TW312611B - Amino acid amides as fungicides - Google Patents

Abstract

Amino acid amides of the formula I (see figure I) in which n is the number zero or one; R1 is C1-C12alkyl, which is unsubstituted or can be substituted by C1-C4alkylsulfonyl; C5-C6cycloalkyl; C2-C4alkenyl; C1-C4halogenoalkyl or a group NR13R14; in which R13 and R14 independently of one another are hydrogen or C1-C6alkyl or together are tetra- or pentamethylene; R2 and R3 independently of one another are hydrogen; C1-C6alkyl; C1-C6alkyl which is substituted by hydroxyl, C1-C4alkoxy, or C1-Calkylthio; C3-C6cycloalkyl, or in which the two groups R2 and R3 together with the carbon atom to which they are bonded, form a three- to six membered carbocyclic ring; R4 is hydrogen or C1-C4alkyl; R5 is hydrogen; C1-C4alkyl or phenyl, which is unsubstituted or can be substituted by halogen, and R6 is a group G (see figure G) in which R7 and R8 independently of one another are hydrogen, p is the number zero or one; and R9 R10 and R11 independently of one another are hydrogen, C1-C4alkyl, C1-C4halogenoalkyl, C1-C4alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkylthio, halogen or nitro. They can be employed in crop protection in the form of suitable compositions, for example for controlling fungal diseases.

Description

312611 Ministry of Economic Affairs Central Standard Falcon Bureau Staff Consumption and Costume A7 B7 V. Description of the invention (/) The present invention relates to the novel α-amino acid amines of formula I below. It is related to the preparation of these substances and to agrochemical compositions, which include at least one such compound as the active ingredient. The present invention is also related to the preparation of the mentioned composition. Once related to this active ingredient or composition, it is used as a pathogenic microorganism for controlling or preventing plant cover plants, with preference for the control and prevention of fungi. 'The compound of the present invention is a compound of formula I 0 R2 R4

Ri -S-NH--NH--Rs

0 I (0) n R3 Re where the substituent is defined as follows: η is 0 or 1; is (^ _Ci 2 alkyl, which is unsubstituted or can be substituted by Ci — C4 alkoxy plus M, h — C4 alkyl sulfide, Ci — C 4 alkylsulfonyl, C3 _C8 cycloalkyl, nitrogen * h -Cs alkoxy This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)- r --_---- f .installed ------ ordered ----- Yi (please read the notes on the back before filling in this page) 312611 A7 B7 5. Description of the invention (>) Carbonyl , C3-Cs alkenyloxycarbonyl or C3-C6 alkynyloxycarbonyl; C3_C8 cycloalkyl; C2-Ci 2 alkenyl; C2-C! 2 alkynyl; Ci-Ci 2 haloalkyl or a group NRi 3 Ri 4; where Ri 3 and 14 are independent of each other

Stand for hydrogen or (^ — C§ alkyl or together tetra- or pentamethylene; R2 and R

3 are independently hydrogen; h-C8 alkyl; h_C8 alkyl, which is substituted by hydroxyl, Ci-C4 alkoxy, sulfhydryl or Ci-C4 alkyl sulfur plus K; C3-C8 alkenyl; C3-C8 Absent group; C3—C8 ring group or C3-Cs ring group—Cl—C4 group, or two groups R2 and R3, together with the carbon atom they bind to form a three- to eight Member carbocyclic ring; R4 is hydrogen or Ci_C6 alkyl; Rs is hydrogen; Ci_CS alkyl or phenyl, which is unsubstituted or can pass through halogen, nitro, Ci-C4 alkyl, Ci-C4 haloalkane Group, Ci_c4 alkoxy group or "a c4 alkyl sulfur plus κ substitution; and R6 is a group G (please read the precautions on the back before filling in this page)

G Where R7 and Rs are independently hydrogen or Ci — C6 alkyl; P is 0 or 1 -8- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 312611 A7 B7 V. Description of invention (9 )

; And 1? 9 'Ri 〇 and Ri 1 are independently nitrogen * Ci _C6 burned group, C 1 _C (3 tooth courtyard group, C3-Cs dilute group, C3-Cs fast group, Ci-Cs alkoxy group, C3 — C6 alkenyloxy, C3-C6 alkynyloxy. Ci-Cs alkyl sulfur, halogen or nitrile. Forms an important group of compounds of formula I, where η is 0 or 1; Ri is Ci —'Ci 2 alkyl; Ci — Ci 2 alkyl which is substituted by Ci — c4 alkoxy, Ci · _C4 alkylsulfur or {^ — c4 alkylsulfonyl plus κ; c2 _

Ci 2 dilute group; C 2 — Cl 2 block group; Cl — Cl 2 dentate group or a group NR! 3 I 4; wherein Ri 3 and Ri 4 are independently Ci — Cs alkyl or four to one or five together Methylene; R2 and R3 are independently hydrogen; Ci-c8 alkyl; Ci-C8 alkyl, which is substituted by hydroxy, Ci-c4 alkoxy, sulfhydryl or Cl-C4 alkyl sulfur plus M; c3-c8 alkenyl; c3 _c 3 alkynyl; c3-C8 cycloalkyl; or C3-c8 cycloalkyl-Ci-c4 alkyl, or two of them, R2 and R3, together with which they are bonded Carbon atom, forming a three- to eight-membered carbocyclic ring; R4 is hydrogen or Ci-C6 alkyl; RS is hydrogen; Ci-Cs alkyl or phenyl, which is unsubstituted or halogenated, nitro, Ci — C4 alkyl, Ci — C4 haloalkyl, (^-c4 alkoxy or Ci — C4 alkyl sulfur plus M substitution; and R6 is a group G: -9- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 11 · ..--'--- Μ -installed ------ ordered ----- {line (please read the precautions on the back before filling this page) 312611 A7 B7 V. Description of the invention (屮)

R

R 10 11 wherein R7 and Rs are independently hydrogen or Ci-C6 alkyl; P is 0 or 1; and 1 ^, Ri. And 1 i are independently hydrogen, Ci—Cs alkyl, C 1 —Cs halo, _3_Ce dilute, C3—C6 block, Ci—Cs alkoxy, C3—cs alkenyloxy, C3— Cs alkynyl oxygen, Ci — Cs alkyl sulfide, halogen or nitro (subgroup A). Forming an important group of compounds of formula I, wherein η is Q or 1 and 1 ^ is (^ — Ci 2 alkyl; Ci — Ci 2 alkyl which is via h — C4 alkoxy, “_C4 alkyl sulfide Or Ci-C4 alkylsulfonyl group plus M substitution; C2-Ci 2 alkenyl; C: _Ci 2 haloalkyl or a group NRl 3 Κι 4; wherein Ri 3 and Rl 4 are independently Cl _C6 alkyl, Or Ri 3 and 1 4 together are tetra- or pentamethylene; R2 is hydrogen; R3 is ci-C8 alkyl; C 1 -C8 alkyl via hydroxyl, C i-C4 ^ 齐 郎中 矢 * 霁 gou 3 ^ Xiao Qian " At first. See Todo (please read the notes on the back before filling this page)

Alkoxy, sulfhydryl or Cl — C4 alkyl sulfur plus M substitution; or C3 _c8 cycloalkyl; IU is hydrogen; Rs is stupid, which is unsubstituted or halogenated, nitro, Ci-C4 alkyl Group, Ci-C4 haloalkyl, Ci-C4 alkoxy or C i _C4 alkyl sulfur is substituted and Rs is a group G, where p is 0; and ", Ri. And I! Are independently hydrogen , Ci — C6 alkyl, C i —C6 haloalkyl, Ci —C6 alkoxy, C3 — C6 alkenyloxy, C3 -1 0-This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm ) Employee consumption of the Central Standard Falcon Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (<) —C6 alkynyl oxygen, halogen or nitro (subgroup B). Form a particularly important group of compounds of formula I , Where η is 0 or 1; R i is "-Ci 〇 alkyl; Ci-C4 haloalkyl C2-Cs alkenyl; C 5-C6 cycloalkyl; Ci-C6 alkyl, which is cyanide Group or "—C4 alkoxycarbonyl group | or (^ _C2 dialkylamino group plus K substitution; R2 is halogen; R3 is C2- CS alkyl or C3- Cs cycloalkyl; R 4 is hydrogen; Rs is benzene Radical, which is unsubstituted or substituted by halogen; Rs is a group G, wherein p is 0; R9 is hydrogen;.!, And ^ and Ri independently of each other hydrogen or halogen (sub-group AA).

Forming another important group of compounds of formula I, wherein η is 0 or 1; Ri is (^ — C! 〇 alkyl; Ci — C4 haloalkyl; C 2-Cs alkenyl, or C 1 — dialkyl Amino group; R2 is hydrogen; R3 is C2-C5 alkyl or C3-C6 cycloalkyl; R4 is hydrogen; Rs is phenyl, which is unsubstituted or substituted by halogen plus K, and Rs is a group G, where P is 0; Rg is hydrogen; and Ri 〇 and i are independently hydrogen or halogen (subgroup C). Among these compounds, compounds in which η is 1 (subgroup Ca) are preferred Ο of subgroup C Among the compounds, preference is given to where η is 1 and R3 is c3-C4 alkane-11- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) (please read the precautions on the back before filling this page). Binding < Line ---- 312611 A7 B7 V. Description of the invention (Ιί7) group of compounds (subgroup C d). The important compound of subgroup AA in formula I, where η is 1; and 1 ^ is Methyl, ethyl * vinyl, cyclopentyl, cyclohexyl or dimethylamine compounds (subgroup AAa). Compounds of formula I forming another important group are those in which Ri is (^ 一 (^ 2 院Base; C3-C8 Alkyl; Ci-Ci 2 alkyl which is Ci-C 4 alkoxy, Ci-C4 alkyl sulfide, Ci- (; 4 alkylsulfonyl, C3-C8 cycloalkyl, cyano, Ci_CS Alkoxycarbonyl, C3 _C6 alkenyloxycarbonyl or Ci _C6 alkynyloxycarbonyl plus M substitution; C2 — Ci 2 alkenyl; C i — Ci 2 haloalkyl or a group NR! 3 R! 4; where Ri 3 and 1 4 are independently hydrogen or (^-Cs alkyl or jointly four- or pentamethylene printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page); R2 Is hydrogen; R3 is "-C8 alkyl; Ci-C3 alkyl which is substituted by hydroxyl, Ci- (: 4 alkoxy, sulfhydryl or Ci-C4 alkyl sulfur plus K; or 〇3-C8 cycloalkyl ; R4 is hydrogen or Ci-C4 alkyl; R5 is argon; or 〇1_C6 group; and Rs is a group G wherein β7 and Re are independently of each other hydrogen or Ci-C4 alkyl; P is 1; and R9 , Ri 0 and Ri 1 are independently hydrogen, Ci — Cs alkyl, Ci — C6 haloalkyl, C 3 — Cs alkoxy, C 3 —C 6 alkenyl oxygen, C 3 — CS alkynyl oxygen or halogen (subgroup F) 〇 The important compound of subgroup C in formula I is where η is 1 and Ri is A − 12- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. V. Invention description (/) group; ethyl; vinyl or dimethylamine Based compounds (subgroup Cc). A compound of formula I forming an important subgroup is where η is 0 or 1 and Ri is Ci_Ci 2 alkyl; Ci — Ci 2 alkyl, which is via (^ — C4 alkoxy, C: — C4 alkyl Sulfur or Ci_C4 alkylsulfonyl group is substituted; C2-Ci.2 alkenyl; Ci-Ci 2 haloalkyl or a group NRn 3 Ri 4; wherein R 3 and 1 4 are independently Ci_CS alkyl Or collectively tetrakis or pentamethylene; R2 is hydrogen; R3 is Ci-C8 alkyl; C1-C8 alkyl which is hydroxy, Ci-C4 alkoxy, sulfhydryl or Ci_C4 alkyl Sulfur is substituted; or C3-C8 cycloalkyl; IU is hydrogen or "-C4 alkyl; Rs is hydrogen or Ci-(] 6 alkyl and R6 is a group G, wherein R7 and R8 are independently gas or Ci—C4 alkyl, p is 1, and R9, i are independently hydrogen, Ci—C6 alkyl, Ci—Cs haloalkyl, Ci—c6 alkoxy, c3_cs alkenyloxy, c3_c6 alkynyloxy Or halogen (subgroup D). A compound of formula I forming a preferred subgroup is where η is Q or 1 and other substituents are defined as follows: Ri is "-Ci. Alkyl, Ci_C4 haloalkyl, C2_C6 Alkenyl or Ci_C2 dialkylamine; R2 is hydrogen; R3 is C2_Cs alkyl or C3-C 6 cycloalkyl; R4 is hydrogen or Ci-C4 alkyl; R5 is hydrogen; and R6 is a group G where R7 is hydrogen, R8 is hydrogen or ci-C4 alkyl; p is 1; and R9, Ri 〇 And Ri i are independently hydrogen, Ci — C6 alkyl, Ct — C6 haloalkyl, Ci — C6 alkoxy, C3 -1 3- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page)

A B7 V. Description of the invention (2) 3 C oxyalkene group / IV elemental halide or oxyalkyne is η 4 of which -C is 2, C type 'compound alkylated halide of 4 EC-group-times 1 of > c good ^ a alkane or alkene

1 C is 1 R alkane and hydrogen. It is a) E 9 ih R group; subgroup ί amine compound and oxaloxane in the group of a group of E is better in 1 C alkyl group is as follows: Ri group in which the amine group is a methyl group Two-in-one or bis-albene terephthalate, t-alkyl halide (please read the precautions on the back before filling out this page). Install it in the group. It ’s for preference. Ia formula Ea 'group In the secondary a (ε group, the base 4 of 4 is in C3 is the member of the Central Sample Falcon Bureau of the Ministry of Economic Affairs. Consumer consumption. Fi ^ in the secondary group Ea and the preferred compound class is the compound of formula I, where IU is hydrogen; and R6 Is a group G wherein R7 and Rs are hydrogen; P is 1; R3 is hydrogen; and 10 and Ri i are Ci-Cs alkoxy (subgroup Eac). In the preferred subgroup Ea, formula I The preferred compound class is & 1. It is Cl-C4 alkoxy group at position P ~ and Ri i is alkoxy group at m ~ position 1 (subgroup Ead). Subgroup preferred in the scope of formula I The compound of Ead is 14-this paper

R 1 is C CNS) Α4 · (210X297mm)

S12611 A7 B7 5. Description of the invention i — C4 alkyl; vinyl or dimethylamino and Ri i is ra — methoxy (subgroup Eada) =. Is P-methoxy. An important compound in the scope of formula I is where η is 1; and it is (^ -Cio alkyl; "-C4 haloalkyl; C2-C4 alkynyl; Cs-Cs ring

Alkyl .; C i — C4 alkyl, which is substituted by cyano or C C4 alkoxycarbonyl SCi′—Cz dialkylamine plus K; R9 is hydrogen; and R: 0 and 1 t are ^ — Cs Alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy (subgroup H). The preferred subgroup Η compound is where Ri is "-C4 alkyl > Ci_C4 haloalkyl, vinyl, dimethylamino or CS-Cs cycloalkyl (subgroup Ha). In the formula Compounds further preferred in the scope of I are those in which R3 is a C3-C4 alkyl group (subgroup Hb). (Please read the precautions on the back before filling out this page)-Pack · Order 1 k%

£? I The particularly preferred subgroup formed by compounds within the scope of formula I is where Ri 〇 is P-Ci-C4 oxy, P-C3_ [4 dilute oxygen or P-C4 block oxygen; And Ri 1 is a compound of m_Ci-C4 oxy group (subgroup He). The important compound of the subgroup He is where Ri is 0 C4 alkyl, ethylene -15- This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm)

Employee consumption cooperation of the Central Standardization Bureau of the Ministry of Economic Affairs. She printed Pei or dimethylamino; R1 〇 is p-methoxy, P-allyloxy or P-propargyloxy; and Ri 1 is m- Methoxy compounds (subgroup Hca). A particularly important compound of the subgroup Hca * is where Ri 〇 is a methoxy group and Ri 1 is "• -methoxy (subgroup Hcb). In the above formula I, "halogen" includes fluorine, atmosphere, bromine and iodine. Alkyl, alkenyl and alkynyl groups can be straight-chain or branched, and this can also be applied to dentyl alkyl'alkylsulfonylalkyl'alkenyloxy'alkynyloxy, alkyloxy and alkyl The alkyl'alkenyl * or alkynyl group of thiol and other groups. The alkyl group itself or components of other substituents are understood to be, for example, depending on the number of carbon atoms mentioned in M, 'epimethyl'ethyl'propyl'butyl, pentyl, dodecyl and their isomers Species, such as isopropyl, isobutyl, tertiary-butyl or second-butyl. Depending on the number of carbon atoms mentioned, cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl | cyclohexyl, cycloheptyl or cyclooctyl. A haloalkyl group may include one or more (same or different) halogen atoms, such as CHC12, CH2F, CC13 'CH2Cl, CHF2, CF3, CH2 CHz Br, C2 Cls, CH2 Br, CHBrCl and the like Thing. At least one asymmetric carbon atom and / or at least -16 appear in the compound of formula I- This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297mm) I — * ------, 'installed-- ---- Order (please read the precautions on the back before filling this page) A7 _____B7 V. Description of Invention (W) An asymmetric sulfur means that the compound can occur in the form of optical isomers. The geometric isomer case also occurs due to the appearance of fatty _c = c-double bonds. Formula I is intended to include these possible isomer forms and mixtures thereof. Some ct-amino acid derivatives of different structural types have been proposed to control plant-damaging fungi. (E.g. in EP-3 9 8 Q 7 2, EP-4 2 5 9 2 ^ 5 > DE-4026966 > EP- 477639, EP- 4 9 3 6 8 3 > DE-403 5.8 51, EP- 4 8 7 1 5 4 * EP-496239, EP-550788 and EP-554729). However, the effectiveness of these preparations is not satisfactory. Surprisingly, a highly effective microbicide was found to have the compound structure of Formula I. Description of the method for preparing compounds of the present invention Preparation of compounds of formula I a) By substituting substituted amino acids of formula II O R2

·. I

RrS —NH—C — COOH (〇) n R3 One | 'Flying one paper scale applies China National Standard (CNS) Α4 specification (210X297mm) 11 ^ -----, -installed ------ Order ----- (elephant (please read the precautions on the back before filling in this page) 312611 A7 B7 5. Description of the invention (//)

_—_ I has a definite statement that there are diluents with Π and 3 R and 2 R 1 R groups which are either absent or absent in the presence of an agent. Activating agent derived from the existence of the compound II-based carboxylic acid and its. One, or at the time, lack of amine deficiency

4 R 5 R 1 • C 1 N 2 Η

6. In R R it should go in reverse

There are legal formulas with 6 R and 5 R a) on the right side, which are clearly prepared by those who can go through this book and need to know that they have prepared the I _I formula for the derived amino amine for their own species. % Additives are known to the middle school chemical machine as I- _ I type paper ruler of Changtong amine and the Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the notes on the back first (Fill in this page) A7 B7 5. Description of invention (G) The activated derivatives of the carboxyl group of the amino acid of formula II are all carboxyl-activated derivatives, such as halogen acids, such as chloric acid; and further symmetry Sex or mixed hydrazones, such as mixed Q-alkyl-carboxyl oxazones; and further activated brews, such as p-nitrophenyl esters or fi-hydroxysuccinic succinimide esters, K and amines The activated form of the base acid is made in situ using a condensing agent buccal (for example, using dicyclohexylcarbodiimide or carbonyldiaminoazole). The halogen acids related to the amino acid of formula II can be produced by adding the amino acid of formula II with a halogenating agent, such as pentachlorophosphorus, thionyl chloride or oxalyl chloride, by known methods. Halogen acids related to amino acids of formula II can be obtained by combining amino acids of formula II with chloroformates, such as alkyl chloroformates * preferably butyl chloroformate, in the presence or absence of an acid binder Next, such as inorganic or organic bases, for example, a tertiary amine, such as triethylamine, pyridine, N-methyl-pyridine or N-methylmorpholinyl. The activated derivatives of the amino acid of formula II or the carboxyl group of the amino acid of formula II react with an amine of formula III in an inert diluent. Examples are: aromatic, non-aromatic or denatured hydrogen carbides, such as chlorohydrocarbons, such as methylene chloride or toluene; ketones, such as acetone; esters, such as ethyl acetate; Acetamides, such as dimethylformamide ·, nitriles, -1 9- This paper scale is applicable to China National Standard (CNS) Α4 specifications (210Χ297 mm) (please read the precautions on the back before filling this page) Pack.-Ordering the ball S12611 Jing Qilang Zhongya * Falcon staff two Xiao She " first. £ A7 B7 V. Description of the invention (order) such as acetonitrile, or ®, such as tetrahydrofuran, dioxane, diethyl Ether or tertiary-butyl methyl ether; or water or a mixture of these inert diluents. The acid-binding agents that may be present are (no) organic bases, such as an alkali metal or alkaline earth metal hydroxide or carbonate, For example, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, or, for example, a tertiary amine, such as triethylamine. * Pyridine, N-methylethridine or N-methylmorpholinyl. The temperature is A 80 to + 1'50 death, preference is -20 to + 60 C. Preparation of compounds of formula I Can by b) a sulfonic acid derivative of formula IV or sulfurous acid derivative Ο Ri -S-X IV (Ο) η wherein Ri and [eta] defined above and wherein X is a halogen (chlorine or bromine), a group! — S〇2 — 〇—or group Ri _S0— 0— 'reaction with amine of formula V into ίτ-2 0-(please read the precautions on the back and then fill out this page) China National Standard (CNS> Α4 specification (210 X 297 mm) A7 B7 V. Invention description (ί <) (Please read the precautions on the back before filling this page)

Rz FU

Hz N-C-C-NH-C-Rs V R3 0 Re where R2, R3, R4, Rs and R6 have the above definitions. The sulfonic acid derivatives or sulfurous acid derivatives of formula IV required for method b) are known per se. The amines of formula V which may be required are also known per se or can be prepared by the method bb) plus K described below. Sulphite derivatives or sulfonic acid derivatives of formula IV react with amines of formula V in an inert diluent. Examples are: aromatic, non-aromatic or halogenated hydrogen carbides, such as chlorohydrocarbons, such as methylene chloride or toluene; ketones, such as propylene; esters, such as ethyl acetate; Acetamides, such as dimethylformamide; nitriles, such as acetonitrile, or ethers, such as tetrahydrofuran, dioxane, diethyl ether, or tert-butyl methyl ether; or water or these inert diluents mixture. Acid binders that can exist-2 1-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Economy Zou Central Standard Falconer i Consumer Consumption Fi, Flat Yttrium 312611 A7 _B7_ V. Description of the invention (/ ^) Is a (no) organic base, such as, for example, an alkali metal or alkaline earth metal hydroxide hydroxide or carbonate, such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, or, for example, a tertiary amine , For example, triethylamine, pyridine, N-methylethridine or N-methylmorpholinyl. The temperature is -80 to + 15〇υ, the preference is -20 to +60 C. 'The compounds of formula I can also be prepared by c) reacting the compound of formula Γ 0 R2 R4 Ri-S-HN-CC-NH-C-Rs r R3 0 R6 with an oxidizing agent, where R i > Rz 'Rs> R4, Rs and Rs have the above definitions, but the substituents Ri, R2, R3, RS or R6 include a monothiol or alkylthio group. -2 2-(Please read the precautions on the back before filling in this page) The paper size of the binding and binding book is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) A7 5. Description of invention (π) The oxidant is organic Oxidizing agents, such as alkyl gas peroxides, such as cumene hydroperoxide, or inorganic oxidizing agents, such as peroxides, such as hydroperoxide, or transition metal oxides, such as di Chromium oxide, and transition gold oxide salts, such as potassium permanganate 'potassium dichloroformate or sodium dichloroformate. -Reaction of compounds of formula I 'with an oxidizing agent in an inert solvent, such as water or a ketone, such as acetone, or a mixture thereof, in the presence or absence of an acid, or in the presence or absence of a base Below, proceed at a temperature of -80 to + 150 ° C. aa) The required amino acid derivatives of formula II are prepared by combining the amino acid R 2 of formula VI

Hz NC-COOH VI R 3 where R2 and R3 have the above definitions and react with sulfonic acid derivatives or sulfurous acid derivatives of formula IV-23- This paper scale is applicable to China National Standard (CNS) A4 specifications (210X25) 7mm) (Please read the precautions on the back before filling in this page).

S126U Μ Β7 V. Description of the invention (θ) ο

Ri-S-X IV (Ο) n 'where Ri and 11 have the above definition and where X is halogen (chlorine or bromine) · group Ri _S〇2 — or group Ri — S0 — 0 —. The method aa) required sulfonic acid derivatives or sulfurous acid derivatives of formula IV and amino acids of formula VI are known. Solvents (or diluents), acid-binding agents and temperature range refer to the description of reaction a) or b). bb) Preparation of the required amines of formula V by acid hydrolysis of the compound of formula VII This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (21〇Χ297 mm)-: ----- hi ------ Subscribe ----- (Line (please read the precautions on the back and then fill in this page) A7 B7 ----—____—____ V. Description of Invention (ί 1)?? 2 ^ (CH〇) 3C — 〇- C-NH— C — C — NH— C-, I II I 0 甴 6 The Ministry of Economy Central Standard Falcon Bureau employee consumption cooperation madness ¾. 'Formula VII compounds have been disclosed in the literature , For example in EP — 398072, DE ^ 4 0 2 6 9 6 6 > EP-4 9 3 6 8 3 · EP- 4 9 6 2 3 9 > EP- 5 5 0 7 8 8 and EP -554728 ° Compounds of formula VII with an inorganic or organic acid, such as mineral acids (hydrohalic acid or sulfuric acid) or carboxylic acids, such as acetic acid or trifluoroacetic acid, or sulfonic acids, such as methanesulfonic acid or P-toluenesulfonic acid, The reaction takes place in an inert diluent (hydrocarbides such as methylene chloride or toluene; ketones such as acetone; or water) under a temperature of 40 to + 15 ° · Ό. When appropriate, it can also Use different acids and different A mixture of release agents. The acid itself can also be used as a diluent. The compounds of formula I are solids or oils * which can be kept at room temperature and are extremely valuable microbicides Characteristics. It can be used prophylactically or therapeutically in agricultural areas or related fields to control microbes that damage plants. When used at low concentrations plus K, the formula -25 of this invention Standard (CNS) A4 specification (210X297mm) {Please read the precautions on the back before filling this page)

U outfit · The Ministry of Economic Affairs of the Ministry of Economic Affairs of the Ministry of Economic Affairs, the consumer consumption of the company A7 B7 V. Description of the invention (/) The active ingredient is not only has significant microbicidal activity, especially in fungicidal activity, and also Especially tolerated by plants. Surprisingly, it has been discovered that the compounds of formula I have a highly preferred biocidal function, especially fungi, and K meets the practical requirements for controlling plant pathogenic microorganisms. They have highly beneficial therapeutic and preventive properties1 and are used to protect a variety of agricultural plants. The active classification of formula I enables the pests found in plants or parts of plants (fruits, flowers, stalks, stems, tubers, roots) of different useful agricultural plants to be controlled or killed. The protection can be Fight, for example, phytopathogenic fungi or even protect plant parts that will be formed later. The novel active component of formula I, M, has been shown to be effective against fungi incomplete fungi (Fungi imperfecti) (eg Cercospora, Botrytis »Helminthosporium > Fusarium > Septoria > Pyricularia and Alternaria). Basidiomycetes (E.g. Hemileia, Rhizoctonia, Puccinia L.) and ascomycetes (Ascomycetes) (e.g. Podosphaera Monilinaia & Uncinula Cercosporella, Erysiphe and Venturia) and, in particular, against Oomycetes (e.g. Plasiopara > Peronospora > Py And Phytophthora). They therefore serve as an important component in the control of plant pathogenic fungi to control plant pathogenic fungi. Combination of formula 1 -26- This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the notes on the back before filling in this page) Line 3! 26 4. Employees of the Central Standards Bureau of the Ministry of Economic Affairs Consumer cooperation. Shiyin A7 B7 V. Description of invention (> /)% type can be used in the form of K coating agent Μ for the treatment of seeds (fruits, _stems, nuts) and plant cuttings Κ Develop protection capabilities against fungal infections & soil pathogenic fungi against soil plants. The present invention is also related to products containing compounds of formula I as active ingredients, particularly related to the protection of harvested products, and related to their use in agriculture and related fields. _ Furthermore, the present invention also provides a method for preparing these compositions, which includes intimately mixing the active ingredient with one or more substances or substance groups described herein plus K. The present invention further provides a method of treating plants which includes the application of novel compounds of formula I, or novel compositions. The crops targeted for plant protection disclosed herein are within the scope of the present invention, such as the following plant species: cereals (wheat, barley 'rye' oats, rice, corn, sorghum, dink le, wheat and rye Mixed breeds); beets (beets and fodder leaf vegetables); pears and € fruit and soft fruits (apples, pears, peach, peach, almonds, peach, strawberry, raspberry) (Raspberry) and blueberry); legumes (pea, lentil, green beans, soybeans); oily crops (rapeseed, mustard, poppy, olive, sunflower, coconut, fungus plants' cocoa Asia, peanuts); cucurbits (pumpkins, cucumbers, clam shells): fibrous plants (cotton, flax, hemp, jute) A4 size (210X297mm) ~ (please read the precautions on the back before filling in this page)-Packing and ordering the economy of the middle and long-term employees of the Bureau of Economics and Economics A7 __B7____ V. Description of the invention (citrus) Fruits (oranges' lemons 'Sucker' oranges); vegetable crops (spinach, lettuce, reeds' cabbages, carrots, grapes, tomatoes, trotters, paprika); laurels (luo pear) (Av 〇ca do), cinnamon, camphor) or other agricultural plants' such as tobacco, walnuts, coffee, sugar cane, tea, pepper's vines, hops, banana plants and natural rubber plants and 觐Appropriate plants. The active ingredient of Formula I is conventionally used in the form of a composition, and can be used in combination with other active ingredients or on the area or plant to be treated at the same time. These other active ingredients can be Fertilizers, trace element mediators or other preparations that affect plant growth. You can also use selective herbicides, such as insecticides, fungicides, bactericides, nematicides, snails Medicaments or mixtures of several of these preparations, if appropriate, can be used together with the carriers, surfactants or other additives used to enhance the application, which are conventionally used in the art of dispensing. Suitable carriers Additives can be solid or liquid and those commonly used in the field of preparation, such as natural or remanufactured minerals, solvents, dispersants, wetting agents, adhesives, thickeners, Binders or fertilizers. A preferred method of applying the active ingredients of Formula I or agrochemicals including at least one of these active ingredients is to apply to the leaves (絜 子 性 应用 -28- This paper scale applies the Chinese national standard ( CNS) A4 specification (210X297mm) --------- one-installed ------ ordered ----- {line (read the precautions on the back before reading this page) Ministry of Economic Affairs Employees of the Central Sample Falcon Bureau A7 B7 Fifth, invention description ()). The frequency and rate of application depend on the risk of a large number of infections caused by the pathogens to be restrained. The active ingredient of formula I can also be applied to plant propagation materials (seed covers, fruit springs, tubers, buds, cuttings, roots and the like) ' Cut out the shoots and soak them in the liquid composition of the active ingredient 'or coat them with a solid composition. Compounds of Formula I are used in an unchanged form or, preferably, are used in combination with other adjuvants conventionally used in the art of preparation. For this purpose, the compounds of formula I can be advantageously processed to obtain, for example, emulsified concentrated 'shrinking agents, spreadable pastes, directly sprayable or diluted solutions', diluted emulsifiers, which can be wetted Powders, soluble powders' dusts or granules, or methods known by K, such as the use of polymeric substances for the capsule coating. It is actually used for spraying and atomization; the method of dusting and spreading on or dumping, K and the natural characteristics of the formula are selected according to the purpose of the plan and the environment plus K. The rate of application preference is usually 5 g to 2 kg of active ingredient (A.I.) per hectare (ha), with a preference of 10 g to 1 kg of A.1./ha, especially 20 g to 600 Kezhi A. I · / ha. The formula category, that is, containing the active ingredient of formula (I) and if appropriate 'the composition category, preparation category or composition category with a solid or liquid additive' -2 9-This paper scale is subject to the Chinese National Standard (CNS ) A4 specification (210X297mm) (Please read the precautions on the back before filling in this book)-Pack · Order the Central Standard Falcon Bureau of the Ministry of Economic Affairs i Consumer Cooperation f ± Lunch Wear S12611 A7 B7 V. Invention Description (> f ) It is prepared by adding K in a known manner, for example by closely mixing and / or grinding the diffusing agent with the active ingredient > the diffusing agent such as solvents, solid carriers and, if conditions are appropriate In this case, it may be a surface-active compound (surfactant). . Solvents are: aromatic hydrogen carbides, preferentially C 8 to C i 2's, such as xylene mixtures or substituted naphthalenes, peptide acid cools, such as dibutyl titanate or titanic acid Dioctyl esters, fatty hydrocarbons, such as cyclohexane or paraffin alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethyl ethylene glycol Alcohol monomethyl ethers, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfonate or dimethylformamide, and epoxidized or non- Epoxidized vegetable oils, such as epoxidized coconut oil or yellow oil, M and water. Solid carriers, such as dusts or dispersible powders, are natural mineral powders such as calcite, talc, kaolin, montmorillonite or attapulgite. 〇 In order to improve its physical properties, it is also possible to add highly dispersed silicon compounds or highly absorbent polymers. Granular absorbent particulate carriers are porous, such as pu ai ice, brick grit, sepiolite or bentonite, and also -3 0-This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) --- j -----''- installed ------ ordered ------ line (please read first Note on the back and then fill out this page) A7 _____B7___ printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Invention description (> <) May be non-absorbent carrier material, for example, calcite or sand. Furthermore, 'a large amount of pre-granulated materials with inorganic or organic properties can be used' such as dolomite or crushed plant residues. The surface-active compounds are nonionic, cationic and / or anionic active agents, which have good emulsifying, dispersing and wetting properties, depending on the natural characteristics of the active ingredient of formula I to be formulated. Surfactants can also be understood as mixtures of active agents. Suitable anionic surfactants are said to be water-soluble soaps and water-soluble synthetic surface-active compounds. Examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene oxide / ethylene oxide adducts, tributylphenoxy polyextrusion Ethyl alcohol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethyl sorbitan, such as trioleic acid polyoxyethyl sorbitan S, are also suitable. Cationic surfactants are, in particular, quaternary ammonium salts, which include at least one alkyl group having 8 to 22 carbon atoms as N-substituents and lower halogenated or free alkyl groups, Benzyl or lower hydroxyalkyl as -3 1- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page)

, TT A 7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The invention description (less b) is a further substitute. Other surfactants used in the art of preparation have been known to those skilled in the art or may be found in the relevant technical literature. Generally, the agrochemical preparations include Q. 1 to 99% by weight, especially '0.1 to 95% by weight of the formula I active composition, containing 9 9 · 9 to. 1% by weight , Especially 99.8 to 5% by weight of solid or liquid additives, and interfacial activators containing 0 to 25% by weight, especially 0. 1 to 2 5% by weight. However, the concentrated composition is preferred as a commercial product, and usually the final consumer will add M to the composition for dilution. The composition may further include additives such as stabilizers 'anti-foaming agents, viscosity modifiers, binders or adhesives' and fertilizers and other active ingredients that can achieve specific effects. The following examples illustrate the above-described embodiments of the invention without limiting the invention. The temperature is expressed in degrees Celsius (degrees). Preparation examples of compounds of formula I: -32- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) m-—ml nm · 1 (please read the precautions on the back before filling this page) Order 4 A7 B7 Five 'Description of the invention (Η 一 ι · 1 ·: (R * S)-2-(Ν, Ν-dimethylamine hard brewing group) monoamine-3-methyl-butyric acid N- (1 '1 -dibenzylmethyl) -donkey amine [Method a)] 〇I! 0

(CHgLN S ~-NH- CH- C-NH.

[Compound 1.1] 2 · 2 grams of (R 'S) — 2— (Ν ′ Ν—dimethylamine and donkey) monoamine_3-methylmonobutyric acid and 1.1 mL of N -Methyl alcohol in 50 ml of tetrahydrofuran was cooled to a 1QCC 'and stirred. ] 25 mL of isobutyl chloroformate was added dropwise and then the reaction mixture was stirred at _10 < c for 3 Q minutes. 7 ml of 1_aminodiphenylmethane Immediately I pack — I I I I Subscriber line (please read the precautions on the back before filling this page) Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

R. S)-2-(S was added and the mixture was stirred at room temperature for 6 hours. The reaction mixture was added with 200 mL of 2 N hydrochloric acid and extracted twice with 200 mL of ethyl acetate each time. The organic phase is washed once with K20Q ml of 2N hydrochloric acid ', once with 100 ml of saturated sodium chloride solution, twice with 2QQ ml of 2N potassium ammonium carbonate solution and with K10Q ml of saturated sodium chloride solution Washing ... drying on magnesium sulfate and concentrating a dimethylamine sulfonamide) monoamine 3-methylbutyric acid N- (1,1 diphenylmethyl) amide can be passed through Performed in ethyl acetate / hexane. The result is $ -33- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) V. Description of the invention (> J) Α7 Β7

It is obtained by adding K and purifying it. The melting point is 1 5 6-1 5 8 ° C. The compound K shown in Table 1 is obtained by the method similar to this example. Table 1 (Prepared according to method a) 0

Rz R4 (Please read the precautions on the back before filling this page) • Install.

Ri -S-NH- (Ο) η Rs Η Γ -Rb

Re Ordered by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative Printed 2,3-D = 2 > 3-dimethoxy-benzyl, 2,5-D = 2,5-dimethoxy-benzyl, 3 , 4-D = 3,4-dimethoxy-benzyl, 3,5-D = 3,5-dimethoxy-benzyl, 3,4,5-T = 3,4,5-trimethyl The stereochemistry of the alpha carbon atom of oxy-benzyl (known) amino acid: Compounds 1.1 to 1.5, 1

10, 1 · 13 to 1 · 18 are R lines -34- The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) A7 B7 5. Description of the invention (> /)

Compounds 1. 6 to 1.8, 1.11, 1.12, 1.23 to 1.42, 1.44, 1.45, 1.44 9 to 1.83 ^ S Compound Ri, n R2 Rs R4 RS Re physical number data

Melting point C (please read the precautions on the back before filling in this page)-installed · Printed by the Ministry of Economy Central Standard Falcon Bureau Employee Consumer Cooperatives 1.1 Me2 N 1 Η 2-propyl phenylphenyl 156-158 1.2 Me2 N 1 Η 2-propyl Η Η 3,4-D oil 1.3 methyl 0 Η 2-propyl Η Η 3,4-D 1.4 2-propyl 0 Η 2propyl Η Η 3,4-D 1.5 2 -Methyl- 0 Η 2-propyl Η Η 3,4-D 2-propyl 1.6 methyl 0 Η 2-propyl Η Η 3,4-D 1.7 2-propyl 0 Η 2-propyl Η Η 3,4-D 1.8 2-methyl- 0 Η 2-propyl Η Η 3,4-D 2-propyl 1.9 Mez Ν 1 Η methyl Η 3,4-D 1.10 methyl 1 Η methyl Η Η 3,4-D -35- 、 * τ The size of the linear paper is in accordance with the Chinese National Standard (CNS) Α4 specifications (210 X 297 mm) A7 B7 5. Description of the invention (present 1.11 Me2 Ν 1 Η ethyl Η Η 3 , 4-D 108-111 1.12 Methyl 1 Η ethyl Η Η 3,4-D 1.13 Mez N 1 Η cyclopropyl Η fl 3,4-D 1.14 methyl 1 Η cyclopropyl Η Η 3,4- D 1.15 Μβ2 Ν 1 Η cyclopropyl- Η Η 3,4-D methyl 1.16 methyl '1 Η cyclopropyl- Η Η 3,4-D methyl compound R1 η Rz Rs R4 R5 Re Physics (please read the precautions on the back before filling in this page). Packing · Numbering data melting point It is printed by the Ministry of Economic Affairs, Central Bureau of Precinct Employee Consumer Cooperative Printed 1.17 Me2 Ν 1 Me 2-propyl Η Η 3 , 4-D 1.18 methyl 1 Me 2-propyl Η Η 3,4-D 1.19 Mez N 1 Me methyl Η Η 3,4-D 1.20 methyl 1 Memethyl Η Η 3,4-D 134- 135 1.21 Me2 Ν 1 tetramethylene Η Η 3,4-D 1.22 methyl 1 tetramethylene Η Η 3,4-D 152-154 1.23 Me2 Ν 1 H 1- (2-methyl- Η Η 3 , 4-D 2-Propoxy) -ethyl 1.24 Methyl 1 H 1- (2-Methyl-Η Η 3,4-D -36- The size of the linear paper is applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm) A7 B7 V. Description of invention U /) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2-Propoxy ethyl 1.25 ethyl 1 Η ethyl Η (S) -Me phenyl 122-123 1.26 ethyl 1 Η ethyl Η Η 3,4-D 107-109 1.27 ethyl 1 Η ethyl Η (R) -Me phenyl 122-123 1.28 ethyl 1 Η ethyl Η phenyl phenyl 151-153 1.29 ethyl 1 Η 1- (2-methyl-Η Η 3,4-D oil- 2-propoxy) -ethyl 1.30 ethyl 1 H 1- (2- Methyl-Η (R) -Me phenyl 84-86 2-propoxy) -ethyl 1.31 ethyl 1 H 1- (2-methyl-Η (S) -Me Benzyl 138-139 2-propane Oxy) -ethyl 1.32. Ethyl 1 H 1- (2-methyl-Η phenylphenyl 115-116 2-propoxy) -ethyl 1.33 ethyl 1 Η 2-propyl Η methyl 4 -C1- 152-154 Phenyl 1.34 ethyl I Η 2-propyl Η 3,4,5-T resin 1.35 ethyl 1 Η 2-propyl Η 3-MeO- 97-99 benzyl 1.36 ethyl 1 Η 2-propyl H (S) -Me phenyl 177-178 1.37 ethyl 1 Η 2-propyl H phenyl 188-189 1.38 ethyl 1 Η 2-propyl H (R) -Me benzene Base 177-178 -37- (please read the precautions on the back before filling this page)

Y This paper scale applies the Chinese National Standard (CNS) A4 specification (2I0X297 mm) A7 B7 V. Description of invention U) The compound Ri n Rz Rs R4 Rs Re physical number data printed by the Ministry of Economy ’s Central Falcon Bureau Employee Consumer Cooperative Melting point t: 1.39 ethyl 1 H 2-propyl Η 2,3-D 95-96 1.40 ethyl -1 H 2-propyl Η 4-ΜβΟ- 106-107 • benzyl 1.41 ethyl 1 H 2 -Propyl Η Η 3,5-D 85-87 1.42 ethyl 1 H 2-propyl Η Η 2,5-D 85-87 1.43 methyl 1 tetramethylene H phenylphenyl 242-243 1.44 methyl Group 1 Η ethyl Η (R) -Me phenyl 116-117 1.45 methyl 1 Η ethyl Η ⑶-Me phenyl 115-117 1.46 methyl 1 Me methyl Η methyl phenyl 120-121 1.47 methyl 1 Me Methyl H Phenyl Phenyl 173-174 1.48 Methyl 1 Tetramethylene H Methyl Phenyl 163-165 1.40 Methyl 1 H Ethyl H Benzyl Phenyl 190-192 1.S0 Mez N 1 H 2-propyl Η (R) -Me phenyl 114-115 1.51 Mez N 1 Η 2-propyl Η ⑻-Me phenyl 108-109 1.52 Mez S 1 Η 2-propyl H methyl 4-C1- 112 -113 Phenyl 1.53 Μβ2 N 1 Η 2-butyl Η Η 4-MeO- 85-87 benzyl 1.54 Mea N 1 Η 2-propyl Η methyl 4-MeO- 93-96 -38- (please read the precautions on the back before filling this page) The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X2S »7mm) 5. Description of the invention Up A7 B7 benzyl 1.55 Μβ2 Ν 1 Η 2-propyl H (S) -Me 4-Μβ- 161-163 phenyl 1.56 Me2 Ν 1 Η 2-propyl Η (R) -Me 4-Me- 166-168 phenyl 1 Η 2-propyl Η 1.57 Mez 1.58 Me2 Ν. 1 Η 2-propyl Η 1.59 Me2 Ν 1 Η 2 -Butyl H 1.60 Me2 1 H 2-propyl H H 4-MeO- 82-83 benzyl H 3-MeO-resin benzyl H 3-MeO-resin benzylmethyl 4-fluoro- 111-112 phenyl (Please read the precautions on the back before filling this page)-Pack. Order compound L No. n R2 R3 R4 R5 Re

Physical data Melting point C Economy Zou Zhongzuo Falcon Bureau member X Consumer cooperation fiprint ^ 1.61 MeE N 1 Η 2-propyl Η Η 3,5-D oil 1.62 Mez Ν 1 Η 2-propyl Η Η 3,5-D 87-89 1.63 Me2 Ν 1 Η 2-propyl Η Η 2,3-D 90-91 1.64 ethyl 1 Η 2-propyl Η 3-MeO-4- resin PrO-benzyl-39- the paper size Applicable to Chinese National Standard (CNS) A4 specifications (210X297mm) 312611 Α7 Β7 5. Description of invention 〇) 1.65 Me ^ N 1 H 2-propyl Η methyl 3,4-Ρ 105-147 1.66 ethyl 1 H 2-propyl Η Η 4-MeO-3- 101-103 PrO-benzyl 1.67 ethyl 1 H 2-propyl Η Η 3-MeO-4- 112-114 allyl 0-benzyl 1.68 ethyl 1 H 2-propyl Η Η 4-MeO-3- resin allyl 〇-benzyl 1.69 ethyl. 1 H 2-propyl Η Η 3-Et〇-4- 89-91 MeO-benzyl 1.70 ethyl 1 H 2-propyl Η Η 3-MeO-4- 109-11 (propargyl 〇-benzyl 1.71 .Me2 N 1 H 2-butyl Η 3-MeO ~ 4_ resin propargyl 〇-benzyl 1.72 Mez N 1 H 2-butyl Η Η 4-MeO-3- resin PrO-benzyl 1.73 Me2 N 1 H 2-propyl Η Η 4-MeO-3- tree Lipid Me-benzyl 1.74 Mez N 1 H 2-propyl Η 3-MeO-4- resin propargyl 0-benzyl 1.75 Me2 N 1 H 2-propyl Η 4-NeO-3- 84-85 PrO-benzyl 1.76 Me2 N 1 H 2-propyl Η Η 3-Μθ0-4- resin allyl 0-benzyl (please read the precautions on the back before filling in this page) 丨 installed. Order-40- this The paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ 297mm)

Printed by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs 1.77 Me2 N 1 Η 2-butyl Η Η 3-ΕΙ0 ~ 4 ~ 85-88 MeO-benzyl compound Ri η R2 R3 R4 RS Re physical val data melting point υ 1.78 Mez N 1 Η 2-butyl Η Η 3-Me0-4- resin allyl 〇-benzyl 1.79 Me2 N 1 Η 2-propyl Η Η 3-ΕΪ0-4- 87-89 MeO-fluorenyl 1.80 Me2 N 1 Η 2-propyl H Methyl 4-acetophenone-resin phenyl 1.81 ethyl 1 Η 2-propyl H Η 4-MeO-3- 89-91 Me-benzyl 1.82 ethyl 1 Η 2-propyl Η Η 4-EtO-3- 87-89 MeO-benzyl 1.83 Me2 N 1 Η 2-propyl Η Η 4-EtO-3- 84-86 MeO-benzyl 1 84 ethyl 1 Η 2-propyl Η methyl 3,4-D 112-160 1.85 ethyl 1 Η 2-propyl Η 1- (3,4- 114-130 di-MeO-phenyl) -ethyl-41- (please read the back first Note: Please fill out this page again) Policy · The size of the revised paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 5. Description of the invention (1.134 ethyl 1 Η 1.136 ethyl 1 Η 1.137 ethyl 1 Η

1.150 η-butyl 1 H 1.151 η-propyl 1 Η A7 B7 cyclohexyl Η Η 3-ΜΘ0-4- resin propargyl 0-benzylcyclopropyl Η H 3-MeO-4- 101-112 ethyl 0-benzylcyclopropyl H H 3-MeO-4-resin propargyl 0-benzyl 2-propyl H H 4-MeS-benzene 120-123 yl 2-propyl H 4-benzyl 4-C1-benzene Base 174-177 (Please read the precautions on the back before filling out this page) -4H- Printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210XW7mm) A7 5. DESCRIPTION OF THE INVENTION 〇: (R * S) —Methanesulfonic acid N— [2-Methyl-1_aminomethylcarboxamide] —Propyl-amide [Method a)]

CH3-S — NH- CH— C-NH- CH

〇 (Please read the precautions on the back before filling out this page) Pack. [Compound 2 · 1] Order-Bu line 3.9 g of (β, s) monomethylsulfonic acid mono [2-methyl-1 1 A shuttle group] -propyl ~ amide [method a)] and 2.2 ml of the reaction mixture was warmed to ~ 10 ° C and searched for 30 minutes. The reaction mixture was then cooled to -20¾, and 2.2 mL of benzylamine was added dropwise over 5 minutes and the mixture was warmed to room temperature and stirred for 4 hours. The reaction mixture was added to 200 ml of water. The mixture was taken twice with 200 mL of ethyl acetate SM each time. The organic phase is washed once with “^ ml of saturated sodium chloride solution”, mixed, dried over magnesium sulfate and concentrated. (R, S) —Methanesulfonic acid N— [2-methyl-1— ( N-benzyl) monoaminomethylamide-]-propyl-amidoamine can be obtained by recrystallization from ethyl acetate / hexane and purification with K, melting point 1 1 5-1 1 6 -42- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 5. Description of invention (Qiao) The compound K shown in Table 2 is obtained by a method similar to this example. Table 2 (prepared according to method a)) 0 H FU CH3 ~~ S—ΝΗ—C—r ~ -NH--Rs 0 0 The stereochemistry of the alpha carbon atom of the amino acid that has been revealed by Human Re: Compounds 2.1 to 2.2 4, 2, 4 8 is R, S compound 2. 25 to 2.47, 2. 49 to 2. 51 is S compound IU Rs Re physical number data -43- (please read the precautions on the back before filling this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 312611 _ B7 5. Description of invention) 2.1 Η Η phenyl melting point 115-116 ^ 2.2 Η methyl phenyl melting point 132- 134 ^ 2.3 Methyl Φ phenyl 2.4 Η Η in-trifluoromethylphenyl melting point 154-155¾ 2.5 Η methyl P-fluorophenyl melting point 106-109Ό 2.6 Η methyl P-chlorophenyl melting point 150-156TC 2.7 Η, methyl P-methoxyphenyl 2.8 Η methyl m-methoxyphenyl 2.9. Η methyl κι-trifluoromethyl 2.10 Η methyl benzyl 2.11 Η methyl P-chlorobenzyl 2 · 12 Η Methyl 2,5-dimethoxy-4- -methylbenzyl 2.13 Methylmethylbenzyl 2.14 Methylmethyl P-fluoro〒yl 2.15 Methylmethyl p-chlorobenzyl * 2.17 Η phenylphenyl melting point 190-19TC 2.18 Η 'phenyl p-chlorophenyl 2.19 Η phenyl p-methoxyphenyl 2.20 Η phenyl p-methylphenyl 2.21 Η phenyl 3,5-di- Trifluoromethylphenyl 2.22 Η Η 1-phenylethyl 2.23 Η Η 1- (4-chlorophenyl) -ethyl (please read the precautions on the back before filling in this page) -install. Thread-44 -This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 The Ministry of Economic Affairs Central Standards Bureau staff consumer cooperatives print L, invention description (//) Compound R4 Rs Re physical number Data 2.24 Η Η 2-(4-chlorophenyl) -propyl 2.25 Η Η phenyl 2.26 Η-methylphenyl 2.27 methyl'ylmethylphenyl 2.28 Η Η m-trifluoromethylphenyl 2 29 Ή Methyl P-fluorophenyl 2.30 Η Methyl P-chlorophenyl melting point 139-142C 2.31 Η Methyl P-methoxyphenyl 2.32 Η Methyl m-methoxyphenyl 2.33 Η Methyl m-trifluoro Methyl 2.34 Η Methylbenzyl 2 35 Η Methyl P-chlorobenzyl 2.36 Η Methyl 2,5-dimethoxy-4 · -methylbenzyl 2.37 Methylmethylbenzyl 2.38 Methylmethyl P-fluorobenzyl 2.39 Methylmethyl P-chlorobenzyl 2.40 Η Phenylphenyl melting point 19 Bu 1931 2.41 Η phenyl P-chlorophenyl 2.42 Η phenyl P-methoxyphenyl 2.43 Η phenyl P -Methylphenyl 45- --------- ^ installed ------ order ----- * ~ line (please read the precautions on the back before filling this page) This The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 5. Description of the invention () A7 B7 2.44 Η phenyl 3,5-di-trifluoromethylphenyl 2.45 Η Η 1-phenylethyl 2.46 Η Η 1- (4-chlorophenyl) -ethyl 2.47 Η Η 2- (4-chlorophenyl)- Base 2.48 Η Η P-nitrophenyl melting point 167-168C 2.49 Η Η 〇-trifluoromethylphenyl melting point 168-169C 2.50 Η, (R) -Me phenyl melting point 139-142C 2.51 Η ⑶-Me Benzy Melting point 138-139 ^ 0 Η- -3 · 1 ·: (S)-2- (N, N-di 丨 amino- 3-methyl-butyric acid N-[2-(3,4- "ethyl 〕 Monoamide [Method b)]

〇II (CHgLN-S — NH- CH — C — NH-CH2- CH? 〇

1 ♦ ------- ί-installation ------ order ----- first line (please read the precautions on the back before filling in this page) 〇Compound 3 · 1 46- This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) 312611 at B7 V. Description of invention U 丨) 7.2 g (S)-2 -amino-3-methyl-butyric acid N_ [2_ (3, 4 One earth methoxyphenyl) -ethyl] -amidamide and 4 ml of triethylamine were initially added to 120 ml of 1,4-dioxolane at room temperature. When mixing, 2.8 ml The N, N-dimethyl sulfonamide chloride was added dropwise over 5 minutes. The reaction mixture was stirred at room temperature for 20 hours and 8 Q ml of 2 N hydrochloric acid was added. The mixture was extracted twice with 2QQ mL of ethyl acetate each time. Organic phase K 80 ml of 2N hydrochloric acid was washed once, K8Q ml of saturated sodium chloride solution was washed once, each time M80 ml of 5% sodium bicarbonate solution was washed once and M 80 ml of saturated sodium chloride solution Wash once, mix * dry over magnesium sulfate and concentrate. (S)-2- (Ν, Ν-dimethylamine sulfonamide) monoamino-3-methyl-butyric acid Ν- [2- (3, 4-dimethoxyphenyl) monoethyl 〕 _ Acetamide can be obtained by recrystallization from ethyl acetate / hexane and purification by M addition, melting point 1 5 6 1 5 8 ° C. Compounds M and M shown in Tables 3 and 3a were obtained by the method of this example. Table 3 (prepared according to method b)) Ο H OCH3 Rj-— S — C — C — NH — ΟΗ2〇Η2 ~ ^ " " " " OOH ^ II I II 0 R3〇j I -47- (Be sure to read the precautions on the back and then fill out this page)-Pack. The paper size of the binding book is applicable to the Chinese national standard (CNS> A4 specification (210X297 mm) A7 B7 V. Invention description Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy Stereochemical compound of the carbon atom of the disclosed amino acid Ri Rs physical number data 3.1 'NMe2 2-propyl melting point 97-99T: 3.2 NMe2 2-butyl melting point 91-92C 3.3 NMe2 2-methyl-propylene Base resin 3.4 NMe2 2_MeS_ethyl resin 3.5 NMe2 hydroxymethyl 3.6 NMe2 1-hydroxy-ethyl surface 3.7 NMeEt 2-propyl melting point 76-78C 3.8 NMeEt 2-butyl 3.9 NEt2 2-propyl melting point 95-96 ° C 3.10 NEt2 2-butyl melting point 63-69Ό 11 12 (please read the precautions on the back before filling in this page) • Pack and order 2-propyl 2-butyl 13 methyl 2-propyl

Melting point 7S-771C

Melting point 130-132 ° C This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 V. Description of invention (1: H) Printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 3.14 Methyl 2- Butyl melting point 147-148 ^ 3.15 Methyl 2-methyl-propyl resin 3.16 Methyl 2-MeS-ethyl melting point 1 2 6- 1 27¾ 3.17 methylhydroxymethyl 3.18 methyl 1-hydroxy-ethyl Melting point 140-141 ° C 3.19 Ethyl 2-propyl melting point 148-152. . 3.20, ethyl 2-butyl melting point 137-138. . Compound Ri R3 Physical number data 3.21 Ethyl 2-methyl-propyl resin 3.22 Ethyl 2-MeS-ethyl Melting point 79-81. . 3.23 Ethyl hydroxymethyl 3.24 Ethyl 1-hydroxy-ethyl Melting point 82-83. . 3.25 propyl 2-propyl melting point 108-109C 3.26 propyl 7-butyl melting point 95-96Ό 3.27 2-propyl 2-propyl 3.28 2-propyl 2-butyl 3.29 butyl 2-propyl melting point 81-84Ό 3.30 Butyl 2-butyl Melting point 1 0 5- 1 06t: 3.31 2-butyl 2-propyl 3,32 2-butyl 2-butyl-49- (Please read the notes on the back first (Fill in this page) Pack. The size of the printed paper is in accordance with the Chinese National Standard (CNS) A4 (210X297mm). The Ministry of Economy Central Standards Bureau Employee Consumer Cooperative Prints A7 B7. V. Invention Instructions (il4) 3.33 2-Methyl-C 2-propyl 3.34 2-methyl-propyl 2-butyl 3.35 2-methyl-2-propyl 2-biyl 3.36 2-methyl-2-propyl 2-butyl 3.37 pentyl 2 -propyl 3.38 .hexyl 2-propyl 3.39 'octyl 2-propyl melting point 77-78¾ 3.40 decyl 2-propyl melting point 1 0 6- 1 07t 3.41 dodecyl 2-propyl 3.42 vinyl 2 -Propyl melting point 1 3 6- 1 37¾ 3.43 vinyl 2-butyl melting point 149- 150¾ 3.44 vinyl 2-methyl-propyl resin 3.45 vinyl 2-MeS-ethyl melting point 12 9- 1 30TC 3.46 vinyl Hydroxymethyl 3.47 B Alkenyl 1-hydroxy-ethyl Melting point 1 34- 1 35 ^ 3.48 Trifluoromethyl 2-propyl Melting point 12 0-121. . 3.49 Trifluoromethyl 2-butyl 3.50 Chloromethyl 2-propyl Melting point 131-13 2. . 3.51 Chloromethyl 2-butyl 3.52 Dichloromethyl 2-propyl compound R: R3 Physical number data -5 0-(please read the precautions on the back before filling this page). Packing and binding The paper size is applicable China National Standard (CNS> A4 specification (210 X 297 mm) A7 B7 printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs 5. Description of the invention (〆) 3.53 trichloromethyl 2-butyl 3.54 trichloromethyl 2 -Propyl 3.55 trichloromethyl 2-butyl 3.56 2,2,2-trifluoromethyl 2-propyl 3.57 2,2,2-trifluoromethyl 2-butyl 3.58 -3-chloropropyl 2 -Propyl melting point 117-118 = 3.59 .3-chloropropyl 2-butyl 3.60 2-methoxy-ethyl 2-propyl 3.61 2-methoxy-ethyl 2-butyl 3.62 2-methanesulfon Acetyl-ethyl 2-propyl 3.6 3 2-Methanesulfonyl ethyl 2-butyl 3.64 Methylsulfonyl-methyl 2-propyl Melting point 136- 137 ° C 3 .65 2,2,2 -Trifluoroethyl 2-propyl melting point 14 3-14 4 ° C 3.66 Mz 2-propyl melting point 136-137C 3.67 nh2 2-butyl melting point 137-138t: 3.68 NH (CH3) 2-propyl melting point 133- 136 ° C 3 67 NH (CH3) 2-butyl Melting point 142- 144Ό 3.70 NH (ethyl) 2-propyl melting point 105-106 ° C 3.71 NH (ethyl) 2-butyl melting point 1 04- 10 51 -5 1- (please read the precautions on the back before filling this page). The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of invention (0) Table 3a (prepared according to method b) II · I ^ —3 R1— S — NH- C-C-NH -CH2CH2 ^ Q)-〇CH3 R3 Ο

The stereochemistry of the alpha carbon atom of the amino acid that has been revealed: S — ^ ϋ. Mi II 1.- I mi n (please read the precautions on the back and then fill out this page) Printed compound Ri R3 Physical number data 3.90 2-propyl 2-propyl resin 3.91 2-butyl 2-propyl resin 3.92 2-butyl 2-butyl resin 3.93 2-methyl-propyl 2- Melting point of propyl 113-114 ° C 3.94 Melting point of 2-methyl-propyl 2-butyl 1 0 2-1 0 3 C 3.95 Melting point of pentyl 2-propyl 91-92 ° C 3.96 Melting point of pentyl 2-butyl 7 4-7 5 ^ 0 3.97 Hexyl 2-propyl Melting point 94-9 5¾ -52- The size of the linear paper is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) 312611

3.98 Hexyl 2-butyl Melting point 99-100 ° C 3.99 Cyclohexyl 2-propyl resin 3.100 Cyclopentyl 2-propyl resin 3.101 Cyclopentyl 2-butyl resin 3.102 Cyclohexyl 2-butyl resin 3.103 2- ( MeO-forged) -ethyl 2-propyl melting point 121-1231 3.204 ethyl cyclohexyl melting point 155-1561: 3.205 ethyl cyclopropyl melting point 123-124Ό (please read the precautions on the back before filling this page) . Η- 6 · 1 ·: (S) — 2- (isopropylsulfonyl sulfonyl) monoamino-3 monomethyl monobutyric acid N_ [2— (3,4-dimethoxyphenyl)- Ethyl] Monoamide [Method c)] Order

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs [Compound 6 · 1] 3. 7 grams of (S) — 2-amino-1 — 3-methyl-butyric acid N — [2 — (3, 4-dimethyl Oxyphenyl) -ethyl] -amidamide (Example 3.90) -53- This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 〇II RjS 11 〇OCHq OCH,

A7 B7 V. Description of the invention (0) Dissolved in 5Q ml of acetone at room temperature with potassium permanganate plus M saturated propionate solution M was added dropwise to the above stirred solution for 5 minutes until the reaction mixture was maintained Until the purple color of permanganate. The reaction mixture was stirred at room temperature for 45 minutes. The resulting manganese dioxide is removed by filtration on C e 1 i t e. The liquid was evaporated to dryness and the resulting residue was dissolved in 150 ml of methyl acetate. The organic phase was washed once with 2Q0 ml of water, dried over sodium sulfate and concentrated. The resulting residue was chromatographed on silica gel and M part methyl acetate eluted a mixture of n-hexane. (S) — 2 — (isopropylsulfonyl) _amino-3-methyl-butyric acid N— [2— (3,4-dimethoxyphenyl) -ethyl] monoamide Purified by recrystallization from ethyl acetate / hexane, melting point 8 6-8 7 t :. The compound M shown in Table 6 is obtained in a manner similar to this example ° Table 6 (prepared according to method c)) Η

I ΝΗ— C — C — ΝΗ— CH〇CH-I I! 2 'R3 Ο Stereochemistry of the alpha carbon atom of the amino acids disclosed -54- This paper scale applies the Chinese National Standard (CNS) A4 ^ Grid ( 210X297mm) (Please read the precautions on the back before filling in this education). Pack. Order A7 B7 5. Invention description (less Ί)

Compound R i Rs Physical number data 6. 1 2-propyl 2-propyl melting point 86-8 T ° C 6. 2 2-butyl 2-propyl melting point 92- 9 3¾ 6 · 3 2-butyl 2-butane Resin 6 · 4-2-Methyl-propyl 2-propyl Melting point 78- 80 t: 6.5. 2-Methyl-propyl 2-butyl Melting point 74- 7 6¾ 6. 6-pentyl 2 -Propylene melting point 95-96 ° C 6.7 Melting point of 2-pentyl 2-butyl 96-97¾ 6.8 Melting point of hexyl 2-propyl 10 2 -1 0 3 eC 6.9 Melting point of 2-hexyl 2-butyl 102 -1 03 t: 6 · 10 cyclohexyl 2-propyl resin 6. 11 cyclopentyl 2-propyl resin 6 · 12 cyclopentyl 2-butyl resin 6. 13 cyclohexyl 2-butyl resin 6. 14 2-(M e 0-carbonyl) -ethyl 2-propyl 98 -9 9 ° C (please read the precautions on the back before filling in this page) Binding-Order 4 Examples of preparation of intermediate products: Z- 1 · 1: (S) — 2-Amino- 3-methyl-butyric acid N- [2-(3.4-dimethoxyphenyl) -ethyl] monoamide-55- This paper size is applicable to China country Standard (CNS) A4 specification (210X297mm) 3126 A7 B7 V. Description of invention (Θ) NH2-CH — C — ΝΗ — CH2CH2_ 〇

〇CH3) —〇cHg (please read the precautions on the back before filling in this page) [Compound 4 · 1], 23.8g (S)-2-[(1,1-dimethylethyl) Monooxycarbonyl] -amino-3-methyl-butyric acid N- [2- (3,4-dimethoxyphenyl)]-ethyl-amide at room temperature and 7QQ ml of 4 N hydrogen The chloric acid was mixed for 24 hours. The reaction mixture was extracted twice with 25 Q ml of ethyl acetate each time; the organic phase was washed with K2GG ml of 2N hydrochloric acid once and discarded. The mixed aqueous phase is first adjusted to about pH 6 with solid sodium hydroxide and then adjusted to above pH 8 with K solid potassium carbonate. The aqueous phase was then saturated with sodium chloride and extracted twice with 50 mL of ethyl acetate each time. The preserved phase M200ml of saturated sodium chloride solution was washed once, mixed, dried over potassium carbonate and concentrated. (S) —2-Amino-3-methyl-butyric acid N- [2- (3,4-dimethoxy-phenyl) -ethyl] -amide can be obtained from ethyl acetate / hexane It was obtained by recrystallization and K purification in the middle, melting point 5 2-5 4 TC. The intermediate products shown in Table 4 were obtained in a similar manner to this example. Table 4: -56- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) V. Description of the invention ('< /) A7 B7 R2 R4 H2N — C — C — NH-CR, «II I ° r3 o r6

. Stereochemistry of the alpha carbon atom of amino acids: S The cracked compound Rz R3 R4 Rs Re of the Central Standard Falcon Bureau Employee Consumer Cooperative of the Ministry of Economy Physical data 4.1 H 2-propyl H H 3,4-dimethoxybenzyl Base melting point 52-54Ό 4.2. Η 2-butyl Η 3,4-dimethoxybenzyl melting point 86-88C 4.3 Η 2-methyl- Η Η 3,4-dimethoxybenzyl melting point 70- 72 ° C Propyl 4.4 Η 2-Methylthio- Η Η 3,4-dimethoxybenzyl resin ethyl 4.5 Η hydroxymethyl Η Η 3,4-dimethoxybenzyl 4.6 Η 1-hydroxyl -Ethyl Η Η 3,4-dimethoxybenzyl melting point 112-113C Z-2.1: (R, S)-methanesulfonic acid N-[2-methyl-1-yl) monopropyl Yitengamine-57- (Please read the precautions on the back before filling in this page)-Binding-The paper size of the binding is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) V. Invention description A7 B7

0 II CH3-S-NH-CH-COOH compound 1] • 30 g of d, L-valeric acid and 10. 2 g of sodium hydroxide are dissolved in 250 ml of water, and the solution is used during mixing Cool to. 10 • A solution of 2 g of sodium hydroxide in 25 g ml and 20 ml of methanesulfonyl chloride in 250 ml of toluene are added to this solution dropwise at the same time over an hour. The reaction mixture was first stirred at 0 = 2 hours and then at room temperature for 16 hours. The toluene phase is separated in a separatory funnel and discarded. The aqueous phase K concentrated hydrochloric acid is adjusted to below pH3. Each time K1QG0 mL of diethyl ether was extracted twice. The organic phase was washed twice with 200 mL of saturated sodium chloride solution each time, mixed, dried over magnesium sulfate and concentrated 0 (R, S) -methylsulfonic acid N- [2-methyl-1 1-carboxyl ) -Propyl-acetamide can be obtained by recrystallization from ethyl acetate / hexane plus M purification, melting point 9 〇-9 nc. The intermediate products shown in Table 5 were obtained in a manner similar to this example. Table-58 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 10X297mm> = ---. ^^^ 1 ^ ϋ · 1 ^ 1 fm In- ^^ 1 — (please read the notes on the back first Matters refill this page) Order S12611 A7 B7 V. Description of the invention (彡 巧) _ S-NH-C-COOH " I (〇) n R3 Stereochemistry of the oc carbon atom of the amino acid revealed by: Compound 5 · 1, 5 · 3, 5 · 5 to 5 '.7 is R, S compound 5 * 2,5 I · 4,5 ι · 8 to 5. 1 5 is S compound Ri η Rz Rs Physical number data 5.1 A Base 1 Η 2-propyl melting point 90 5.2 methyl 1 Η 2-propyl oil 5.3 Mez N-1 Η 2-propyl oil 5.4 Μθ2 Ν-1 Η 2-propyl resin 5.5 methyl 0 Η 2-propyl 5.6 2-propyl 0 Η 2-propyl-59- _ _ _ _ _ _- ^ ^ _________ _____ "^ J ^ ¾. Ί 1 " (Please read the notes on the back before filling this page ) This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm) A7 B7 V. Description of invention (Clock)

7 2-methyl-2-0 Η 2-propylpropyl 8 methyl 0 Η 2-propyl 9 2-propyl 0 Η 2-propyl 10 2-methyl-2- 0 Η 2-propyl .Propyl 11 'ethyl 1 Η 2-propyl resin 12 • Me2 N 1 Η 2-butyl resin 13 ethyl 1 Η 1- (2-Me-oily 2-Pr) -0- ethyl 14 Methyl 1 Η ethyl resin 15 ethyl 1 Η ethyl resin 16 methyl 1 Me methyl melting point 109-111 ^ 0 17 methyl 1 tetramethylene melting point 133-135 ° C (please read the notes on the back first (Fill in this page again). Binding · Thread 2 · Example of the adjustment of the active ingredient of formula I (% = weight percent) Example F 2 · 1: Wettable powder a) b) c) from tables 1,2,3, The active ingredients of 3a and 6 25% 50% 75% -6 0-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 5. Description of invention () sodium lignosulfonate 5% laurel sulfate Acetate sodium 3% diisobutyl naphthyl sulfonate-octanol polyethylene glycol ether (7-8 moles of ethylene oxide) high. Highly dispersible silicic acid 5% kaolin 62% 5% 6% 2% 10% 27% 5% 10% 10% active ingredient Mixed with the additives and the mixture in a suitable mill grinding is carried out completely. The wettable powder can be diluted with K water. • A suspension with the desired concentration is obtained. Example F 2 · 2: Emulsion concentrate ingredients from Tables 1, 2, 3, 3 a and 6 active ingredients octylphenol polyethylidene glycol ether (4 to 5 moles of ethyloxy units) Calcium dodecyl benzene sulfonate castor oil polyethylene glycol ether (36 moles of ethyloxy units) Cyclohexanone 10% 3¾ 3% 4% 30% (Please read the precautions on the back before filling in this Page) • Binding. Thread-61- This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) * 12611 A7 B7 V. Description of the invention (β) Xylene mixture 50% Any desired dilution It can be prepared from these emulsified concentrates by adding M using water. . Example F 2 · 3: Dusts from the active ingredients talc kaolin from Tables 1, 2, 3, 3a and 6 a) b) 5% 8% 95% 92% of the available dust, and the Ministry of Economics Central Falcon Bureau employees consume Hefei fi Zhonghuan. The mixture is ground in a suitable grinder. Example F 2.4: Extruded granules. The active ingredient from table 1, 2, 3, 3a and 6 is sodium carboxyl lignosulfonate Methylcellulose kaolin 10% 1% 1% 87% The active ingredients and additives are mixed and ground, and the water is moistened -62- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) I- ------- ^ 装 ------ 定 ----- "line (please read the precautions on the back before filling in this page) 3 96 3% 94% A7 B7 5. Description of invention (β ) Mixture. The mixture is extruded and then dried in a stream of air. Example F 2 · 5: The coated particles from Tables 1, 2, 3, 3a and 6 of the active ingredient poly-extruded. Ethylene glycol (mu 1. wt. 2 0 0) Kaolin's finely ground The active ingredient is uniformly mixed with kaolin in a mixer, and humidified with M-polyethylene glycol plus M. Non-dust-coated particles are obtained in this way. Ben Example F 2 · 6: Concentrated suspension The active ingredients from Tables 1, 2, 3, 3a and 6 40% Ethylene Glycol 10% Nonylphenol Polyethylene Glycol Ether 6% ( 1 5 molar ethylene oxide) sodium lignosulfonate 1Q% carboxymethyl cellulose 1% 3 7% formaldehyde aqueous solution 0.2% 75% emulsion solution type silicide oil Q · 8% water 32% -6 3-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the notes on the back before filling out this page)

Printed by the Employee Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention () The finely milled active ingredients are intimately mixed with additives, and the resulting concentrated suspension fatigue is stored steadily at low temperatures and quite high temperatures. Dilute with water to get the desired Hudu. Biological Example Spring Example B-1: Active anti-Plasmopara Viticola on grapevine vines Seedling seedlings of grapevine vines at the stage of 4-5 leaves K-spray mixture (containing 〇. 0 2% of the active ingredient) spray, the sprinkler irrigation is prepared with a wettable powder of the active ingredient of the mixture K. 24 hours later, the treated plant M. sporangia suspension of the fungus was infected. After incubation at atmospheric relative humidity of 95-100% for 6 days, a large number of fungal parasites were evaluated by M. The active ingredients 1.2, 3. 1, 3, 19, 3. 25, 3. 29 and other compounds can completely prevent a large amount of parasitism (〇_1〇% large amount of parasitism). In contrast, the untreated but infected control plants had 100% parasitic fungi parasitism. Example B-2: Fighting against the fungi of the genus Bacteria on tomato plants (-64- (please read the note $ item on the back and then fill in this page). Stupid. The paper size is applicable to China National Standard (CNS) Α4 specifications ( 210X297mm) A7 __B7 ___ printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Activity of Phy tophthora) a) Residue protection Active growth of tomato M for 3 weeks-Spray with a mixture (containing 0.02% of active ingredient), which is prepared with a wettable powder of the active ingredient of the mixture K . After 48 hours, the treated plants were infected with the sporangia suspension of the fungus. After incubation at 2〇υ and atmospheric relative humidity of 90-100% for 4 days, a large amount of fungal parasitism was evaluated by K. b) Tomato M grown whole plant sexually active for 3 weeks-spray mixture (containing 0.02% of active ingredient relative to soil volume) for spraying, the spray is prepared with wettable powder of active ingredient of mixture K to make. Use care so that the spray mixture does not touch the aerial parts of the plants. After 4 days, the treated plants were infected with the sporangia suspension of the fungus. At 2Qt: and atmospheric relative humidity of 90 -10 0% after 4 days of incubation, a large number of fungal parasites were evaluated by M. Active ingredients 3. 1, 3. 19, 3 * 25, 3. 29 and other compounds can actually completely prevent a large number of parasites (0-5% of large parasites). In contrast, the untreated but infected control plants had 100% parasitic phytophthora. -65- This paper scale is applicable to China National Standard (CNS) Α4 ^ # · (210X297mm) l ^ i-m J 丨 -called I—ILH ^^ 1. ^ Ϋ ^ I (Please read the notes on the back first Please fill in this page for details.) A7 B7 Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5. Description of the invention () Example B-3: Fighting residues of Cercospora arachidicola in peanuts Peanut plant M sprinkling mixture aqueous solution (0.02% active ingredient) with a high protective activity of 1Q to 15 cm is sprayed to the dripping stage, and the spray is prepared with a wettable powder of the mixture M active ingredient. 4 After 8 hours K, the treated plant K was infected with a conidia suspension of the fungus. The plant was incubated in 2HC at high atmospheric humidity for 72 hours, and then placed in the greenhouse until the typical leaf spots appeared. Twelve days after infection, the effect on the active ingredient was evaluated based on the number and size of leaf spots plus M. The active ingredient of formula I reduces the leaf spots below the leaf surface area. In some instances the disease is completely suppressed (0-5% parasitic mass). Compounds 1.1, 1.11, 1.22, 1.26, 1.28, 1.31, 1.36, 1.42, 1.47, 1.52-1.60, 1.69, 1.76, 1.84, 1.134, 1.137, 1.150, 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14, 3.20 , 3.42-3.45, 3.71, 3.93-3.98, 3.205 and 6.1 reduced fungal invasion II to 10 to 0%. B-4: Against the activity of Puccinia graninis on wheat (Puccinia graninis activity-66- This paper scale is applicable to the Chinese National Standardization (CNS) A4 ^ grid (210X2.97mm) (Please read the notes on the back first (Fill in this page again) Packing.-Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Contains 12611 A7 B7. 5. Description of the invention () a) Residue protection activity 6 days after sowing, an aqueous solution of wheat plant K Penxiao mixture (0 · 0 2% of active ingredient) spray * to the dripping stage. After 24 hours K, the treated plant K was infected with a suspension of uredospore of the fungus. After 48 hours of incubation (condition: at 2〇υ and atmospheric relative humidity of 95-100%), the plant was placed in a greenhouse of 22Ό. Twelve days after infection, K was added to assess the development of rust spots. b) Whole plant sexual activity Wheat plants five days after sowing, M-spray mixed water solution (containing 0.0006% active ingredient relative to soil volume) for spraying. Be careful to ensure that the spray mixture does not touch the aerial parts of the plants. After 4.8 hours K, the treated plant M. uredo spore suspension of the fungus was infected. After 48 hours of incubation (environment: at 2〇υ and atmospheric relative humidity of 95-100%), the plant was placed in a greenhouse at 22 =. Twelve days after infection, K was added to assess the development of rust spots. The compound of formula I significantly reduces the fungal attack, in some cases to 10-0%. Compounds 1.1, 1.11, 1.22, 1.26, 1.28, 1.31, 1.36, 1.42, 1.47, 1.52-1.60, 1.69, 1.76, 1.84, 1.134, 1.137, 1.150, 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14 , 3.20,3.42-3.45,3.71, -67- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling in this page). Packing. Order A7 B7 _ 5. Description of the invention () 3.93- 3.98, 3.205 and 6.1 reduce the fungal infestation to 1D to 0% ° Example B-5: The protective activity against the residue of Curvularia fungi (Venturia inaetualis) on apples is highly 10 to A 20 cm sprout of apple shoots M sprinkled with an aqueous mixture solution (0.02% active ingredient) was sprayed to the dripping stage. The spray badger was prepared with a wettable powder of the mixture K active ingredient. After 24 hours, the treated plant K conidia of the fungus was infected. The plant is cultivated for 5 days at a relative atmospheric humidity of 90% to 100% and then placed in a greenhouse of 20 to 2 for 10 days. Fifteen days after infection, a large number of spot infections were evaluated with K. Compounds of formula I from Tables 1, 2, 3, 3a and 6 mainly show the mineral-holding effectiveness against spot disease (less than 10% of large infections) ° Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the back page first Note f and fill in this page again) Compounds 1 · 1, 1.1. 1 1, 1 2 2, 1. 2 6, 1, 2 8, 1. 3 1, 1, 3 6, 1 · 4 2, 1, 47, 1.52 -1.60, 1.69, 1.76, 1.84, 1.134, 1.137, 1.150, 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14, 3.20, 3.42-3.45, 3.71, 3.93- 3.98, 3.205 and 6.1 reduce fungal infestation to 10 to 0%. Example B-6: Activity against barley fungus (Erysiphe graainis) on barley-68- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) B7 V. Invention description () about 8 The barley plant M high in centimeters is sprayed with water-soluble mixture (the active ingredient of o ·) and sprayed to the dripping stage. After 3-4 hours, the treated plant M. conidia dust of the fungus is infected. The infected plant was placed in a 22 * 0 greenhouse. Ten days after the infection, M was evaluated for the fungal attack. Compounds of formula I are usually able to reduce the mass infection of the disease to below 20% Μ, and in some cases achieve complete inhibition. Compounds 1.1, 1.11, 1.22, 1.26, 1.28, 1.31, 1.36, 1.42, 1.47, 1.52-1.60, 1.69, 1.76, 1.84, 1.134, 1.137, 1.150, 2.1, 2 4-2 · 6, 2. 17, 2. 48, 3.1, 3.14, 3 · 20, 3. 4 2-3. 4 5,3 · 71, 3.93-3.98, 3.205 and 6.1 reduced fungal infestation to 10 to 0%. B — 7: Anti-residual protection against vine fungus (Botyris cinerea) on apple fruits Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Apples after artificial injury A spray mixture (〇 * 02% active substance) was dropped onto the damaged area for treatment. The treated fruits were then injected into the fungus and the spores were suspended and cultured under high atmospheric humidity and 20 ° C for one week. The fungicidal activity of the test substance is extrapolated based on the number of damaged areas on the surface. The active components of Formula I from Tables 1, 2, 3, 3a and 6 can be -69- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) Employee consumption cooperation Duin of the Central Sample Bureau of the Ministry of Economic Affairs System A7 B7__ 5. Description of the invention () To prevent the spread of rot, in some instances it can be completely prevented. Compounds 1.1, 1.11, 1.22, 1.26, 1.28, 1.31, 1.36, 1.42, 1.47, 1.52-1.60, 1.69, 1.76, 1.84, 1.134, 1.137, 1.150, 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14, 3.20 , 3.42-3.45, 3.71, 3.93-3.98, 3.205 and 6.1 reduced fungal infestation to 10 to 0%. B-8: Effect on rice against Rhizoctonia solani a) Suspension made by applying a 10-day-old rice plant K from a test substance plus K-regulator to a protective local soil (spray mixture) ) Wet and do not contaminate the above-ground parts of plants. Three days later, infection was carried out between rice plants in each pot by placing straw infected with Rhizoctonia solani. After 6 days of incubation in a climate-controlled room with a daytime temperature of 29 ° C and a nightfall temperature of 26 ° C and 95% relative atmospheric humidity *, evaluate the situation of fungal infection. Less than 5% of the rice plants show parasitism. The plant has a healthy appearance. b) Protective local leaf application of 12-day-old rice plants using the self-test substance to adjust the suspension -70- This paper scale is applicable to China National Standard (0?) 8 4 * 1 ^ (210 father 297 Cli) (Please read the precautions on the back before filling in this page) Binding · Order A7 B7 312611 5. Description of the invention () Floating liquid (spilling mixture) to carry out the rotten. One day later, infection was carried out between rice plants in each pot by placing straw infected with Rhizoctonia solani. The evaluation was conducted after 6 days of cultivation in a climate-controlled room with a day temperature of 29Ό and a night temperature of 26C and 95% relative atmospheric humidity. The untreated but infected control plants showed 100% mass parasitization. The compound of formula I almost completely inhibits the massive infection of the disease in some cases. Compounds 1.1, 1.11, 1.22, 1.26, 1.28, 1.31, 1.36, 1.42, 1.47, 1.52-1.60, 1.69, 1.76, 1-84, 1.134, 1.137, 1.150, 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14 , 3.20, 3.42-3.45, 3.71, 3.93-3.98, 3.205 and 6.1 reduced fungal infestation to 10 to 0%. B-9: Action against Helminthosporium graminearum fungus (Helminthosporium g r a m i n e u m) Infect and dry the spore suspension of wheat spore K fungus. The suspension of the contaminated particles M test substance is coated (active ingredient based on the weight of the seed 60 ρρη). After 2 days, the grains were placed on a suitable agar plate, and after 4 days, fungal colonies around the grains were evaluated. The number and size of fungal colonies are used to evaluate the test substance. In some cases the test compound of formula I shows a very good effect, i.e. complete inhibition of fungal colonies. -7 1- This standard is applicable to China National Standard (CNS) Α4 specification (210X297mm) J—ί — * ---- γ Packing ------ order ------ f (please Read the precautions on the back first and then fill out this page) Printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs 312611 A7 B7 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of the invention () Compound 1.1, 1.11, 1.22, 1.26 , 1.28, 1.31, 1.36, 1.42, 1.47.1.52- 1.60, 1.69, 1.76, 1.84, 1.134, 1.137, 1.150, 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14, 3.20, 3.42-3.45, 3.71, 3 .9 3-3.98, 3.205 and 6.1 reduce fungal attack to 10 to 0%. Example B-10: Action against Phythium debaryanuia on sugar beet The fungus grows on sterile oat grains and is added to a soil / sandstone mixture. The pots are filled with this infected soil and the beet seeds are planted. Immediately after the next planting, the M-wettable powder. The type of the test preparation is poured into the soil (the active ingredient is 20PPIII relative to the soil volume). The flower pot is then placed in a greenhouse at 20-24C for 2-3 weeks. The soil is kept evenly moist by spraying water. When the test is evaluated, the number of beet plants and the proportion of healthy and diseased plants are determined. After treatment with the active ingredients of formula I *, the occurrence rate of plants exceeds 8ϋ%, and these plants have a healthy appearance. However, only a few plants with disease appearance appeared in the pots of the control group. Compounds 1. 1, 1. 1 1, 1.2 2, 1.2 6, 1.2 8, 1.3 1, 1.3 6, 1.4 2, 1.47.1.52- 1.60, 1.69, 1.76, 1.84,1.134,1.137,1.150, -72- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page). A7 B7 V. Description of invention ( ) 2.1, 2.4-2.6, 2.17, 2.48, 3.1, 3.14, 3.20, 3.42-3.45, 3.71, 3.93-3.98, 3.205 and 6.1 reduce fungal attack to 10 to 0%. (Please read the precautions on the back before filling out this page)

, 1T

• Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -73- This paper scale applies the Chinese National Standard (CNS) Α4 specification (210X297 mm)

Claims (1)

— A compound of formula I 0 Ra r4 Ri —S—NH (0) n -NH- -Rs 0 Re where n is 0 or 1; Ri is h _Ci 2 alkyl, which is unsubstituted or passable ( ^ —C4 alkylsulfonyl group is substituted with M; Cs cycloalkenyl group: 2 — C4 alkenyl group; Ci _ C haloalkyl group or a group 1 ^ 1 3 Rj (please read the precautions on the back before filling this page ) Outfit · Printed by the Employee Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs; where R! 3 and Ri 4 are independently hydrogen or Ci-Cs alkyl or together are tetrakis or pentamethylene; R2 and R3 are independently hydrogen ; Ci-Cs alkyl; Ci a (: 6 alkyl, which is substituted by hydroxy, Ci _C4 alkoxy or (: ^ alkylsulfide plus M substituted; C3-Ce ring burning group, or wherein R2 and R3 two bases , Together with the carbon atoms they bind to form a tri- to six-membered carbon ring; IU is hydrogen or Ci_C4 alkyl; hydrogen; Ci_C4 alkyl or phenyl, which is unsubstituted or can be passed Halogen; Re is a group G -1 This paper scale adopts the Chinese National Standard (CNS) Α4 specification (210 X 29 7 mm), and the patent application range in the year G A8 B8 C8 D8 R1 R1 wherein R7 and R8 are independently hydrogen; p is ο or 1; and r9.,. And Ri 1 are independently hydrogen, Cl-C4 yard group, C 1 — C4 _ yard group C 1 C 4 alkoxy group, C 3-Cs alkenyl group oxygen, c 3 — C, (please read the notes on the back before filling in This page). Packing · Oxygen alkylsulfide, halogen or nitro. If the compound of formula I of the first item of the patent scope is set to 0 Rz R4 R Guang S-NH -NH- -Rs 0 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (Ο) η R3 R6 where n is 0 or 1; R! Is C!-C -2- alkyl; C i alkyl paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 VI. The scope of patent application, which is based on Ci — c4 alkyl Sulfonyl group is substituted with κ; c2-c4 alkenyl; Ci-c4 haloalkyl or monoradical NRI 3 Ri 4; wherein R! 3 and R i 4 are independently Ci-Cs alkyl or four together One or pentamethylene; R2 and R3 are independently hydrogen; Ci — C6 alkyl; Ci — C6 alkyl, which is substituted by hydroxy, ci — C4 alkoxy or Ci alkyl sulfur plus κ; 3-cs cycloalkane Group; or two groups of R2 and R3, together with the carbon atom to which they are bonded to form a three one to six member carbocyclic ring; R4. Is hydrogen or C1-C4 burned group; R5 is hydrogen; Cl- C4 courtyard group or phenyl group, which is unsubstituted or substituted by halogen; and is a group G: 丨 _Γ __.---- 一 — 装 ------ 定 ------ ^ Travel (Please read the notes on the back first (Fill in this page) The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative printed R and ο hydrogen is independent 8 R and 7 R ο is P hydrogen is independent 4 C 9 R 1 C and, 1; base Or alkyl alkane 4 C oxyalkyne 6 C nitrate or element, halo, oxysulfanyl 4 alkane C 3 C 3 C oxyalkene 6 C compound C combined with its chemical I term base 2 alkane 2 Fan C. Lee I Special 1 0 C, 1 * If the 4 C C1 sulfur in the alkane R is the base 1 alkane 10 R · R This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 312611 A8 B8 C8 D8 々, patent application scope 1-C4 alkylsulfonyl group with M substitution; C2-C4 alkenyl; Ci -Cl 2 haloalkyl or a group NRi 3 Ri 4; wherein R 1 3 and Ri 4 are independently Ci- (] 6 alkyl, or together are tetra- or pentamethylene; r2 is hydrogen; R3 is C!-Cs alkyl; C 1-ce alkyl which is a hydroxyl group, C! A C4 oxy or Ci sulfide plus' to replace; or C3 ~ ~ Cs cyclic alkyl; R 4 is hydrogen; R5 is Phenyl, which is unsubstituted or substituted by halogen plus κ and RS is a group G where P is 〇; and r9, Ri 〇 and Ri i are independently hydrogen, Ci-C4 alkyl, Ci-C4 halogen Alkyl group, Ci — C 4 alkoxy group, C 3 -C 6 alkenyl oxygen group, C 3 -Ce block oxygen group, halogen or nitro group. 4. The compound as claimed in item 1 of the patent application, where η is 0 or 1; R 1 is Cl — Ci 〇 burned base; Cl _ C 4 toothed base; C2 — .C4 dilute base; Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives printed (please read the precautions on the back before filling this page) C 5 1 C 6 ring courtyard; C 1 _ C 6 Group, which is substituted by C 1 -C 2 —-homoylamino group with K; Rz is hydrogen; R3 is C2-C5 alkyl or C3-Ce cycloalkyl; 1U is hydrogen; Rs is phenyl, which is not Substituted or substituted by halogen plus K; and R6 is a radical G, where P is 〇; Rg is hydrogen; and Ri 〇 and 1 ^ 1 are independently hydrogen or halogen. Compounds, where η is 0 or 1 * R 1 is "-C !. alkyl; Ci-C4 haloalkyl; C2-C4 alkenyl, or ^ -C2 dialkylamine; Rz is hydrogen; R3 is C2 — C5 alkyl or C 3 — Cs cycloalkyl; R4 is hydrogen; Rs is phenyl, which is unsubstituted -4- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Economy A8 B8 C8 D8 is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry. Six, patent-applicable or substituted by halogen; and R6 is a group G, where p is 0; R9 is hydrogen; and Ri and independently are Hydrogen or halogen. 6 • The compound as claimed in item 5 of the patent application, where η is 1. 7 • The compound as claimed in item 5 of the patent application, where η is 1; and Ri is methyl, ethyl, ethylene Or dimethylamino. 8 * The compound as claimed in item 4 of the patent application, where η value is 1; and R: methyl, ethyl * vinyl, cyclopentyl, cyclohexyl or dimethylamino . 9. The compound as claimed in item 5 of the patent application park, where η is 1; and R 3 is C3-C4 alkyl. 10. The compound as claimed in item 1 of the patent scope, which is (: 1 —C 1 2 alkyl group; C5 — C6. Cycloalkyl group; Ci — Ci 2 hospital group • Its ci _ C4 alkylsulfonyl group, To be substituted; C2-C4 alkenyl; C i -C 4 haloalkyl or monoradical 3 Ri 4; where R! 3 and 1 4 are independently hydrogen or Ci-Cs alkyl or are collectively Siyi or Wuya Methyl; R2 is hydrogen; R3 is Ci-Ce alkyl; Ci-C6 alkyl. It is substituted by hydroxyl, Ci-C4 alkoxy or h alkylsulfur plus M; or C3_C6 cycloalkyl; R4 is hydrogen or h — C4 alkyl; Rs is hydrogen; or “-C 4 -5-This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) ---- 1 ---- JI Pack ------ Subscribe ------ ^ Travel (please read the precautions on the back before filling in this page) A8 B8 C8 D8 々 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy 々, apply for patent scope alkyl; And R6 is a group G, wherein R7 and Rs are independently hydrogen; P is 1; and 11 g, Ri. And Ri i is independently hydrogen, Ci-C4 hospital group, Ci — C4 tooth hospital group, Ci — C4 home. Oxygen, C3-C6 base oxygen, C3-Cs alkynyl oxygen or halogen. 11. The compound as claimed in item 2 of the patent scope, wherein Ri is (^ -h 2 alkyl, Ci — C: 2 alkyl, which is substituted by Ci — C 4 alkylsulfonyl; C 2 — C 4 alkenyl; C : — C4 haloalkyl or a group NR 1 3 Rt 4; wherein Ra 3 and Ri 4 are independently Ci — Cs alkyl or together are tetrakis or pentamethylene; Rz is hydrogen; R3 is “_CS alkyl Group; h_C6 alkyl, which is substituted by hydroxyl, h-C4 alkoxy or Ci alkyl sulfur plus M; or C3-C6 cycloalkyl; IU is hydrogen or C i-C4 alkyl; Rs is hydrogen or Ci- C4 alkyl; and Rs is a group G, wherein R7 and Rs are independently hydrogen; P is 1; and R9, Ri 〇 and Ri i are independently hydrogen, Ci-C4 alkyl, Ci-C4 haloalkyl , H—C4 alkoxy, C3_C6 alkenyloxy, C3—Cs alkynyloxy or halogen. 12. Compounds as claimed in item 2 of the patent application, where η is 0 or 1; R 1 is Ci — Ci 〇 院Base · Ci — C4 dentate group * Cz — Cs lay group or C i — c2 dialkylamine group; R2 is argon; R3 is c2 — c5 alkyl group or c3 — C6 cyclic group; R4 is hydrogen or Ci _C4 Hospital group; Rs is hydrogen; and is a group G where R7 is hydrogen; Ra is hydrogen; P is 1; and R 9, Ri 0 and R! Are independently hydrogen, Ci —C4 alkyl, Ci —C4 haloalkyl-6- This paper scale is applicable to China National Standard (CNS) Α4 specifications (210Χ297 mm) — ^ --- ------ 一 丨 装 ------ 定 ----- Η 旅 (please read the notes on the back before filling in this page) A8 Βδ C8 D8 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 々. Scope of patent application, Cl-C4 oxygen, C3-C6 dilute oxygen, C3-C6 deficient oxygen or halogen. 13. The compound as claimed in item 12 of the patent application, wherein η is 1; Ri is Ci — Ci 〇 trace group, Ci — C4 ′ tooth burn group * C2 _C4 laying group or Ci-c2 dialkylamine group; R9 is Hydrogen; and ^. And Ri i is "-C4 alkoxy. 14 ♦ Compounds as claimed in item 13 of the patent application * wherein Ri is (^ -C4 alkyl; h-C4 haloalkyl, vinyl or dimethylamino. 15 · For example, the compound in the 13th range of the patent application, where R3 is C3-C4. 16. For the compound in the 13th range of the patent application, where R4 is hydrogen; and R8 is hydrogen * 17 * If the range of the patent application is The compound of item 13, wherein O is P-Cl-C4 alkoxy; and Ri 1 is ffl-Ci-'C4 oxy. 18. The compound of item 17 as claimed in the patent application, wherein Ri is (^ -C4 Alkyl, vinyl or dimethylamino; Ri 0 is P-methoxy; and Ri 1 is m-methoxy. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) .---- 一 丨 installed ------ ordered ------ j-point (please read the notes on the back and then fill in this page) 312611 Bismuth C8 D8 VI. Patent application scope 19. If apply The compound of the 1st item of Patent Fan Yuan, where η is 1; and R is (^-Ct 〇alkyl; Ci — C4 haloalkyl; C 2 — C 4 alkenyl; C 5 — Cs cycloalkyl group; or C 2 — The second house base amino group; Nitrogen; and R i 〇 and Ri 1 are Ci — C # hospital oxygen * Cs — Cs oxyl oxygen or C 3 — Cs oxy oxygen deficiency. 2 0 · For example, the compound of claim 19, wherein R i is C i -C4 alkyl group, Ci _C4 haloalkyl group, vinyl group, dimethylamino group or CS-C 6 ring hospital group. 21. The compound as claimed in item 19 of the patent application, where R3 is C3-C4 house Based on the item printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, its physical and chemical items 9 1A are included, and the bases are based on oxygen oxanes, such as 4 PP or oxyene P, which is-^ ------ -Install ------ order ------ ^ *! 1 (please read the precautions on the back before filling in this page) Oxygen is an oxoalkane item 2 2 Please enumerate as alkane P or oxypropenyl R amine and methoxydiyl or propylalkyne I Ethyl is a group 1 oxy R in the middle-its P, is a compound of 1 RP group oxymethyl group I m is its compound Item 3 2 Special Applicant of &Fan; If P is the paper size, the Chinese National Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 々, apply Li a range methoxy and R! I m- is methoxy. 25 ·-A method for preparing a compound of formula I as claimed in item 1 of the patent application, which includes a) by replacing the substituted amino acid of formula II 0 Rz Ri -S -NH-C-COOH (0) n R3 II, in the presence or absence of an acid binder and in the presence or absence of a diluent, printed with the amine of formula III R 4 Employee 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) Η 2 Ν-C-R 5 IR 6 The size of this paper is in accordance with Chinese National Standard (CNS) 84 specifications (210Χ297 mm) 312611 A8 B8 C8 D8 6. The patent application range is -80 to 150 = temperature Fan Xi conducts the reaction, or b) the sulfonic acid derivative or sulfurous acid derivative of formula IV 0 Ri — S—X IV (Ο) η in the presence or absence of an acid binder and the presence of a diluent In the absence or absence, the amine of formula V Rz R4 nn ll · II n IIII n —I nn T nn I nn 洚 、 言 id-i today (please read the precautions on the back before filling in this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperatives Hz NCC-NH-CR: R3 0 Ri -10- This paper standard is used China National Standard (CNS) A4 specification (210X297 mm) 312611 μ D8 Printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the patent application range is within a temperature range of 180 to 150¾, or c) Formula I’ Compound 〇R2 R4 R1-HN-CC-NH-i-Rs I7 R3 0 Re and an oxidizing agent * in the presence or absence of an acid or base and in the presence or absence of a diluent The reaction is carried out in the temperature range of 1501. Among them, in formulas II * III, IV, V and 1 ′, the substituents IU, Rz, R3, IU, Rs, Rs and η have the definitions in formula I and X is halogen, Ri— S〇2_〇—or Ri_S0_0_〇-11- (please read the precautions on the back before filling in this page). Pack. Book Travel_ This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) 312611 a C8 D8 VI. Patent application scope 2 6-A composition for controlling and preventing plants from being attacked by fungi, which includes a compound of formula I as an active ingredient, and a suitable carrier substance 27 A method for controlling and preventing plants from being infested by fungi, which includes combining the formula I The substance is applied as an active ingredient to the plant * part of the plant or the nutrient medium of the plant. 28. If the compound of formula I in item 1 of the patent scope is applied, it is used as a fungicide β .. (Please read the precautions on the back before filling out this page) The I-standard is printed by the Consumer Labor Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs One country, one country, one country, one middle school, one use, one fitness · I Ligong 7 9 2