be used directly in ULV applications. (D) Following the method described in (A), but using 10 g of compound No. 279 as a synergist active agent. 3. Manufacture granules In a mechanical granulator, mix 300 g of carbofuran, 300 g of compound No. 418, and 1500 g of polycarboxylic acid phosphonium osmium salt (Sorphol, Toho >, 500 g of dodecyl) Sodium besylate (Harlon TP 370, Hills), 500 g of beet sugar and 72 D0 g of kaolin. The resulting powder mixture was mixed with a high shear (v = 10ffl / s) mixer with 8300 ml of water. The mixture was finally sprayed Dry particle size distribution of the product is 0.1-0. 4 1811. 4. Manufacture of gaseous solvents In a liter device equipped with a stirrer, mix 1 kg of bioallethrin, 0.5 kg of compound No. 441, fl.l kg of gaseous solvent air 9 7 2.1 kilograms of ethylene glycol monosalicylate, 15 kilograms of odorless petroleum, and 50 kilograms of propanol. After dissolving, it is mixed with 3 3.3 kilograms of liquid cyanohydrin (2 5 -7 5) gas. ， Filling into the gas tank 〇-56- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back of the factory first. \ Write this page): Packing--, tT. A7 B7 V. Description of the invention (55) 5. Manufacture the evaporator to dissolve 5 g of S-bioallethrin in 60 ml, 5 g of 2 7 9 inner tube Steamed at a temperature of 5 ° C ο 5 ° C in a liquid-soluble material lemon lemon g 1 ± and Wuhe 1, .--, ------- packing-(Please read the precautions on the back of the factory first \ (This page) Ordered by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm).

Claims (1)

A8 B8 C8 D8 6. Application for patents Fan Yuan (Article of King Wang) 1 · -β Compound represented by formula (I) or its optical isomer or salt: Ar · (CRlR2) m · (YR3R4) n. X. (cr5r6) 〇. (CR7R8) p-c ® C-Ε Among them, Ar is printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperative, and Ar is tetrahydroceryl, naphthyl, benzodioxo, benzene, and benzofuranyl tetra ^ benzene. Benzyl, indenyl; optionally substituted by one or more alkanoyl, methyldioxy, alkyl, halogen or nitro groups; hydrogen, alkyl, phenyl, cycloalkyl, R 2 is hydrogen, R3 and R4 are hydrogen alone, or R 3 and R 4 together form gas; Y is c, or R θ I YR 3 R 4 together form -C = N-group; X ^ -0-; NRio-; R 9 is hydrogen and alkyl; Ri0 is hydrogen and alkyl; ^, position 6, ^ 7, 1 ^ is uncovered as chain, alkyl, or Ar- (CRl R2 > m_ (YR3 R4) n_b) Carbaminimide formation: ... E is hydrogen, methyl; B is 0, 1, 2: η is 0, 1; 0 is 0.1, 2; P is 0 · 1, 2; (CR1 R2) m- (CR3 R4) n -X- (CRS Re > 〇 (CR7Re) p The sum of the atoms or radicals is 3, and-CsC-E side frame and (锖 E first read the back of the note Then fill out this page) book (0 China 0 Paper scales applicable standard (CNS > A4 size (210X297 mm) A8 B8 C8 D8 6. Application for patents Fan Yuan (Article of King Wang) 1 · -β Compound represented by formula (I) or its optical isomer or salt: Ar · (CRlR2) m · (YR3R4) n. X. (cr5r6) 〇. (CR7R8) p-c ® C-Ε Among them, Ar is printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperative, and Ar is tetrahydroceryl, naphthyl, benzodioxo, benzene, and benzofuranyl tetra ^ benzene. Benzyl, indenyl; optionally substituted by one or more alkanoyl, methyldioxy, alkyl, halogen or nitro groups; hydrogen, alkyl, phenyl, cycloalkyl, R 2 is hydrogen, R3 and R4 are hydrogen alone, or R 3 and R 4 together form gas; Y is c, or R θ I YR 3 R 4 together form -C = N-group; X ^ -0-; NRio-; R 9 is hydrogen and alkyl; Ri0 is hydrogen and alkyl; ^, position 6, ^ 7, 1 ^ is uncovered as chain, alkyl, or Ar- (CRl R2 > m_ (YR3 R4) n_b) Carbaminimide formation: ... E is hydrogen, methyl; B is 0, 1, 2: η is 0, 1; 0 is 0.1, 2; P is 0 · 1, 2; (CR1 R2) m- (CR3 R4) n -X- (CRS Re > 〇 (CR7Re) p The sum of the atoms or radicals is 3, and-CsC-E side frame and (锖 E first read the back of the note Then fill out this page) book (0 China 0 Paper scales applicable standard (CNS > A4 size (210X297 mm) A8 B8 C8 D8 central Ministry of Economic Affairs Bureau of Standards staff t consumer cooperatives printed The scope of the patent application is that the bridge atoms form a straight chain, containing 6 掴 atoms, and the terminal is preferably a methyl group. Furthermore, for example, Ar represents a drug group, Y means a sulfonic atom, X means an oxygen atom, and R 3 and R 4 cannot represent oxygen together. In addition, if Ar refers to naphthyl, "" is 0, η is 0, and X is oxygen; RS, Re, R7, and R8 are Η, and E? Is free, or if Ar refers to phenyl or naphthyl substituted as necessary , 刖 m is 0, η is 1, Υ is c, X is 0; R3, R4, Rs, ret R7 # R8 is H, or ^ 冏 is oxygen; R θ I or YR 3 R 4 — The same represents -C = fj- group, in which R 9 is hydrogen, or alkyl, and E = Η. A compound represented by the general formula (IA) or an optical isomer or salt thereof: Ar-(CRl R2) m-Υ-0-(CR5r6) 0-(CR7R8) p-c 3 C-Ε 〇 (IA ) Where A r, R 1, R 2, R 5, R e, R 7, R 8, γ, E, η, 0, p have the same meaning as the first item in the scope of the patent application e. A general formula (IB) The compound or its optical isomer or salt: Ar-(CRlR2) m-γ-N. (CR5r6) 〇_ (CR7R8) p-c Ξ C-E OR10 (IB) where Ar, R1,! ^, The meaning of R5, Re, R7, RS, Ri0, YE, n, 〇, P is the same as the one in the scope of patent application. For the compound or the optical isomer or salt of the first scope of patent application, the formula is: Ar-(CRlR2) m-(CR3R4) n-〇- (CR5r6) 〇- (CR7R8) p-C 兹 C-E (IC) where Ar.R1, R2, R3, R4, rs, Re, R7, r8 -2-(Please read the notes on the back before filling this page) The size of the order paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 Patent application park, E, m, η, ο, p has the meaning as claimed in item 1 of the patent scope β 5. Such as the compound or the optical isomer or salt thereof in the scope of patent application 1 , The formula is Ar-(CR ^ R2) m-(CR ^ R4) n-N-(CR ^ r6) 〇- (CR ^ R ^) p-C = C-E, ~ ------ -j ^ l0 (ID) where Ar, R1, R2, R3, R4, R5, R6, JJ7, R8, Rω, E, ra, η, ο, P have the meanings as those in the first scope of the patent application. 8. If the first compound in the scope of the patent application, or its | optical isomer or salt, its formula is Ar-(CRlR2) m _ (cR3R4) nn-(CR5r6) 〇_. (CR7r8) p _ C Three C-EI… R10 (IE) (Please read the notes on the back before filling out this page) where Ar, R 1, 2 R3, R4, R5, R®, R7, R8 Ar-(CRlR2) m-C- = N… Ο-(CR5r6) 0-(CR7R8) p-C is C-E. In the economic year, the staff and consumer cooperatives of Xin Bureau of Xining Bureau have the sincerity. R1Q, E, ra, n, o, p have the meanings as in the scope of patent application. One of the items < | 7. If the first conjugate of the scope of the patent application or its optical isomer or .salt:,. 丨 its formula is 'R9… i (IF) where Ar', R 1, R 2, R s, R 6 5 R 7, R a, R 9 n, n, 〇, p have the meanings as described in item 1 of the patent application scope 8. Such as the first compound in the patent application scope or its optical isomers Body or salt, 1-naphthylmethyl-2-butynyl ether, -propynyl-1, 3-phenoxacene-5-carboxylic acid ester, 1-[(2-butynyloxy) ethyl 〕 -3,4-dimethoxybenzene, 2,6-dichloro-1- (2-butynyloxymethyl) benzene, E, This paper is in accordance with China National Standard (CNS) 8-4 ( 210XW7 male ) Printed by the Bureau of Economic Standards, Bureau of Labor, Cooperatives, A8, B8, C8, and D8. 6. Scope of Patent Application 1-[1- (2-butynyloxy) propyl] Policy, R- (+)-2- [l- (2-butynyl) ethyl] pyrene, 5-[(2-butoxy) methyl] -1,3-benzodioxo, 5- [2-methyl-1- (2 -Butynyloxy) -propyl] -1,3-benzodioxo, 5-[(2-butynyl) benzyl] -1,3-benzodioxo, 2- [ (2-butynyloxy) methyl] -1,4-benzodioxo, 2, 3 -dihydro-2,2-dimethyl-7- (3-pentyloxy) benzopyran By. 3. —A method for preparing compounds of general formula I, | Ar-(CR! R2) m-(YR3R4) n-X- (CR5r6) 〇 · (CR7R8) p-C is C-E (I where Ar, R1, R2, R3, R4, R5, rs, R7, Rs, R9, R1Q, X, Y, E, m, η, o, p have the same meaning as the first item in the scope of patent application, and their holding is U). Compounds of formula (IAK: Ar-(CRlR2) m-Y-0-(CR surface 0-(CR7R8) p-c 3 C-E i (IA) (wherein Ar, R 1, R 2, R 5, R β , R 7, R 8, Y, E, m, o, p have the same meanings as in the first patent claim). Let the compound of general formula (II) Ar-(CRlR2) m-Y-AII 〇 and the following general formula (ra ) Compound Reaction-4-(Please read the notes on the back first 卩}: Fill in this page) Binding and binding _ II This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 Apply for patent Fangu-B-(CR5r6) 〇. (CR7R8) p-C ^ C-E (where Ar / R1, R 2, R 5, R 6, R 'n, 〇, p meaning as the scope of the patent application Item 1, a group forming an ester bond); (b) Production of a compound of general formula (IB): Ar-(CR1 R2) m-Y-N-(CR5R6) 0-(CR7R8) p-C i IIO RlO (ra, R 8, Y, E, and A and B are suitable for CE (IB) (where Ar, R 1, R 2, R 5, R 8, R 7, R 8, R 10, Y, E, B, 0, p have meanings If the scope of patent application is item 1), let the compound of general formula (IV): Ar- (CRlR2) mYC »0 (IV) (please read the precautions on the back before filling in this tile) Order _ with the compound of general formula (V) Reaction D-(CR5r6) 〇. (CR7R8) p. CC-EV (Where AR R2, R5, R8, R7, R8, Y, E, printed by the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs a, 〇, P Meaning For example, the scope of the patent application of item 1, and C and D are groups suitable for the formation of amido bonds); (c) for the production of compounds of general formula (1C): .............. : Ar-(CRlR2) m-(CR3R4) n. 〇- (CR5r6) 〇- (CR7R8) p-C s C · E ⑽ (where Ar, R 1, R 2, R 5, R e, R7, R 8, E, m, η, 〇, P have the meanings as in the first patent application scope, and R 3 and R 4 refer to hydrogen, alkyl, alkenyl, haloalkyl, phenyl, and substituted phenyl, respectively.) Paper size逋 Use China National Standard (CNS) A4 specification (210X297 mm) 6. Apply for patents Fanyuan A8 B8 C8 D8, let the compound of general formula (VI): Ar- (CRlR2) m- (CR3R 4) nF (VI) reacts with the compound of general formula (VI) 1 G-(CR5R6) 〇- (CR7R8) p-C is C-E (VI) (where Ar. R 1, R2, Rs, Re, R7 , R8, E, n, n 〇 · P meaning as in the scope of the first patent application, R 3 and R 4 refer to hydrogen, alkyl, alkenyl, haloalkyl, phenyl, substituted phenyl, and? And G are groups suitable for forming an ether bond);. (D) is a compound of general formula (ID): Ar-(CRlR2) m-(CR3r4) 〇- N-(CR5r6) 0-(CR7r8) p-C -C-E Rio (ID) (where Ar-URiR2} ra-(CR3 R4) n -N-stands for Carboximimine, R s, Re e, R 7, R 8, E, ο, p meaning as applied Patent Scope Item 1 > Let the general formula (VIII) Carboximidine: Ar-(CRlR2) m-(CR2R3) n-NH (VIII > I ---- ^ — * Γ 一 装-( Please read the notes on the back and fill in this page first) • Order # Central Standards Bureau of the Ministry of Economic Affairs β: Industrial and consumer cooperatives printed with compounds of general formula (IX) Lg-(CR5r6) 〇- (CR7r8) p-C ^ C-E (IX) (where Rs, Re, R7, Rs., E, o, p have the same meanings as those in the application. · The scope of the first item. And L represents Weng · Laji); (e) is a crack Compounds of general formula (IE): This paper uses China National Standards (CNS) A4 specifications (210X297 mm) A8 B8 C8 D8 S82〇23 VI. Patent application parks Ar-(CRlR2) m-(CR ^ h -N-(CR5r6) 〇. (CR7r8) p-C ^ C-E rIO (IE) (where Ar, R 1, R 2, R 3, R 4, R s, Re, R7 · R 8, R10, E, a, n, o The meaning of p is as the first item in the scope of patent application. Let the general formula (XMb compound Ar- (CRlR2) m- (CR3R4) nH (X) react with the compound of general formula (XI) I-(CR5R6))-(CR7R8 ) p-C is C-E (XI) (where Ar, R8, E, in, η, ο, ρ have the meanings as in the scope of patent application, H and I represent the bases suitable for forming -N-, where RiC > Meaning as in the application of the patent I R10 range item 1); (f) is the production of compounds of the general formula (IF): R9 I | Ar-(CRlR2) m-C & N ... 0-(CR5r6) 〇- (cr7r8) p-C is C-E (if) (where Α Γ, R 1, R 2, R 5, R 6, R 7, R e, R 9, E, n, o, p have the same meaning as in the patent application Item 1), let the compound of general formula (XII)! ...... R9 ..... | j! Ar- (CRlR2) mC-N-OH (XII) .. react with the compound of general formula (IX) This paper size uses Chinese National Standard (CNS) A4 specifications (2! 0X297 mm) (please note on the back of stt before filling out this page) Order-Printed by the China Standards Bureau of the Ministry of Economic Affairs and printed by the Ministry of Economic Affairs Standard Printing Bureau Male Workers Consumer Cooperatives Printing A8 S82623. S D8 VI. Application for Patent ♦ _..: · Lg- (CR5R%-(CR7R8) p. C a E:.. (IX)................... ··· · (where Ar, R1, R2 ·. Re · R7, R9 · E, a,. · N, 〇 · p has the same meaning as in the patent application scope item 1 and Lg represents a residue), if there is In order to convert the obtained compound (I > into its salt) or to release it from the hair, the optically active isomers may be separated if necessary. 10. —An insecticidal pupa composition, including, for example, a compound of the general formula (I) or its optical isomer or salt, as described in the first patent application scope, 01 ~ 39.9%. · The mass is the active ingredient, of which Ar, R \ · R 2 · R3 · R4. Rs, R β, R 7, R®. R9, R10,!》, Η, ο, ρ The meaning is the same as the first item in the scope of the patent application, except for loading and other rib materials, Yes, as needed • · * " To add other pesticide active ingredients #. 11. Ruo Shen _ Patent Item No. 10 Depleted Composition • Includes such as applying for Meng Li. Scope No. 1 compound of general formula (I) or its optical isomer or salt-0.0001 ~ 39.9% by mass as the active ingredient, of which Ar, R1, R2, R3, R4, R5, Re, R7., R8, Re, R10, a, n, \ 〇, P have the same meaning as the first item in the scope of patent application, except for carriers and other auxiliary rib materials, If you need to add other active ingredients of pesticides *. «· · 12 · If you apply for the 11th composition in the scope of benefits, the other active ingredients include: ..... · ·. Bronojpropylate, aninocarb), got • · ·.. · ♦ Λ < ·, * · a 1 dicarb, bendi 〇carb) · Guarantee decision-.... '; (carbofuran), two Di-oxacarb}, butyl metronid Q •... *…,-(Fenobucarb}, metronid S (isoproc'arb),. Naide., _ • _: · (nethonyU · 比Pirinicarb, propour «, 8-., •................. CNS) A4 Specification (210X297 She Xiao) One ~~... '~~~: ... HI iMmw fin §WB§ —ϋ ta-ϋ ^ «Shi ^ —ϋ I. 丨 //. (Please read the note on the back before filling in this tile) Order a d Ί 椟 Central Ministry of Economic Affairs Ministry of Economic Affairs only works for consumption Cooperatives Indy 38262S.? 1 _ D8 _ · VI. Patent Application Park • /. '·., Thiodicarb, fipronil, iBidaclopri < i) _, bye Yusong (quinalphos) · + 谷 速 松 \. ·. ··, _ ·.:: ... (azinphos-nethyl), Pyrazophos, bio-poem. Diallethrin (bioallethrin) (.esbol), pernethrinV, teteethrin, cyiJ.er_iB.ethi * in, ch.lorpyriphos, fenazaquin, Lindane, Tebufenpyprad; Triazanate (both pesticides and commercial products). 13. The composition according to item 11 or 12 of the scope of patent application, including one or more of the following compounds: One or more of the compounds of the general formula (I) or its optical isomers •. ·.. Or active ingredients of salts: 2- 2-alkynic acid,;...: ... 2-propynyl-1, 3-benzodioxo-5-carbonyl,. '1-[(2-butynyl) Ethyl] -3,4-dimethoxybenzene, • 2, 6-dichloro-b (2-butynyloxymethyl) benzene, 1- [1 .- (2.-butynyl)} Qiaoji]. Cai, ", R-(+)-2- [l- (2-butynyloxy) ethyl], 5-[(2-butynyloxy) methyl] -1,3 -Benzodioxo,........ 5-. [2-methyl · 1_ (2-butyroyl) propyl.benzyl] benzo- * »•.. ' ', .... 5-[. (2-butynyloxy) benzyl] -1,3-benzodioxo-m »» · 2- [(2-butynyl) methyl]- 1,4-Benzodibenzoic acid ,, • I 2, 3-dihydro-2, 2-dimethyl-7- (3-pentyl chloride S) benzofuran. 1 4 /. As applied. Please The scope of the patent No. 1 is covered by the composition. General formula ((1) chemical combination '.'-', 'too. Paper size d is standard for temple countries (CNS 1 Α4格 ί 210X297 公 奥) --Τ ---;-install-- (please read the note on the back ^ before filling this page)-order · line 382623 έΙ C8 __ _. D8_ · 'VI Solid • I or its optical isomer or salt 0.0001 to 99.9% by mass is the active ingredient, of which A r, R 1, R 2, R 3, R 4, R's, R β, R 7 \.. .., R 8, R 9, R, Β, n, Ό, ρ have the meanings as in the first patent application scope, and _ for the carbamate of the root arthropod, preferably carbamidine (ca rbςί f ur an) 者 0. · 15. The composition of item 14 in the initial scope of the application, including (2-butynyloxymethyl) -3,4-dimethoxybenzene, is of the general formula ( I) Compounds or optical isomers or salts thereof. 16. For example, the composition of item 14 in the scope of patent application, which contains 5-[(2-butynyloxy) methyl] -1,3-benzodi Dimethoate is a compound of the general formula (I) or an optical isomer or salt thereof. 17.-A method for killing insects, comprising treating insects, especially arthropods, with a composition as described in claim 10 or 11 Dispose in appropriate amount, if necessary, by mixing or continuing to use For example, in the scope of the patent application, the general formula (the compound of U compound or its optical isomer or salt, wherein Ar, R1, R2, R3, R4, R5, R6, R7, R 8, R 9,. 8 10, la, η, ο, p ~ The meaning is the same as that in the scope of patent application, and the composition containing known active ingredients β n tpe mimw iim-• Γ :. Read the notes on the back of the page and fill in this page) -m In —II r 线 —! · T 51 51 -10- a ffl ΑΒΙΒΙΦΆΑ (rvs \ (210X297 ^ · ^)