TW211009B - Picolinic acid derivatives the process of manufacturing thereof and herbicide - Google Patents

Abstract

Picolinic acid derivatives or their salts represented by the following formular: (see claim 1) in which R represents hydrogen atom, alkyl group, alkenyl group, alkinyl group, benzil group, halogen-substituted alkyl group, cyanoalkyl group, alkoxyalkyl group, alkoxy-carbonyloxyalkyl group, alkoxycarbonylalkyl group, alkylcarbonyloxyalkyl group, cycloalkylcarbonyloxyalkyl group, cycloalkylalkyl group, alkali metallic atom, alkaline earth metal atom or the cation of organic amine; R1 and R2 may be same or different, and represent C1-4alkyl group, C1-4 alkoxy group, halogen atom, halogen-substituted C1-4alkoxy group or alkylsulfonyl group; X represents the group of the represented by formula (Related N and R3 and R4; see claim) (in which R3 and R4 are the same or different, and represent hydrogen atom, C1-4alkyl group, phenyl group or acyl group); cyano group, phenyl group (the group may be substituted with halogen atom, C1-4alkyl group or alkoxy group), phenoxy group, halogen-substituted C1-4alkyl group, C1-4alkoxy group, C1-4alkenyl group, C1-4 alkynyl group, hydroxyl group, trimethylsililethynyl group, nitro group, 4,6-dimethoxypyrimidine-2-iloxy group or an hydrogen atom represents the groups represented by oxygen atom or the formular (Related N and R5; see claim 1) n represents 0 or 1. however, when X is a hydrogen atom, Y represents the groups shown by formula (Related N and CHO, see claim 1).

Description

A 6 B 6 211009 V. Description of the invention (1) The present invention relates to novel pyridinecarboxylic acid derivatives that can be used as herbicides, and herbicides containing this compound that are suitable for paddy fields, dry fields and non-agricultural arable land. Hitherto, pyridinecarboxylic acid derivatives having herbicidal activity are known as ethyl 3- (4, 6-dimethylpyrimidin-2-yl) pyridinocarboxylates (for example, Japanese Patent Publication No. Sho 64-84 , European Patent No. 249707), methyl 3- (4,6-dimethoxypyrimidin-2-yl) thiopicolinate (for example, Japanese Patent Publication No. Hei 2-121973, European Patent 360 1 63 ). In recent years, a large number of such herbicides have been developed, benefiting from practical use, saving labor in agricultural work, and improving productivity. However, these herbicides have various problems in terms of herbicidal effect and safety of crops in actual use. For example, barnyard grass, wild rose flower, cocklebur, miscanthus, xuansen grass, etc., are very difficult weeds, widely distributed all over the world, in order to control these weeds, various herbicides can be used, but the effect of weeding In terms of reliability and safety to crops, the necessary satisfaction cannot be achieved, and there is an urgent need for more improved herbicides. In order to solve this problem, the present inventors have made intensive studies on the pyridinecarboxylic acid derivatives, and found that the compounds of the present invention in which a substituent such as dialkylamine is introduced into the pyridine ring of the pyrimidinylpyridinocarboxylic acid derivative are effective for 1 year and perennial grasses. The undergraduate and pillai weeds can show excellent effects with very low doses, and the weeding spectrum is very broad, and the present invention has been completed. , That is, the pyridinecarboxylic acid derivative of the present invention is represented by the following general formula: -3 ~ This paper scale is free of Chinese National Standard (CNS) A4 specifications (210x297 public goods) (please read the precautions on the back before writing Page) Apparel · The Ministry of Economic Affairs, the central standard is printed along with the industrial and consumer cooperation 211003 A 6 B6 V. Description of the invention (2)

Progeny hydrogen is R. Chinese-based alkylene 4 C oxygen, alkyl 4 alkane-C halo 1 C 4 C. -Yl clis, 4 yl-C ί 卞 1 acetylene alkane C alkane, oxyaldehyde alkane cyanide 4 base gas alkyl alkane alkane alkane alkane 4 1 c C, alkane alkane epoxy 6 1 sub-C1 original group is cool gold group, alkyl naphthenic gas such as the example of Xiangyang's amine machine Or calcium, such as equivalent amines, alkane-grade pro-low-gold dioxin, tertiary amine, low-potassium grades such as, for example, and 2 the same as C _1 or C1 the same, the daily phase base R3 oxane grade is low Substituted halogen-based gas alkyl-grade low alkyl-alkane grades are sub-primary halogens or alkyl-based sulfanes (please read the precautions on the back before writing this page).

For X in which the yf \ base hydrogen is the same or not in phase with the Ministry of Economy ’s standard and the β-industrial cooperation is printed by-Keji Yiqi (phenyl, benzene), the substitute group is cyano, gas} alkyl level Acyl lower or radical, phenyl, alkyl lower alkane, oligo, atomic protodentyl alkynyl pyrimidyloxy _ methyl 2 di C -6 yl 4 'ene · 4 yl C 6-ene 2 ethyl C group , Alkane, promethane 4 trihydro C4, or 1-yl, C1 nitro ,, gas-based alkane hydroxy 2-halo-yl chlorane This paper standard does not use the Chinese National Standard (CNS) A 4 specifications ( (210X297 male dragon) 2110031 Λ 6 Β6 V. Description of the invention (3 Y is a gas atom or formula -N acetyl group), η is 0 or 1. Base (where R5 is a hydrogen atom or A, CH0 but X is a hydrogen atom) , Y is the group represented by the formula -N \. Here, the lower alkyl group includes methyl, ethyl, propyl, butyl, etc., and the lower alkoxy group includes methoxy, ethoxy, propyl, butyl Oxygen, etc., cycloalkyl has cyclopropyl, cyclopentyl, cyclohexyl, etc., acyl groups include methyl acyl and alkyl sulfonyl, and alkyl acetyl groups have acetyl, propyl, butyl, Pentamethylene, special Acyl, hexyl, etc., and halogen atoms include tritium, bromine, fluorine, etc. Salts of pyridinecarboxylic acid derivatives include hydrochloric acid, sulfuric acid, oxalate, etc. Next, the compounds of the present invention are shown in Table 1, for example. For the compound number, please refer to the descriptions below. (Please read the precautions on the back before filling in this page) Outfit · Ministry of Economic Affairs Standards · Industrial and Consumer Cooperative Co., Ltd. This paper scale is free to use the Chinese National Standard (CNS) A 4 specifications (210x297 ; ":) 211009 Λ 6 Β 6 5. Description of the invention (4)

The compound number XYR R1 R2 printed by the Cooperative Society of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the Central Government's melting point (° c) 1 6-0CHa: 0 CHa och3 och3 148-150 2 6-0CHa 0 H 〇CH, och3 137- 139 3 6-0C.H. 0 ch3 0CHa och3 112-113 4 6-0C.H, 0 H och3 och3 138-139 .5 6-0H 0 CHa och3 och3 186-190 6 6-〇- / ~ \ 〇 CH3 N = ^ 0CHa 0 ch3 och3 och3 131-132 7 6-〇-/) 〇 muscle N ^-0GH3 0 H och3 och3 189-192 8 0 ch3 och3 och3 92-94 9 6〇-F 0 CHa och3 och3 110 -113 10 0 H och3 och3 159-163 11 6 ^ 〇K: l 0 ch3 OCH, och3 146.5-149 12 6〇-ci 0 H 0CHa och3 167-170 13 6- < 〇 ^ ch »0 CH, 0CHa 0CHa 113-116 14 6 ^ 〇 " CHa 0 H 0CHa 0CHa 155-158 15 6 ^ 〇-〇ch ^ 0 ch3 och3 och3 111Ί14 16 6 ^^ K) CH3 0 H 0CHa 0CHa 168-172 17 6-NO, 0 CH, OCH, 0CH3 81. 2. 20,000 (Please read the precautions before filling in this page) This paper uses the Chinese National Standard (CNS) A 4 specifications (210x297 g *) 211009 Λ 6 Η 6 Printed by the Shell Industry Consumer Cooperation Department of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China V. Description of the invention (5) Table 1 continued Compound No. XYR Rl Nature melting point (° C) 18 6-〇hQ 0 CHa och3 OCH, 19 6-N (CH3) 2 0 ch3 och3 0CHa 125-127 2 0 6-N (CH3) 2 0 H och3 0CH, 195 ~ 197.5 2 1 6-N (CHJ, 0 CH, och3 ch3 106 ~ 108 2 2 6-N (CH,), 0 ch3 Cl och3 120-122 2 3 6-N (CH3) 2 0 ch3 Cl CH3 154-158 2 4 6 -N (CH3) 2 0 ch3 ochf2 0CHa 67-69 2 5 6-CN 0 ch3 och3 0CHa 132 ~ 136 2 6 6-NH2 0 CHa 〇CHa 0CH3 67-69 2 7 6-N (C2HJ2 0 ch3 och3 0CH3 109 -112 2 8 0 ch3 0CHa OCH3 2 9 6-NHC0CH, 0 ch3 0CHa och3 3 0 6-NHCO-Q 0 ch3 0CHa OCH ^ 80 ~ 85 3 1 6-H NCHO ch3 OCH3 0CH3 3 2 6-N (CH 丄NCHO ch3 0CH3 och3 3 3 6_N (CH 丄 0 ch3 CH, so2ch3 150 ~ 152.5 3 4 〇. C 0 0 c h3 0 c h3 Ha C N- < N- < > > 132-134 h3 c, 0 c h3 3 5 6_N (CH 丄 0 C, H, och3 0CHa 112-113 3 6 6-N (CH 丄 0 c3h7 0CHa och3 83.5-85 3 7 6-N (CHa) z 0 CaH7-i 0CHa 0CH, 62-68 3 8 6-N (CHa), 0 CH2C00C2H. 0CHa och3 113-115 3 9 6-N (CH3), 0 CHOCOH 0CHa 0CHa Unable to measure ch3 Page) Original paper Λ scale With China β family "quasi (CNS) T4 specifications (210x297 public;":) - 7 · 81. 2. 20,000

α AC 66 ΛΠ Printed by Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: t 饫 切 c ·-V. Description of the invention (6) Table 1 continued XYRR * R * Physical property number Melting point (° c) 4 0 6 -N (CH,) 2 0 chocooc, h5 1 0CHa och3 1.5215 CHa 4 1 6-N (CH3) i 0 CH20CHa och3 och3 91-96 4 2 6-N (CH3), 0 CH2CN och3 och3 143-145.5 4 3 6-N (CH 丄 0 ch2ch: ci och3 och3 94-97 4 4 6-N (CH3): 0 CH2C5CH och3 0CHa 127-130 4 5 6-N (CH 丄 0 ch2ch = ch2 OCH, och3 92-94 4 6 6-N (CHJ2 0 0CHa och3 126-130 4 7 6-N (CH3) 2 0 Na @ 0CH3 OCH, 148-157 4 8 6-N (CH3) s 0 och3 och3 240-245 4 9 6-N (CHJ2 0 l / 2Ca® ^ och3 och3 169-182 5 0 0 CH0C0C, HT) 0CH3 och3 46-48 ch3 5 1 6-N (CH3) 2 0 CH0C0C4Hs 1 och3 0CHa 59 ~ 60 ch3 5 2 6-N ( CHj2 0 CH0C0C.H ,, 1 0CHa 0CH :) 63-64.5 CHa 5 3 6-N (CHa): 0 CH20C0C (CH3), och3 OCH, 113.5-115 5 4 6-N (CHJ2 0 CH2OC〇d och3 och3 101-102 5 5 6-N (CH 丄 0 ch2-〇och3 och3 65-67 5 6 6-CH = CH, 0 ch3 och3 och3 65-67 5 7 6-CH = CH, 0 H och3 och3 106-107 5 8 6-CsCH 0 ch3 och3 och3 5 9 6-C ^ CH 0 H och3 0CHa 6 0 6-CF, 0 ch3 0CHa 0CHa 6 1 6-CF3 0 H och3 OCH, {please read the back first Note for Sun to fill out this page) This paper scale is used in China National Standards (CNS) < f 4 specifications (210x297 g *) -8- 81. 2. 20,000 21ί0'φ ^ secret; Fifth, Issue 11 1st Table continued Λ ί) 1 \ 0 Compound number

X Υ

R R '

R Physical properties Melting point (° C) 6 2 6 3 CH, I 6-CsCSi-CHa CHa CH = OCHa OCH: 95-97

Ha C N- C Ο Ο Η O c HN (188-189

H, CN: HC 1 0 C H3 6 4 6-IUCHJ, 0 NH (CaH7-i) 2 0CH3 0CH, 6 5 6-N (CH3) 2 NH H och3 och3 6 6 6-NHCH3 0 H OCH, och3 6 7 6-NHCH, 0 H och3 och3 6 8 6-NHCH3 0 Nae 0CH3 och3 6 9 6-NHCH, 0 0CH3 och3 7 0 6-NHCH3 0 l / 2Ca secret 0CH, 0CHa 7 1 6-NHCH, 0 C3H7-i OCH, 0CHa 7 2 6-NHCH, 0 CH, 0CHa 0CHa 0CHa 7 3 6-NHCHa 0 CH0C0C, Ha CH, 0CH, 0CHa 7 4 (please read the notes before filling #fill this page) 137-138 160 -162 Printed C Ο Ο H 〇CH CHaNH- " 'V 〇

HC 1 0 C Ha 7 5 ch3 6-N < C2H. 0 CHa 0CH3 7 6 ch3 6-N < CaH. 0 4 H 0CH, 7 7 CH, 6-N < CaH, 0 CHa 0CH, 0CH3 0CH: OCH, 94-97 168-170 86 ~ 87 ♦ ^ 夂 們 用 中 《National «Ping (CNS) IM specifications (210x297 g; Jt) 9_ 61. 2. 20,000 A β B6 V. Invention description (ill No.) Table mineral compounds No. XYR R1 R2 Physical melting point (° C) 7 8 ch3 6-N < c3ht 0 H 0CH3 0CHa 99 ~ ”〇7 9 ch3 6-N < CH, 0 CHa 0CH3 0CHa 88-90 8 0 ch3 6-N <; CH, 0 H 0CH3 0CHa 105-107 8 1 δ-ΝίΟ, Η.), 0 H OCH, och3 159-161 8 2 6-N (CaHJi 0 CH, 0CHa och3 8 3 6-N (CaH7), 0 H och3 och3 140-143 8 4 6-N (CaH7-i) i 0 ch3 0CHa och3 Unable to determine 8 5 6-N (CaH, -i) I 0 H och3 OCH, 131-132 8 6 6-NH2 0 H 0CHa 0CHa 235-237 8 7 6-NHC.H, 0 ch3 0CH3 och3 95 ~ 96 8 8 6-NHC, H, 0 H och3 OCH, 17C ~ Ί71 8 9 6-NHCaH, 0 ch3 0CH3 0CHa 9 0 6- NHCaH, 0 H 0CHa 0CH3 182 ~ 185 9 1 6-NHCaH, -i 0 CHa OCH3 0CHa ”6 ～ 119 9 2 6-NHC3H7-i 0 H 0CHa 0CHs 177 ~ 181 (Please read the precautions on the back before filling in this Page) Ministry of Economy The central standard is that the physical properties of compound 40 in Table 1 printed by the Cooperative Societies Co., Ltd. represent the inflection rate (20 t nano-D line). The paper is used on the 5 gram scale. The national standard (CNS) < P4 Specifications (210X297) «: 21100 ^ A 6 B6 V. Description of the invention (9) The method for producing the compound of the present invention includes the following methods, but it is not limited to these methods .: Method A>

C 0 0 R R1

R

Printed by the β-Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs [n] [m] [I-η In the formula, R1, R2 and X have the same meaning as above, R6 means R except hydrogen atom, L is halogen, alkylsulfonaldehyde Group, or benzylsulfonyl, Y1 / CH0 is an oxygen atom or a group represented by the formula -N \\. That is, the compound represented by [1-1] may be a compound represented by formula [I] and a pyrimidine derivative represented by formula [II], in the presence of age, preferably in an inert solvent, at a temperature ranging from room temperature to the boiling point of the solvent It is produced within a few minutes to several hours. Here, the solvent can be a hydrocarbon strip solvent such as benzene and toluene, a halogenated hydrocarbon strip solvent such as methylene chloride and chloroform, an ether strip solvent such as tetrakifuran and 1,4-dioxane, and a ketone strip solvent such as acetone and methyl ethyl ketone. Ester strip solvents such as methyl acetate and ethyl acetate, aprotic polar solvents such as dimethylformamide and dimethylacetamide, and others include acetonitrile. For age, you can use gold halide, potassium intestinal potassium and other age golden catenaries, sodium hydride, potassium hydride, calcium hydride and other hydrogenated age gold hurricanes and hydrogenated sickle gold hurricanes, sulfonate, potassium silicate, calcium monate Hydrogenated gold, sodium hydrogenate, potassium hydrogenate, calcium hydrogenate, etc. -11 The size of this paper is easy to use China Sleepless Family Standard (CNS) Grade 4 (210x297mm) (please read the precautions on the back before filling in this page) Pack-.V * _ τί100ί &gt; Λ 6 Β 6 5. Invention Explanation (10) In addition, the compound where Y is -NH- can be prepared by acting with acid or age when Y is -N. <Method B>, CH0 compound COOR1 R * WWA acid

X COOM R 'COOH R *

N

[1-2 〔I-3] (1-4) (Please read the precautions on the back before filling out this page) In the standard printed by the Ministry of Economic Affairs along the Employee Consumer Cooperative, R1, R2, X and Y1 have the same meaning Formerly, Μ is an aged metal or «earth gold, R7 is an ester-forming group in R. That is, the compound represented by formula [1-3] can be represented by the compound represented by formula [1-2] in the presence of _ The solvent, water, or a mixed solvent of polar solvent and water is made from a reaction in the temperature range from room temperature to the boiling point of the solvent for several hours to tens of hours. It is made of organic acids such as citric acid and acetic acid, or hydrochloric acid, Acid solution of sulfuric acid and other sulfonic acid aqueous solution can be made into the compound represented by formula [1-4]. The solvent can be dissolved in two alcohols such as methanol and ethyl alcohol, 1, 4-dioxane, tetrahydrofuran and other ethers. _, Dimethyl formaldehyde amine, dimethyl acetamide and other amide strips polar soluble _ etc., but not limited to this. And the age can be used sodium silicate, potassium monate, calcium silicate and other sulfonic acid, oxidized Hydrogenated gold hurricanes such as pin, squash hydroxide, calcium hydroxide, etc. 12 The paper size is free to use Chinese National Standard (CNS) A 4 specifications (210x297 g *) 2il (Kr3- 5 、 Description of the invention (11) <C method> Λ 6 Β6 C Ο 0 M R1 C Ο Ο RT R1 Ν- R7 L 1 (IV)

V Ν:

X

R

The Ministry of Economic Affairs of the People's Republic of China ^ only works on consumer cooperation Du Yan 51 (where R 1, prime). Namely, the polar solvents of formula [and formula [IV, within the range of degrees, the solvent can be used as a hydrocarbon hydrocarbon solvent ketone, methyl ethyl ketone, etc., dimethyl formaldehyde solvent, sodium acetonitrile, hydrogenated sodium, acid-breaking, vaporized potassium propane Ethyl ethylamine, [I-3] 1, R 2, [I-5] Μ, X and Υ1 have the same meanings as before, L1 represents a halogen compound represented by I-5], which can be compounded by the formula [I-3]] The compound shown is prepared in the presence of emu, or without _, and in a preferably inert solvent, from room temperature to the boiling point of the solvent over a period of minutes to hours. Hydrocarbon strip solvents such as benzene and toluene, halogens such as methane and cyanoform, ether-based solvents such as 1,4-dioxane and tetrahydrofuran, acetone strip soluble I, ester solvents such as methyl acetate and ethyl acetate , Dimethyl acetamide and other aprotic strips and other aprotic properties. The age can be used for gold metal, potassium metal and other age metals, potassium hydride, calcium hydride and other hydrogenated «metals and hydrogenation _ earth gold, potassium sulfonate, calcium nitrate and other nitrate, sodium hydrogen hydride, calcium hydrogen hydride, etc. Gasification Jinyang, triethylamine, diisopyridine and other organic _. -13 The size of this paper is easy to use the China Sleepless Family Standard (CNS) A 4 specifications (210x297 mm) (please read the precautions on the back before filling in this page) 21100 ^ Λ 6 Β6 V. Description of invention (1 test <D method 〉

C〇〇R

[Acid] [I-6] [I-7] In the formula, R.R1,! ^ 2,) (and Υ1 have the same meaning as before. That is, the compound represented by formula [1-7] can be represented by formula [1- 6] The compound shown is prepared in an inert solvent at a temperature ranging from room temperature to the boiling point of the solvent, with an acid for a few minutes to several hours. The solvent can be benzene, toluene and other hydrocarbon strip solvents. Dichloromethane, Halogenated hydrocarbon strip solvents such as chloroform, 1,4-dioxane, tetrahydrofuran and other brewing solvents, acetone, butanone and other ketone solvents, methyl acetate, ethyl acetate and other ester solvents, dimethylformamide, di Acetamides such as methylacetamide collect aprotic polar solvents, acetonitrile, etc. In addition, acids can be hydrochloric acid, sulfuric acid, oxalic acid, etc. Acids can be added directly to inert solvents or gases can be added. (Please read the notes on the back first (Fill in this page again) -install-

Ministry of Economic Affairs standard and β industrial consumer cooperatives printed M

<Method E> C Ο Ο R

C Ο Ο R 14

R

The paper standard is universal Chinese National Standard (CNS) A4 specification (210X297 mm) 211009 A 6 B6 Central Standard of the Ministry of Economic Affairs along with shellfish consumer cooperation du printing 5. Invention description (13) In the formula, R, R 1, R 2, X and Y1 have the same meanings as above. That is, the compound represented by the formula [I-9] can be prepared by adding a peroxide to the compound represented by the formula [I-8] in an inert solvent at a temperature ranging from -20¾ to the boiling point of the solvent. The following examples illustrate the preparation method of the compounds of the present invention. Fen Shi Example 1 2- (4. ft-Nitrosporine, a preferred pyridine-?.-a &gt; g servant, -6- (N. Err pro-M) pyrazone, methylpyridine (compound No. 19): &gt; Synthesis of methyl 6- (Ν, Ν-dimethylamino) -3-hydroxypyridinecarboxylate 1.4g (7mmol), 4,6-dimethylamino-2-methylsulfonyl pyrimidine 1.6 g (7 mmol), 0.6 g (4 mmol) of potassium metaborate, added to 100 mL of DMF, and reacted at 90¾ for 2 hours. After the reaction was completed, it was poured into water, extracted with diethyl alcohol, washed with water, It was dried and concentrated, and the resulting oil was crystallized with isopropyl carp. The crystal was recrystallized from ethyl acetate / n-hexane to obtain the target compound. Yield 1.6 g (yield 66%) Melting point 125-127TC. Examination Example 2 3 -(4. fi -Diuronium is favored by Sui-2-some) argono- fi-fluorine BH; synthesis of pyridinium methyl ester (Compound No. 8) Take 6-phenyl-3-hydroxypicolinic acid methyl Ester 1.0 g (4.4 mmol), 4, 6-dimethyl «yl-2-methylsulfonylpyrimidine 0.8 g (4 mmol), potassium citrate 0.6 g (4 mmol), Add 20 ml of DMF and react at 80 ° C for 0.5 hour. After the reaction is completed, pour into water and extract with ethyl acetate. The organic layer is used Wash and dry with water and saturated food, with an appropriate amount of -15- (please read the precautions on the back before writing this page). The paper standard is common in the Β jia standard (CNS) A 4 specifications (210X297 male dragon ) A 6 B 6 V. Description of the invention (14) flor * isil treatment. Ethyl acetate was distilled off under reduced pressure, and 20 ml of hexane was added to the resulting residue, which was left for three days to crystallize and washed with hexane / isopropyl ether , To obtain the target compound. Yield 0.85 g (yield 58%). Melting point 92-941C. Example 3 3- (4..6-dishenmo favored pyridine-2-some) argon-6- ( ^. &gt; &lt; -Diur argon ___________ (Compound No. 20) Synthesis of 3- (4, 6-dimethoxypyrimidin-2-yl) gaso-6- (H, N-dimethylamino) 2.5 g (7.7 millimoles) of methyl picolinate, mixed into 100 ml of methanol solution, mixed with 6 ml of 10% potassium hydroxide aqueous solution, stirred at room temperature overnight. After the reaction was completed, poured into water. Acetic acid Ethyl ester extraction. The aqueous phase was made acidic, extracted with chloroform, washed with water, dried and concentrated. The resulting crystals were washed with isopropyl ether to obtain the target compound. Yield 1.6 g (yield 64%). Melting point 1 95- 1 97.5 f. Example 4 3- (4. -Dishen nitrogen favors pyridine-2-some) argono-fi-Dimethyone favors pyridine-2 -Pyrodione 1- (7, a certain compound) Z, SS (Compound No. 40): &gt; Will be taken 3- (4, 6-Dimethylaminopiperidin-2-yl) Gaso-6-dimethyl atmosphere, the Ministry of Economic Affairs, the standard of the Ministry of Economic Affairs, persuaded only the workers to print it out by the cooperative (please read the back first Please pay attention to this page and write this page) Pyrimidine-2-carboxylic acid potassium 2.0 g (5.6 mmol), 1- (ethoxycarbonyl) ethyl ethyl 0.8 g (5.7 mmol), suspended Within 5 ml of dimethylformamide. Stir at room temperature for 6 hours. The anti-orbital substance was poured into water and extracted twice with ethyl acetate. The organic layer was washed with water, dried and mashed to remove the solvent. The resulting viscous body was purified by column to obtain the target compound. Yield This paper scale uses the Chinese National Standard (CNS) A4 specifications (210X297 g *). Λ 6 Β 6 V. Description of the invention (15) 0.5 g (yield 33%), and the refractive index (Na-D line) 1.5215. Endeavour Example 5 (4. ft-Dimethyl M certain pyridine-2-some) Aromatic-fi-Dimethyl certain gas certain preferred pyridine-2-Yun-Yu-Yong (Compound No. 48) evening synthesis take 3- (4 , 6-dimethylaminopyrimidin-2-yl) aero-6-dimethylaminopyrimidine-2-carboxylic acid methyl ester 9.2 g (27.5 mmol), soluble in formazan 30 L, plus 10% 1.55 g of potassium oxide (27.5¾ pods), add 20 ml of water, and stir at room temperature. After the inverse liquid was concentrated under reduced pressure, acetone I was added, and the precipitated crystals were filtered and washed with hexane to obtain the target compound. Yield 9.8 grams (98% yield). Melting point 240-245 ° (:. Endeavour case 6 3- (4. fi-dimethyl argon favors pyridine-2-some) argon-fi-dimethyl methine sulfonate Chenidine-2-jundi potassium ( Huahuiwu No. 49) will take 3- (4, 6-dimethylaminopyrimidin-2-yl) oxo-6-dimethylaminopyrimidine-2-carboxylic acid potassium 1.0 g (3.1 mmol) , Dissolve in 10 ml of tetrahydrofuran, add 0.15 g (1.5 mmol) of precipitated calcium silicate, add 10 ml of water, and stir at room temperature. After shrinking the reaction solution under reduced pressure, add acetone to precipitate crystals Filter and wash with hexane to obtain the target compound. Produce 1.0 g (yield 91%), melting point 169-182. Printed by the Ministry of Economic Affairs, Standard Industrial Engineering Cooperative (Please read the precautions on the back before reading (Fill in this page) 銀 抡 立 7 (4. R-Dishen M favors Pyridin-2-V) Argon-fi-Di-methyl-pro-Pyridine-2-Hetose-S-M-Shen Ester No. 41) Evening synthesis takes 3- (4,6-dimethylaminopyrimidin-2-yl) amino-6-dimethyl atmosphere-17- This paper scale is universal Chinese National Standard (CNS) A4 specifications (210X297 Public; ¢)

V. Description of the invention (16) A6 B6___ Pyrimidine-2-carboxylic acid 0.4 g (1.25 mmol), dissolved in 15 mL of dichloromethane, add 0.17 g (1.31 mmol) of diisopropylethylamine under cooling ), React for 15 minutes. At 0 ° C, 0.12 g (1.49 millimoles) of methylpyrrolidine was added dropwise, and slowly returned to room temperature, and reacted for 4 hours. After the reaction was completed, 30 ml of dichloromethane was added, washed with water, washed with 10% aqueous citric acid solution, saturated brine, dried, concentrated, and purified by silica gel column chromatography to obtain the target compound. Yield 0.4 g (84% yield), melting point 91 -96 υ. In addition, the raw material compound of the compound of the present invention can be manufactured as follows (please read the precautions on the back before filling in this page)

Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

〔Π-4〕 / / / C00Re / Η method L-^^-OCH, [Π-5] -1 8- This paper standard general trapped "Household Standard (CHS) A 4 specifications (2) 0x297 male dragon) Λ 6 Β6 21100 ^ V. Description of the invention (17) In the formula, R 6, L and X have the same meanings as above. That is, the compound represented by formula [I-2] is derived from the compound represented by formula [E-1], and the compound represented by formula [1-3] can be prepared by the contact addition method of hydrogen. In addition, it is well known to produce compounds represented by formula [E-4] and compounds represented by formula [H-5] from compounds represented by formula [1-1] [for example, Pharmacological Journal 67:51 (〗 947)]. Can be manufactured according to its method. Η These methods are detailed below. (Please read the precautions on the back before filling in this page) 〈F Law〉 Ο C 0 0 R '

(C Η3) 3 S i R · [V] -► Ra C O C [VI] or

C〇0 R

C Ο 0 R

Binding · Ordering-The Ministry of Economic Affairs, Standards of the Ministry of Economic Affairs, printed by 51. In the formula, R6 has the same meaning as above, R8 is nitrogen. Dimethylamino, or diethylamino, R3 is dimethylamino, diethylamino , Alkyl, or phenyl: that is, let the compound represented by formula [H-1] and the trimethylsilyl derivative represented by formula [V], or the aldehyde cyanide represented by formula [VI], in an inert solvent, in the room The temperature is within the range of the boiling point of the solvent, and the reaction can be made within a few hours. It can be made into the formula -19- This paper scale uses the Chinese National Standard (CNS) A 4 specifications (210X297 mm) Λ 6 Β6 thermal 1 coffee- V. Description of the invention (1 sentence [1-6] or [1-7]. The solvent can be benzene, toluene and other hydrocarbon solvents, difluoromethane, helium and other halogenated hydrocarbon strip solvents, tetrahydrofuran, 1, 4-dioxane Such as ether solvents, ketone solvents such as acetone and butyl, ester ester solvents such as methyl acetate and ethyl acetate, aprotic polar solvents such as dimethylformamide and dimethylacetamide, and acetonitrile, etc. Chloroform is better. &Lt; G method> (Please read the precautions on the back before writing this page)

Printed by the Ministry of Economic Affairs of the People's Republic of China along with A Gong Consumer Cooperatives, R6 has the same meaning as before, R 10 is alkyl, substituted alkyl, or 4, 6-dimethylpyrimidinyl, and L2 is a halogen atom. However, when 1 to 1 (3 is 4, 6-dimethoxypyrimidinyl, L2 is a halogen atom or an alkylsulfonyl group. That is, the compound represented by formula [1-4] and the compound represented by formula [VI], In the presence of _, in an inert solvent, at a temperature ranging from room temperature to the boiling point of the solvent, the reaction can be made for several minutes to several hours to make the compound represented by the general formula [H-8]. Here, the solvent can be benzene, toluene Isohydrocarbon solvents, dimethane, helium and other hydrocarbon solvents, tetrahydrofuran, 1,4-dioxane and other ether strip solvents, acetone, butanone and other ketone solvents, methyl acetate, ethyl acetate and other esters Article -20- This paper uses the Chinese standard (CNS> A4 specifications (210x297 g)) ^ ^ A 6 _-Jii__ V. Description of the invention (19) Solvent, dimethyl methanolamine, dimethyl ethyl Aldamine and other aprotic polar solvents, as well as acetonitrile, etc. Alkali can be alkali metal such as gold hurricane, metal potassium, hydrogenated age metal such as sodium hydride, potassium hydride, calcium hydride and hydrogenated earth metal, sodium nitrate, Potassium metaborate, calcium silicate, and other metabolic acids, sodium hydroxide, potassium hydroxide, helium vaporized calcium, and other hydrogenated gold halide. <Η 法(Please read the back of the precautions to fill out this page) installed · C 0 0 R * R '1 Β (Ο Η), C 0 0 R &quot;

(Π-5) [Π-9] where R6 and L1 have the same meanings as before, and R 11 is substituted phenyl. That is, the compound represented by formula [E-5] and the compound represented by formula [VII] are reacted for several hours in the temperature range from room temperature to the boiling point of the solvent in the presence of emu and a catalyst in an inert solution, ie The compound represented by the general formula [Π-9] can be prepared. Here, the solvent can be a hydrocarbon strip solvent such as benzene or toluene, an alcohol paste solvent such as methanol or ethyl yeast, an ether paste solvent such as 1, 2-dimethylaminoethane, tetrahydrofuran, ether, etc., and an ester strip such as methyl acetate or ethyl acetate. Solvents, aprotic solvents such as dimethyl formate, dimethylacetamide, and acetonitrile. As catalysts, four (triphenylsulfone) rake (0), triphenylphosphine and acetic acid rake, tri (o-tolyl) thrush and acetic acid rake, etc. can be used. _Usable sodium silicate, potassium silicate and other silicate salts, sodium silicate and other hydrogen silicate salts, or triethylamine, pyridine and other organic _. -2 1-This paper standard uses 8 standards (CNS) A4 specifications (210 father 297 mm), \ 5. Printed by the Ministry of Economic Affairs Standards and Staff Cooperative Society Λ 6 Β6 aii Coffee-Five 2. Description of the invention (20) In addition, the raw material compound can be prepared in the following manner. <Method I>

〔Π — 1 1 (Please read the precautions on the back before filling out this page)

C Ο〇R R; N- / ^ ~ \ = yNHz [Π-1 〇] where R 3, R 4 and R 6 have the same meaning as above. That is, the compound represented by the formula [E-1 1] can be prepared by reacting the compound represented by the formula [I-10] and formic acid within a range of room temperature to boiling point for several minutes to several hours. Further, the compound represented by formula [1-11] can be prepared by reacting the compound represented by formula [1-10) with anhydrous acetic acid-formic acid mixed solution or dicyclohexyl formate diimine. However, it is not limited to these methods. Η The following reference examples are given to illustrate the preparation of raw material compounds. Example 1 Employee's consumption cooperation of the Ministry of Economic Affairs's Central Standards Bureau produced 3-benzyl gas-6- (Ν.Ν- 二 申 某 亲 某) methyl benzoate for synthesis and 3-benzyl gas pyridine Formic acid methyl-N-vaporide 15 g (58 mC), trimethylsilyl nitrile 6.7 g (67 mC), N-dimethylcarbamate 8.3 g (61 mC), added to Chlorinated methane 100ml, placed under stirring at room temperature. The organic layer was washed with water, dried and concentrated, and the resulting residue was purified by column chromatography to obtain the target compound. Yield 2.4 g "Production -22-This paper standard uses Chinese National Standards (CNS) A4 specifications (210X297 mm) 21100 ^ Λ 6 Central Standard of the Ministry of Economic Affairs Printed along the Beigong Consumer Cooperatives V. Description of invention (21) Rate 14%), melting point 71.5-7310. Participant Example 2 Methyl 3-benzyl-6-bromopyridinecarboxylate can be obtained by the same method. Yield 3.1 g (yield 20%), melting point 103.5-10510. Participant's Example 3 Synthesis of benzyl methacrylate-methyl ester of 3-benzyloxy-6-hydroxypyridinecarboxylic acid 5.0 g (19 mmol) and ethyl bromide 2.1 g (19 mmol) Ear), potassium monate 2.9 g (21 mmol), added to 100 ml of DMF, and reacted at 801C for 8 hours. After the reaction was completed, it was poured into water, extracted with ethyl acetate, washed with water, dried, and concentrated. The resulting residue was purified by column chromatography to obtain the target compound. Yield 4.1 g (yield 74%). Melting point 45-46C. Participant Example 4 Narrow helium-fi-jumous scorpion is brewed into a 100-ml three-necked flask equipped with a thermometer, a cooling tube and a nitrogen introduction tube, and four (triphenylbenzene) is introduced (〇) 〇.6 grams (0.5 millimoles), and 1,2- dimethyl gas ethane 5 ml, under nitrogen flow, will be dissolved in 1,2- dimethyl gas ethane (20 ml) of 3-benzyl gas 2.7 g (10.0 millimoles) of methyl-6-hydropyridinium formate, added in one portion. After stirring at room temperature for 3 hours, 1.8 g (15.0 mmol) of phenylboronic acid dissolved in 1,2-dimethylaminoethane (15 ml) was added, followed by stirring for 1 hour. Add 2M aqueous sodium sulfonate solution (40 ml) and heat to reflux for 50 minutes. After cooling, add an appropriate amount of water and extract with ethyl acetate. The organic layer is saturated with water-23- (please read the precautions on the back and then fill out this page) Pack &lt; Order_ Line Standard (CNS) A4 specifications (210 father 297 male dragons) 211 coffee __ 5. Invention description (22) The brine was washed, dried and concentrated, and the resulting residue was purified by column chromatography to obtain the target compound. The yield was 1.9 g (yield 5 9.4%). For example, F5 3-sulfonium-6-jumous ketone methyl ketoxiuxi synthesis take 3-benzyloxy-6-phenyl-pyridinium methyl ester 1.9 g, 10% reduction of 琪 / methanol, to The column chromatography was refined to obtain the target compound. Yield 1.0 g (yield 76.9%), melting point 100-1011C. Participant example fi fi- (N. N-two certain pro-some)-. Ί-thine pyridine succinic acid methylpyridine synthesis take 3-benzyloxy-6- (N, N-dimethylamino) pyridine 2.3 g (8 mmol) of methyl formate, 0.3% of 10% sodium acetate, added to 100 ml of ethyl acetate, and hydrogenated at normal pressure. After the reaction is completed, it is filtered and concentrated to obtain crystals. Yield 1.4g (yield 92%), melting point 118.5-12010. Specific examples of raw material compounds prepared in the same manner as in Reference Examples 1-6 are listed in Table 2. (Please read the precautions on the back and then fill out this page) Installed _ Printed by the β-Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -24- This paper scale uses the Chinese National Standard (CNS) A 4 specifications (210x297 g)

211〇fA Λ 6 Η 6 5. Description of the invention (23) Table 2

Employee Consumer Cooperation of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China Printed Intermediate Number X R'1 Melting Point (° c) 1 N (CHJ, 71.5 ~ 73 2 N (CHJ, H U8.5 ～ 120 3 CN CH々103.5〜 105 4 CN H 5 Ο H 100 ~ 101 6 och3 H 7 oc2h. H 8 CH: ^ 〇140 ~ 143 9 H 84.5 ~ 86 10 Ocl years Ό 127 ~ 130 11 〇-ci H 142 ~ 145 12 Of H 124.5 ~ 127 13 H 82 ～ 85 -25 • (Please pay attention to the comments and comments # fill in this page) Pack · Order · Thread.

• This paper is printed using the Chinese National Standard (CNS) f 4 specifications (210x297 g *) 81. 2. 20,000 Printed ftp 9 ~ _bj6_ Fifth, the invention description (24 ) The herbicide of the present invention is based on the derivative of phthalic acid represented by the general formula [I] as an effective ingredient. When the compound of the present invention is used as a herbicide, it is used in paddy fields, dry land, tree gardens, non-agricultural land, etc., and the active ingredients can be used as appropriate dosage forms depending on the purpose. Normally, the active ingredient is diluted with an inert liquid or solid carrier. If necessary, surfactants, dispersants, ribs, and other forms are mixed and used as a preparation. For example, the active ingredients and solid carrier can be mixed and crushed to make a powder. The active ingredient, solid carrier, surfactant and dispersant can be mixed and crushed to make water and agent. The active ingredient, liquid carrier, interfacial active agent and dispersant can be mixed to make an emulsion. Granules are composed of active ingredients, solid carriers, surfactants, dispersants and rib supplements, etc., can be mixed and granulated. Solid carriers, surfactants, dispersants and rib supplements can be mixed and granulated, which will be effective The ingredients are covered and made. Carriers used for these formulations include, for example, slip powder, bentonite, clay, kaolin, diatomaceous earth, white rock, Zhishi, slaked lime, silica sand, ammonium sulfate, urea, etc. Cyclohexane, isophorone, methyl naphthalene and other liquid carrier, etc. Surfactants and dispersants are, for example, alcohol sulfate esters, alkylaryl sulfonates, #sulfonate formaldehyde condensates. Lignin sulfonates, polygasification oxalase », polygasification ethylene Aryl ether, polygasified ethylene sorbitan monoalkylate, etc. Examples of rib supplements include carboxymethyl cellulose, polyethylene glycol, and gum arabic. The mixing ratio of effective ingredients can be selected according to the needs, powders and granules 2 6-(Please read the precautions on the back before writing this page) This paper is used in the standard Β Η family standard (CNS) A 4 Specifications (210x297 g; *) 2li ^ 9 A 6 li 6 5. Description of the invention (2¾ When the Ministry of Economic Affairs, Bureau of Standards, Beigongxiao #Cooperative Duyin preparation is 0.01096 weight, preferably 0.05-5¾ weight, For emulsions and water additives, it is 50% by weight, preferably 5-20% by weight, but not limited to this. When used, it can be diluted to an appropriate concentration, spread on stems, leaves, soil or water, or applied directly. The compound of the present invention is preferably applied from 0.1 g to 5 kg of active ingredient per 10 acres, preferably from 1 g to 1 kg. In addition, when used in the form of emulsion and water and other liquids, 0.1-50,000 ppm is preferably used, preferably 10-10,000ppm, but not limited to this. In addition, the compounds of the present invention may be mixed with insecticides, fungicides, other herbicides, plant growth regulators, fertilizers, etc. Secondly, the preparation method will be specifically described with representative preparation examples, In the following description, "parts" means the preparation of Example 1 powder in 1 part of compound (2 0) and mix 99 parts of diatomaceous earth were crushed to obtain powder. Example of cutting 2 Aqueous agent was added to compound (19) 10 parts, mixed with polyoxyethylene alkyl aryl ether 0.5 parts sodium naphthalenesulfonate formaldehyde condensate 0.5 parts, diatoms 20 parts of clay and 69 parts of clay, which were crushed to obtain a water and agent. Example 3 A compound of water and 10 parts of compound foot, mixed with 0.5 parts of polygasified ethylene aryl ether, naphthalenesulfonate sodium formaldehyde condensate 0.5 Parts, 20 parts of diatomaceous earth, 5 parts of CarPleX 80, and 64 parts of clay, mixed and crushed to obtain water and agent. -27- This paper scale uses the Chinese National Standard (CNS) A 4 specifications (210x297 male dragon) ( Please read the precautions on the back before writing this page) Packing · Line-Ministry of Economic Affairs Standard Λ; β Industrial and Consumer Cooperation Du Printed A 6 2li〇〇a-V. Description of Invention (26) Formulation Example 4 Emulsion To 30 parts of compound (20), add 60 parts of the equivalent mixture of xylene and isophorone, 10 parts of polygasified ethylene aryl ether polymer and alkylbenzenesulfonic acid gold intestine salt, and stir well Emulsion. Formulation Example 5 10 parts of compound (3), 80 parts of bulking agent mixed with slip powder and bentonite in a ratio of 1: 3, 5 parts of Baishuo, polyoxyethylene 5 parts of aryl ether polymer and gold salt of alkylbenzenesulfonate, add 10 parts of water, mix thoroughly to form a paste, press it out from a sieve with a diameter of 0.7 mm, and after drying, cut into 0.5-1 mm length to obtain granules Effects of the invention The compound of the present invention represented by the general formula [I] can effectively control weeds in dry land problems at low doses, such as wild morning flowers, Xanthium sibiricum, Da Ma Liao, Qing M, Li, Stellaria, white hemp, American Sida Spinosa and other broad-leaved weeds, sedge, papyrus, centipede, miscanthus, snow willow and other perennial and annual miscanthaceae weeds, miscanthus, sedge grass, barnyard grass, rice straw, Green weeds such as bristlegrass, sparrow barnyardgrass, and lily wild barnyardgrass. In addition, it has excellent weeding effects on non-agricultural problem weeds, such as Italian rye, tubegrass, Miscanthus, Commelina, Amaranthus, Pueraria, Tall Stem Chestnut, American Ixora, etc. In addition, edible barnyard grasses, umbrella trees (umbrella plant), two-year-old flowers and other annual weeds that occur in paddy fields, as well as perennial weeds such as champignons, water grass, yam, reed pen, and Alisma orientale, grow from germination to growth A wide range of paper standards for this period, the National Standard (CNS) A4 specification (210X297 male dragon) for easy use (please read the precautions on the back before writing this page) Order-Line-ijf U. Λ 6 B6 桃 充 五1. Within the range of km (27) of the invention, it can exert excellent herbicidal effect at a very low dose. Next, the effects of the compound of the present invention will be explained by test examples. In the test, the following compounds were used as comparison agents. Compound A — 3-((4,6-Dimethylpyrimidin-2-yl) Gasified Pyridine® Ethyl Formate (compound contained in the specification No. 64-8 of No. 4). Compound B-3- (4, 6-dimethoxypyrimidin-2-yl) thiopyr «methyl formate (compound contained in the instruction No. 2-1 2 1 9 7 3) Test Example 1 Using paddy soil The herbicidal effect test of the treatment was to fill the paddy field soil in a 100 on 2 plastic bowl. After turning the soil, the seeds of edible barnyard grass (E c), Yu Jiuhua (Mo) and reed pen (Sc) were sown and irrigated to 3 cm water depth. The next day, the water and agent prepared according to Preparation Example 2 were diluted with water and dropped on the water surface. The application rate is an effective component of 100 grams per 10 acres. Then, they were bred in the greenhouse, and on the 21st day after the treatment, the herbicidal effect was checked according to the criteria in Table 3. The results are shown in Table 4. (Please read the precautions on the back and then fill out this page) Printed by the Ministry of Economic Affairs, Central Standards, Industry and Consumers Cooperatives 29- This paper is ife-sized and used in the BB home sample standard (CHS) A 4 specifications (210x297 male dragon) 2110 ° 9 5 3. Description of the invention (28) Table 3 Λ 6 Β 6 The index of the herbicide effect (degree of fertility suppression) printed by the Ministry of Economic Affairs, Standards, Industry and Consumer Cooperatives 5 5 The herbicidal effect of more than 90% inhibition 4 The herbicidal effect of more than 70% but not 90% 3 More than 50% less than 70% herbicidal effect 2 More than 30% less than 50% herbicidal effect 1 More than 10% less than 30% herbicidal effect 0 0% more than 10% herbicidal effect -30- (please first Read the precautions on the back and then write this page)-Binding · Order _ This paper uses the Chinese National Standard (CNS) A4 specifications (210x297 male dragons) Λ β Η 6 Central Ministry of Economic Affairs, Ministry of Economic Affairs, ΚΧ 工 Consumer Cooperation Du Print

This paper uses the Chinese National Standards (CNS) A4 specifications (210X2 Machi *)-:} 1 _ 81 _ 2. 20,000 recognized 1〇⑹ 5. Description of the invention (30) Λ 6 Β6 5 8 5 5 5 . 6 3 5 5 5 6 6 5 5 5 6 7 5 5 5 8 1 5 5 5 Test Example 2 Weeding effect test by dryland soil treatment Fill the dryland soil with 100 cm 2 plastic bowl and plant edible barnyard (Ec), large Seeds of Ma Liao (Po), Qingmi (Am), Li (Ca), and Michelia serrata (Ci), covered with soil, diluted with the water and preparation water prepared according to Formulation Example 2, and applied with active ingredients per 10 acres 100 grams, with a small sprayer spreading 100 liters evenly on the soil surface. Then, they were harvested in the greenhouse. On the 20th day after the treatment, the herbicidal effect was checked according to the criteria in Table 3. The results are shown in Table 5. Table 5 (please read the precautions on the back before writing this page) Ministry of Economic Affairs: 汮 央 潒 准 ^ ¾Community cooperatives print compound number weeding effect Ec Po Am Ch Ci 1 5 5 5 5 5 2 5 5 5 5 5 19 5 5 5 5 5 2 0 5 5 5 5 5 2 1 5 5 5 5 5 2 2 5 5 5 5 5 2 2 4 5 5 5 5 5 2 5 4 5 5 5 4 2 6 5 5 5 5 5 -32- The size of this paper is easy to use China Sleepless Family Standard (CNS) A 4 specifications (210X297 mm) ii〇〇 ^ Λ 6 Β6 V. Description of the invention (31)

(Please read the precautions on the back before filling in this page) Pack ·: 11- Line · The Ministry of Economic Affairs Standards Printed along the Employee Consumer Cooperatives Test Example 3 Weeding effect test by dry land stem and leaf treatment in 100 cm 2 plastic bowl Fill the dryland soil and sow the seeds of edible barnyardgrass (Ec), Polygonum (Po), Amaranthus (Am), Li (Ch &gt;, Miscanthus (Ci), and cover the soil. After two weeks in the greenhouse, press Formulation Example 2 Tiao-33- This paper scale is free of Chinese B Family Standards (CNS) A4 specifications (210X297): 211009 V. Description of the invention (32) Λ 6 Β6 water and _, diluted with water, every 10 Apply 100 grams of active ingredients to acres, use a small sprayer from the top of the plant, press each 10 acres to spread 100 liters of the whole M leaves. Then, grow them in the greenhouse, according to the 14th day after treatment Table 3 benchmarks, check the weeding effect. The results are shown in Table 6. (Please read the precautions on the back before filling in this page) Outfit-Ministry of Economic Affairs Standard 'Αβ 工 消 # Cooperative Society Printed 34 This paper size Xiao Use the Chinese Standard (CNS) A4 specifications (210X297 g; ¢) _ V. Description of invention Λ 6 Π 6 Table 6 in the Ministry of Economy Central Bureau of Standards, Employee Digestion Cooperative Print 51 Compound Number Weeding Effect Ec Po Am Ch Ci 1 5 5 5 5 5 2 5 5 5 5 5 1 9 5 5 5 5 5 2 0 5 5 5 5 5 2 1 5 4 5 5 5 2 2 5 4 4 5 5 2 3 4 5 4 5 5 2 4 5 5 5 5 5 2 6 5 5 5 5 5 2 2 7 5 5 5 5 5 2 9 5 4 5 4 4 3 5 5 5 5 5 5 3 6 5 5 5 5 5 3 7 5 5 5 5 5 3 3 8 5 5 5 5 5 3 9 5 5 5 5 5 4 4 0 5 5 5 5 5 4 1 5 5 5 5 5 4 2 5 5 5 5 5 4 3 5 5 5 5 5 4 4 5 5 5 5 5 4 4 5 5 5 5 5 5 4 6 5 5 5 5 5 -3 ^ A- (please read the precautions and notes before writing this page) -This paper is used in the "Sleeping Home (CNS), Regulations (21P &297;; :)) 81. 2. 20,000 2ll〇〇9 A 6 B6 V. Description of the invention (33) 4 8 5 5 5 5 5. 4 9 5 5 5 5 5 5 6 5 5 4 5 5 5 7 5 5 5 4 5 6 3 5 5 5 5 5 6 6 5 5 5 5 5 6 7 5 5 5 5 5 8 1 5 5 5 5 5 Test Example 4 Low-dose herbicidal effect test by dryland stem and leaf treatment Fill a dryland soil with a 600 cm 2 plastic bowl and sow barnyardgrass (Ec>, Hygrocybe (So), Polygonum (P〇), Qing Mi (Am), Li (Ch), Wild Morning Glory (Ip) and Xanthium (Xa), covered with soil. After two weeks in the greenhouse, the water and the predetermined amount of preparation (gW〇a) prepared according to Preparation Example 2 are diluted with water, and the whole stem and leaves are spread from the top with a small spray gun, which is equivalent to every 10 acres. For 100 liters. Then, they were bred in a greenhouse, and on the 14th day after the treatment, the herbicidal effect was investigated according to the criteria in Table 3. The results are as shown in Table 7. Table 7 (please read the precautions on the back before filling in this page). Installed. The Ministry of Economic Affairs Standards 揓 A Gongxiaozhi Cooperative Co., Ltd. Compound No. Active Ingredient Limit (g / 10a) Weeding effect Ec So Po Am Ch Ip Xa 19 6.3 5 5 5 5 5 5 5 2 2 0 6. 3 5 5 5 5 5 5 5 5 2 6 6.3 5. 5 5 5 5 5 3 3 5 6.3 5 5 4 4 4 3 3-3 5-This paper scale uses Chinese National Standard (CNS) A4 specifications (210X297 public) 2ii〇〇9

Λ 6 l \ G V. Description of the invention (34) 3 6 6.3 5 5 5 3 4 4 5 3 8 6.3 5 5 5 5 5 5 5 3 3 9 6.3 5 5 5 5 5 5 5 4 0 6.3 5 5 5 5 5 5 5 4 1 6. 3 5 5 5 5 5 5 5 4 4 2 6.3 5 5 5 5 5 5 5 4 4 6.3 5 5 5 5 5 5 5 4 5 6.3 5 5 5 5 5 5 5 4 6 6.3 5 5 5 5 5 5 5 4 7 6.3 5 5 5 5 5 5 5 4 8 6. 3 5 5 5 5 5 5 5 4 4 9 6.3 5 5 5 5 5 5 5 6 3 6. 3 5 5 5 5 5 5 5 6 6 6.3 5 5 5 5 5 5 5 6 7 6.3 5 5 5 5 5 5 5 A A 6.3 1 4 4 5 4 1 1 B 6.3 0 2 3 1 3 0 0 Please read the back first and note the items • 4 Fill out this binding Printed by the Ministry of Online Economics and the Central Bureau of Economic and Trade Affairs Beigong Consumer Cooperative 36 sheets of paper in a small format for use in a family (CNS) T4 (210X297: ¢) 8]. 2. 20,000

Claims (1)

6. Patent application No. 81101558¾ "Pyridinecarboxylic acid derivatives, their cracking methods and herbicides" Patent case application (amended in May 1982) 1. Species of pyridinecarboxylic acid derivatives and their salts as shown in the following general formula (〇) n C 0 0 R R1 (Please read the precautions on the back before writing this page.) In the printed formula of the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, R is a hydrogen atom, Ci-+ alkyl group, C 2-+ alkenyl group, C 2-4 alkynyl group, Benzyl, halogenated Ci-4 alkyl, cyano Ci-4 alkyl, Ci-+ alkanoyl Ci-+ alkyl, Ct-* alkanoyl aldehyde aldehyde (^-4 alkyl, Ci-+ Alkane-based aldehyde group Ci-* yard base, C2-7 yard base chopped gas base Cl-* yard base, C *-7 陳 銆 醪 醯 "base Ci-4 alkyl, c3-β 陳 alkyl Ci-4 alkyl group, chrysanthemum-atom atom, sickle-gold atom, or cation of organic amine, R1 and R2 are the same or different, and are Ci-+ alkyl, Ci-4 alkyl gas, halogen atom, halogenated Ci-4 alkyl gas group, or Ci-+ alkylsulfonyl group, R3) (for the formula-! &Lt; / group (where R3 and R + are opposite or different, hydrogen \ R4 atom, Ci-* alkyl , Phenyl, or Ci-5 acetyl group), cyano group,... Γ line. This paper is again applicable to China National Standards (CNS) A 4 specifications (210 X 297 mm) A7 B7 C7 D7 VI. Application Patent Fanyuan Phenyl (can be substituted by halogen, Ci-4 alkyl, or Ci-4 alkyl), benzene , Ci-4 Ci-4 alkyl, Ci-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, hydroxy, trimethylsilyl, nitro, 4, 6-dimethylpyrimidine- 2-base gas group, or hydrogen atom Rs (please read "Precautions on the back and then write this page") Y is a gas atom or formula (where R5 is a hydrogen atom or a methyl group is 0 or 1, CHO but X When it is a hydrogen atom, Υ is a group represented by the formula 2. As shown in item 1 of the patent application, the pyridinecarboxylic acid derivative or its H, where R is a hydrogen atom or a Ci-4 alkyl group, R1 and R2 are the same or Different, it is C! -4 alkyl group, Ci-4 alkyl gas group, halogen atom, halogenated Ci-4 ^ gas group, or Ci-4 alkylsulfonaldehyde group, R3 X is the formula-Jie / shown group ( In the formula, R3 and R + are the same or different-binding. Binding. Line · R4 printed by R Industry and Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs is hydrogen atom, Ci-+ alkyl group, phenyl group or (^-5 acetyl group), Cyano, phenyl (may be substituted by halogen atom, Ci-★ alkyl, or Ci-4 alkyl group), phenyl group, Ci-* alkoxy, hydroxyl, nitro or 4, 6-dimethyl gas Jibu 2- # oxy, -2-This paper is again applicable to the Chinese National Standard (CNS) 4 Specifications (210 X 297 mm) A7 B7 C7 2 Bamboo Goa_D7_ 6. Patent application R6 Y is an oxygen atom or a group shown (where R5 is a hydrogen atom or a methyl group), and η is 0 or 1 . 3. For example, if you apply for the pyridinecarboxylic acid derivative or its mule in item 1 of the Fanfan Garden, where Υ is a gas atom and η is 0. 4. For example, the pyridinecarboxylic acid derivative or its derivative in item 1 of Shinjuku Fanpu, where R is a hydrogen atom, methyl, ethyl, ethyl, methyl, propanal, ethyl, 1-ethyl Alkyloxyethyl, methoxymethyl, cyanomethyl, 2-chloroethyl, 2-propenyl, allyl.benzyl, sodium or potassium f R1 and R2 are methyl groups, X It is dimethylamino or vinyl, Y is a gas atom, and η is 0. 5.—Species weeding_composition, containing a herbicidally effective amount of the pyridinecarboxylic acid derivative or its salt as the active ingredient as shown in item 1 of Shenzhao Patent Fan Garden (please read the precautions on the back before writing this page ) 丨 Installed. Ordered. Line. The Ministry of Economic Affairs Central Bureau of Standards 8 Industrial and Commercial Cooperatives printed a copy of the profit and made a special application. The effect is as effective as the amount of salt. In addition to the 2 species of the pyridine compound, the first item is 6th. The pyridine compound is 1x tnf *. The range of benefits is specific to the application of Shen-grass, such as the use of salt, and its methods or herbs. In addition to derivatized acid, this paper is also applicable to the Chinese National Standard (CNS) A4 specifications (2 丨 0 X 297 mm) 2ϋ〇〇3 A7 B7 C7 D7 VI. Patent application fan circle 8.-The following general formula Preparation method of pyridinecarboxylic acid derivatives shown C 0 0 RR : 2-4 quasi-yl group c2-4 alkynyl group, benzyl group, halogenated Ci-4 alkyl group, "Ci-4 (please read the precautions on the back before writing this page) alkyl group, Ci-4 alkyl gas Group Ci-+ alkyl group, Ci-4 alkyl gas group. Packing. Order · Aldehyde gas group (^-4 alkyl group, Ci-4 alkyl gas sulfonyl group Ci-* alkyl group, c2-7 alkyl group Aldehyde group Ci-* alkyl, 7 cycloalkyl group awakening gas group "-4 alkyl group, C3-β alkyl alkyl Ci-+ alkyl group, aging gold atom, futu gold atom, or organic amine Cation, line. R1 and R2 are the same or different, and are Ci-+ alkyl, Ci-4 alkyl gas group, bismuth atom, halogenated Ci-4 alkyl group, or Ci-4 alkylsulfonyl group, R3 X It is a formula group (where R3 and R3 are the same or different, and are hydrogen R4, Central Bureau of Standards® of the Ministry of Economic Affairs; Atom, Ci-4 alkyl group, phenyl group, or Ci-s acetyl group), nitrogen group, Phenyl (may be substituted by fensu, Ci-4 alkyl, or Ci + + alkyl group), benzyl, halogenated Ci-4 alkyl, Ci-4 alkyl gas, C2-4 alkenyl, C2- * Alkynyl, hydroxy, trimethylsilyl acetylene This paper is again applicable to China National Standard (CNS) A4 specifications (21 0 X 297 mm> Λ7 B7 C7 D7 VI. Patent application base, nitro, 4, 6-dimethylpyrimidine q?-2 -base gas, or radium atom R5 Y is a gas atom or formula -Νγ (In the formula, Rs is a radium atom or a methyl group), η is 0 or 1, CHO but X is a hydrogen atom, Υ is the group shown in the formula -Νκ \\, and its support is as follows: Dipicolinic acid derivatives (please read the precautions on the back before writing this page)--Pack · XC 0 0 Re Y * Η (where Re is "-4 alkyl, C alkenyl, C set_ Hydrocarbon Ministry of Central Rectification and Quarantine Bureau R Industry and Consumer Cooperatives printed t alkynyl group, benzyl group, halogenated Ci-+ alkyl group, cyano Ci-4 alkyl group, h 4 alkyl gas group Ci-4 alkyl group, Ci-* alkane gas base Acyl group Ci-4 alkyl group, Ci-+ alkoxy group acetyl group Ci-4 alkyl group, c2-7 alkyl sulfonaldehyde gas group Ci-* alkyl group, C4-7 alkyl group aldehyde gas group " -4 alkyl group, C3-beta alkyl group Ci-4 alkyl group, alkali metal proton, metal atom, or Kuma ion of organic amine, X and Y1 are 0 or> ^ [10) and the following formula Derivatives of the indicated pyridine 5- This paper ruler is suitable for China National Standards (CNS) A 4 specifications (210 X 297 mm) .Line. A7 B7? Ύ〇〇3_D7 VI. Patent application scope R ' R2 (where R1 and R2 are the same as above, L1 is a bismuth atom, Ci-4 alkylsulfonyl, or benzyl acetyl) reactant in the presence of a chain. 9. A preparation method of pyridinecarboxylic acid derivatives as shown in the following general formula (please read the precautions on the back before writing this page). Pack. C 0 〇 M R * R2 is defined. Among them, R1, R2, X and Υ1 are as described in item 1 of Shenzhanlifanyou, and M is a salty metal atom or an old-earth metal atom), and its special characteristics are as follows: Formic acid derivatives. Line. Central China Bureau of Standards, Ministry of Economic Affairs 利 专 謮 0 Applicants If it should be a copy of this paper, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is again applicable