TW201021702A - 2-[(1-cyanopropyl)carbamoyl]-5-methoxymethyl nicotinic acids and the use thereof in manufacturing herbicidal imidazolinones - Google Patents

Abstract

2-[(1-cyanopropyl) carbamoyl]-5-methoxymethyl nicotinic acids of formula (I) where Z is hydrogen or halogen; Z1 is hydrogen, halogen, cyano or nitro; R1 is C1-C4 alkyl; R2 is C1-C4 alkyl, C3-C6 cycloalkyl or R1 and R2, when taken together with the atom to which they are attached, represent a C3-C6 cycloalkyl group op-tionally substituted with methyl, and R3 is hydrogen or a cation preferably selected from the group consisting of alkali metals, alkaline earth metals, manganese, copper, iron, zinc, cobalt, lead, silver, nickel, ammonium and organic ammonium; are useful intermediates for the synthesis of herbicidal imidazolinones.

Description

201021702 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to the acid-reaction of 2-[(1-cyanopropyl)amine-carbamoyl]-5-methoxyne, the preparation and manufacture of such compounds The use of herbicidal scented sage (methyl oxime). (1)·]] [Previous technique] 2-(2-Mi (4) Shiki) is a derivative of acid test, such as methoxyphyllin [(RS)-4-isopropyl-4-methyl-5-side oxygen Alkyl-2-imidazoline methyl 'mercapto nicotinic acid), oxygen group

It is an effective selective herbicide for ALS-inhibitors and can be applied after emergence and after. Various methods for synthesizing such compounds are known from the literature, for example, ΕΡ-Α 0 322 616 ^ ΕΡ-Α 0 747 360 ^ ΕΡ-Α 0 933 362^Q. Bi et al., Mordern Agrochemicals 6(2) ( 2007) 10-14 〇Although the synthesis on the industrial scale can be carried out by these methods, there is still room for improvement', especially in terms of economic and ecological aspects, such as increasing the overall yield or avoiding certain solvents or reagents. ΕΡ-Α 0 322 616 discloses the synthesis of 2_[(1_胺甲醯基α二) by the reaction of 5-methoxymethyl-2,3-pyridine phthalic anhydride with α-amino-α-methylpentamidine A 144469.doc 201021702 propyl)amine carbhydryl]-5-methylmethyl terminal..%. The base is acidified, and the compound is further converted by reaction with NaOCH3. T-Oxygen Grass Tobacco and Subsequent Acidation [Summary] One of the targets of the month is to provide a useful novel intermediate for the synthesis of herbicide (tetra)linone and the preparation methods thereof. The re-target of the present invention provides an improved method for the manufacture of weeding (four) butterflies such as methoxy π mica.

2- 2-[(1)Cyanopropyl)amine-based]5-methoxymethyl-final acid has been found to be a useful intermediate for the manufacture of herbicidal imipenones. ΕΡ-Α 0 m 027 and ΕΡ·Α 〇 142 718 describe the reaction of pyridine_23_dicarboxylic anhydride with 2-amino-2,3-dimethylbutyronitrile and further conversion to herbicidal imidazolidinone, however, An example of a compound substituted with 5-methoxymethyl group is not disclosed. [Embodiment] According to this aspect of the invention, 2-[(1-cyanopropyl)amine oxime of formula (I) is provided. Mercapto]-5-methoxymethylnicotinic acid, Ζ

Wherein hydrazine is hydrogen or halogen; hydrazine 1 is hydrogen, halogen, cyano or nitro; 144469.doc 201021702 R1 R2 R3 is (^-(:4 alkyl; system (VC4 alkyl, c3_c6 cycloalkyl or when Rw When the atomic bond of the bond is bonded, it represents a C3_c6 cycloalkyl group which is optionally substituted by a methyl group, and a dentate or a cation selected from the group consisting of the following: metal, soil test, and fierce , copper, iron, U, silver, lanthanum, ammonium and organic ammonium. Another aspect of the invention provides a preparation of 2 [(1 cyanopropyl)amine fluorenyl]-5-chloro of formula (1) A method of methylnicotinic acid comprising the steps of: (1) 5-(methoxy)methyl-pyridine-2,3-diphthalic anhydride of formula (11) and 2-aminoalkanecarbonitrile (III)' I^N -CR^R^-CNGn) reaction, wherein the rule 1 and the rule 2 are as defined in the formula (I),

(") where 'Z' Z1 is as defined in equation (1). Another aspect of the invention provides the use of a compound of formula (I) for the preparation of a herbicidal imidazolidinone of formula (IV), 144469.doc -6 - (IV) 201021702 z

R1 where Z, Z1, Rl, R2 3 , ^aa are as defined in formula (I). Another aspect of this month

(d) a method of the compound, ', - species & the herbicidal taste of the formula (Iv) which comprises the following steps: (1) hydrolyzing the nitrile of the formula (1) to obtain the amine of the formula (V),

Z

R1

Wherein Z, Z1, R1, R2, R3 are as defined in formula (1); and (11) compound (V) and MOH/CH3〇H (wherein the lanthanide metal is more lanthanide

The Na or hydrazine reaction is followed by acidification as needed to form the herbicidal imidazolinone (IV). The use of the novel intermediate (1) in the synthesis of the herbicidal imidazolinone improves the yield of the guanamine (V)' and thus increases the overall yield of the synthesis process. The zone selectivity of the open anhydride is excellent, even without the need to add a nitrogen test as recommended in EP-A 0 144 595. Surprisingly, the methoxymethyl group is stable in addition to the (four)-step synthesis. The sign of the formula (I) preferably has the following meaning: z is preferably hydrogen. Z1 is preferably hydrogen. R1 is preferably a CVC4 alkyl group. R2 is preferably a CVC4 alkyl group. R3 is preferably hydrogen, an alkali metal or NW3, wherein R4 is hydrogen or R5, and the ruthenium 5 is more preferably hydrogen. Preferred are compounds of formula (1) in which all symbols have a preferred meaning. The compound of the formula (I) is a compound (la) and a salt thereof.

The compound (I) can be produced by reacting an acid anhydride (11) with an amino nitrile (111), as shown by the synthesis of a preferred compound (la), wherein the ruler 1 and the ruler 2 are as defined in the formula (ΙΠ) :

(Ha) ch3

H2N--CN ——^ (la) CH(CH3)2 (Ilia) Aminonitrile (III) is commercially available or can be prepared by methods known in the art (cf. 144469.doc 201021702, for example, EP- A 〇095 105). In general, the compound is used as the 5' parent equivalent compound (II), and 8 to 1.2 equivalents of the amino nitrile are used, preferably 〇% to }. Preferably, it is selected from the group consisting of aromatic hydrocarbons (preferably toluene, = (iH ^ ^ ~ ~ toluene), gasified aromatic hydrocarbon chlorine, gas benzene), chlorinated aliphatic hydrocarbons (such as ^• dichloroethane and - The reaction is carried out in a solvent of smoldering, acetic acid, and a mixture thereof. / Without acetic acid as the main solvent, it is advantageous to add 〇5 to 1 〇 equivalent to (1) to 3 equivalents (based on the compound (II)).

U.S. Patent No. 4,562,257, the disclosure of which is incorporated herein by reference to the entire disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the present disclosure of It is not necessary in the present invention to employ such additives 'and in the examples, the listed additives are not present in the reaction mixture. Generally, the reaction is from about 40 to about 12 (TC, preferably from about 6 to about 10). The reaction time is generally from about 1 to about 3 hours. In a preferred embodiment, the compound (11) is dissolved in a solvent and introduced to the reaction temperature, and the amino nitrile (111) is gradually added. After completion of the reaction and cooling, the nitrile compound β is separated by a standard method. However, in the preferred embodiment, the compound (1) is not isolated, but the reaction mixture is directly used for the hydrolysis of the following nitrile. In a preferred embodiment, the anhydride (II) for the preparation of the compound (I) is obtained by a process comprising the following steps: (0 reacting a compound of the formula (VI) with a dehydrating agent in the form of a base, 144469.doc -9 - 201021702 Ζ

I- in COOH

COOH (VI) where Z is hydrazine or halogen; Ζ 1 system, halogen, CN or Ν〇2. The dehydrating agent is preferably acetic anhydride. The molar ratio of diacid (VI) to anhydride is generally from 1.0 to 丨.05. The synthesis of diacids (VI) is disclosed, for example, in EP-A 0 747 360. In a preferred embodiment, the diacid (VI) is prepared by the following steps: (i) comprising at least 20% by weight water (based on water and bromine at a closed vessel pressure and at a temperature of from about 75 to 11 ° C) The compound of the formula (VII) is reacted with a base containing MOCH3 and/or MOH (wherein a lanthanide metal or an alkaline earth metal) in a methanol/water mixture of the total amount of the compound (VII).

Br' Q+H2C Z1>

1/ (VII where Q is a tertiary aliphatic or cyclic, saturated, partially unsaturated or aromatic amine; Z system or sulphate; 144469.doc -10· 201021702 Z1 system 卤素, halogen, CN or N02; Y1 and Y2 are each independently OR4, NR4R5, or when combined, Υ*Υ2 is -Ο-, -S- or -NR6-; R4 and R5 are each independently Η; Alkoxy-substituted alkyl or phenyl substituted by one to two Ci-C alkyl, CrC4 alkoxy or halogen atom, or optionally one to three CrC4 alkyl, Ci-C* alkoxy Or a phenyl group substituted with a halogen atom; R6 is 11 or (: 1-(:4 alkyl, compound (VII) can be prepared as disclosed in, for example, EP-A 0 548 532. In methanol and at least 20% by weight The reaction is carried out in a solvent of water (based on the total amount of water and bromide (π)). Preferably, the amount of water is from about 25 ° / ❶ to about 75%, more preferably from 30 to 70%, specifically about 40 to About 50%. The remainder of the solvent mixture is methanol and up to about 50%, preferably up to about 20% other solvent, preferably selected from the group consisting of toluene, benzene and ethanol. sterol to bromide (II) Weight ratio 〇_5-25:1, preferably 1-2〇: 1, more preferably 1-10:1, specifically 2_3:1. The base contains MeOM, MOH or a mixture of MeOM and MOH, wherein the ruthenium alkali metal Or alkaline earth metal, preferably Na or yttrium, specifically Na. When it is a mixture MeOM/MOH, lanthanum may be the same or different, preferably the same. If MeOM is present, MeOM (preferably MeONa) is bromide The molar ratio of (VII) is generally 1-10:1, preferably 1-7.5:1, more preferably 1.25-7:1, specifically 1.25-2:1. 144469.doc -11- 201021702 Right exists For MOH, the molar ratio of MOH (preferably NaOH) to bromide (VII) is generally from 0.5 to 10:1, preferably from 1 to 7:1, more preferably from 3 to 5:1. If a mixture of MeOM and MOH is used. As a base, the molar ratio of 1 〇 11 to bromide (νπ) is generally in the range of 0.5 to 7.5:1, preferably 1 to 5:1, more preferably 3 to 5:1. In a preferred embodiment, No hydrazine is added to the reaction mixture. Due to economic factors, it is preferred to use an excess amount of hydrazine relative to MeOM. In another preferred embodiment, only 3-10, more preferably 4-7, more preferably 4_5-6 The ratio of the added total test / bromide (VII) molar ratio is generally about 2 · 5-1 〇: 1, compared to It is about 3-7:1, and more preferably about 4.5-6:1. The added MeOM is generally dissolved in methanol. The added MOH is dissolved in water. The temperature range for the reaction is about 75 to 11 〇. . (:, preferably about 80 to 105 ° C, more preferably about 80 to 100 ° C. In a closed container, for example, a Parr pressure reactor, generally about 1 〇 1 to 5 · 〇〇 ' ' preferably about 1.02 The reaction is carried out at a pressure of from 4 to 00 bar, specifically about 03.03 to 3-5 Torr. In the preferred embodiment, 'no external pressure is applied, in a closed vessel, the pressure accumulated by the solvent at the reaction temperature The reaction is carried out. The reaction time is generally from about 5 to 20 hours, preferably from about 6 to 9 hours, in particular about 8 hours. In a preferred embodiment 'will contain about 25 to 75% by weight (based on water and bromide) The bromide (VII) of the water of the total amount of (vii) is dissolved in methanol, and the aqueous NaOH solution is slowly added at a temperature in the range of about 25 to 4 ° C, followed by about 4 to 50 C. Na〇cH3 is slowly added to the decyl alcohol at a temperature. The reaction mixture is then heated to a reaction temperature in a closed pressure reactor (generally 80 to 1 Torr), at which time the pressure rises with the reaction temperature reached. 144469.doc -12· 201021702 After the reaction is completed, cool the mixture and operate according to known procedures, such as cooling, using acid' The sulfuric acid treatment is carried out until the compound (VI) is precipitated and passed through. The compound (vi) obtained above is used for the synthesis of the intermediate of the present invention because of its purity. Therefore, in a preferred embodiment, the method for preparing the compound (1) comprises the following steps. : ' (i·1) in a methanol/water mixture containing at least 20% by weight of water (based on the total amount of water and bromide (νπ)) at a closed vessel pressure and at a temperature of about 75 to 11 CTC (VII) reacting a compound with a base containing MOCH3 and/or ?11, wherein the lanthanide metal or alkaline earth metal,

Wherein Q is a secondary aliphatic or cyclic, saturated, partially unsaturated or aromatic amine; anthracene or halogen; Ζ1 system, halogen, CN or Ν〇2; Υ1 and Υ2 are each OR1, NRk2 Or when combined, γ1γ2 is -〇-, -S- or -NR3-; R1 and R2 are each independently Η; Cl_c4 alkyl substituted by CrC4 alkoxy group as needed or one to two Ci as needed -C: 4 alkyl, CrC: 4 alkoxy or halogen atom substituted 144469.doc • 13· 201021702 base; or optionally substituted with one to three Cl_C4 alkyl, Cl_c4 alkoxy or halogen atom R3 is Η4 (ν(:4 alkyl; (i-2) in the presence of a base and a solvent selected from the group consisting of decyl tertiary butyl ether, diisopropyl ether, cyclopentyl methyl ether, and mixtures thereof, The compound (VI) formed in the step (?) is reacted with a dehydrating agent to obtain an acid anhydride (11), and (1-3) the acid anhydride (II) is reacted with a 2-aminoalkanonitrile (ln), H2_NCRiR2_CN (In), Wherein R1 and R2 are as defined in formula (1). The compound of formula (I) is an intermediate in the synthesis of herbicidal imidazolinone (IV). In the first step, the hydrolyzed nitrile functional group is hydrolyzed to obtain the preferred compound ( L) and (Va) exemplified by guanamine:

In general steps, it is generally about 30. (: to 120 ° C, preferably 50. (: to 9 (at a temperature in the range of TC, adding 8. 8 to 1.2 equivalents (based on (1)) of strong inorganic, preferably sulfuric acid (preferred concentration of 30 to 98) %) and water (for example, 2 to 1 〇田) progressively stir the mixture until complete conversion. The reaction time is generally from 1 to 8 hours, preferably from 1 to 5 hours. Processing and isolation are carried out by standard methods, for example, from aqueous solutions. Precipitation (for example, its salt salt formula I). In the preferred embodiment, the reaction mixture is directly used in 144469.doc 201021702 for the following reaction steps. In another process of the present invention, weeding is prepared by a method comprising the following steps: The imidazolinone compound (IV): (i) the preparation of the guanamine compound of the formula (V); and (ii) the compound (V) with CH3OM or MOH/CH3OH (wherein the ruthenium metal, preferably Na or ruthenium) The reaction is followed by acidification to form the herbicidal oxazolone (IV). In another preferred embodiment, the test is preferably selected from the group consisting of MOH (where the μ system is preferably Na or Κ 'Teru is Na) The reaction mixture from step (1) in step (ii) in the presence of an aqueous solution (generally based on (y) from 2 to 100 equivalents) The sterol (generally based on (V) is from 2 to 100 equivalents) is reacted. The reaction is carried out at a temperature of from 20 to 120 ° C, preferably from 40 to 90. (The temperature is in the range. The reaction is preferably carried out under atmospheric pressure or high pressure, preferably The pressure is formed at the desired reaction temperature. The reaction time is generally from 1 to 8 hours, preferably from 5 to 5 hours. _ The separation of the product is accomplished by standard methods. In the preferred embodiment, Water is added and the organic solvent is distilled off. The residue is dissolved in water and acidified, whereby compound (IV) is precipitated. The crude product can be further purified by filtration, for example, with water or recrystallized. In another preferred embodiment of the invention, Provided is a method for preparing a herbicidal imipenone of the formula (IV), which comprises the steps of: (1) 'initial reaction of compound (1) with M〇H and MOCH3 in sterol containing (aqueous) effluent 2'系-alkali metal, followed by acidification as needed 0 144469.doc • 15· 201021702 h3co

Base +H202 H3CO ~~MeOH~

The reaction is carried out in a similar manner to that described in EP-A 0 144 595. The following examples are intended to illustrate and not to limit the invention. EXAMPLES Example 1 Synthesis of 2-[(1-cyano-1,2-dimethylpropyl)amine hydrazino]_5_decyloxymethylnicotinic acid (la)

a) Synthesis of 5-methoxymethyl·"bipyridine-2,3 dicarboxylic anhydride (na) 1937 g of toluene, 7.3 g (0.08 mol) of ruthenium pyridine and 412 g (4_03 mol) of acetic acid In the device. Add 833 g (3.95 mol) of 5-methoxymethyl-. The reaction mixture was incubated with -2,3-dioxalic acid (Via) and heated to 40 to 60 ° C for 2 hours. After the reaction was completed, the mixture which was not isolated from the product was used in the following condensation step. Yield: 99% (measured by HPLC analysis) b) Synthesis of (la) sodium salt 144469.doc 16 201021702 The reaction mixture containing 755·80 g (3.91 m〇l) (IIa) in step (4) was incorporated. The reactor was kept at 15 to 2 〇〇c. 5400 g of toluene containing 584 g (4 i4 mol) of 2-amino-2,3-dimethyl-butyronitrile was added and cooled, and the temperature of the mixture was maintained at another 30 minutes to complete the conversion. The mixture which was not further isolated from the product (la) was hydrolyzed and further converted to imazamox (IVa). Yield: 89% (measured by HPLC analysis), isomerization ratio (2:3 adduct) 11:1. Example 2 Synthesis of imazamox (IVa) (a) Synthesis of 2-[(l-aminomethylmethyl dimethyl propyl) amine methyl methoxy-methoxy nicotinic acid (Va)

Treatment of 1 〇 74 66 g (3 52 〇 1) with 278 g (15.5 mol) of water (9199 g of the reaction mixture of (4), g (3.45 then '346 ML with a certain rate) of the reaction The mixture allows the temperature to rise to 5 〇 to (9). cg water 'followed 1185

After 2 hours from 50 to 6 ° C, 3138 containing hydrolyzate (Va) was added.

The layer of the next step. 144469.doc •17· 201021702 (b) Synthesis of Imazamox (IVa)-sodium

(IVa-Na was added 1327 g (16.6 mol) of 50% aqueous NaOH solution to the aqueous layer containing (Va) in the step (d), and the mixture was stirred at 80 ° C for 30 minutes. At pH 7, by depressurizing to 300 The residue of toluene was removed by mm Hg. After completion of the crystallization reaction, the sodium salt mixture containing imazamox was cooled to 60° C. The reaction mixture which was not further purified was used in the following acidification step. Yield: 3.22 mol (IVa)- Na, measured by HPLC analysis, 84% (based on (Via)) c) Synthetic imazamox (IVa) ο

Va) Feed 9616 g of the mixture in step (b) to a vessel at room temperature. At 89 ° C, 3700 g of water and 1698 g of sulfuric acid (98%) were added to the mixture to produce a pH of 3.2. The resulting slurry was cooled to 65 ° C and filtered. The filter cake was washed with 3689 g of water and the product wet cake was dried at 60 to 65 °C. 144469.doc 18· 201021702 Yield: 1000 g (3.28 mol) (IVa) 83% (based on (Via)). Example 3 Synthesis of imazamox (IVa) from 5-methoxymethyl-2,3-pyridinedicarboxylic acid (Via) - 2-pot method at 25 ° C, 2-11 g (10 mmole) 5-曱Oxyfluorenyl-2,3-pyridinedicarboxyl acid, 20 ml of toluene, 1.1 g (10.6 mmole) of acetic anhydride, and 0.14 g (1.5 mmole) of methylpyridine fed with a mechanical stirrer, thermocouple, and reflux The condenser is in a 100 ml three-necked bottle unit. The slurry was heated to 50 ° C and maintained at this temperature for 1 hour. Then the reaction was cooled to 25 ° C and 1.75 g of 2-amino-2,3-dimethylbutyronitrile (10.6 mmole) was added over 1 minute. 67% solution in benzene. The reaction was maintained at 25 to 31 ° C for 1 hour. Immediately, 0.54 g of water (30 mmole) and 0.41 g of 96% sulfuric acid (4 mmole) were added and the mixture was heated to 5 0-5 5 °C for 2 hours, then 65-70. (: 2 hours. Then add 2.0 g of water, then add 5.6 g of 50% sodium hydroxide (70 mmole) and heat the reaction to 65-70 ° C for 30 minutes. Then cool the reaction to 5 〇. (: and add φ 10 mL A. The reaction was cooled to 22 ° C and the organic phase was removed from the aqueous phase. Between 30 and 40 ° C, 96% sulfuric acid was added to bring the pH down to 3-4. Another 5 ml of water was added. The mixture was washed with 3 X 1 mL of water to obtain 4.2 g of moist imazamox. The product was dried to afford 2.1 g (yield of 67%). The structure was confirmed by NMR and MS. Example 4 Preparation 5 -(decyloxy)-2,3-«pyridinic acid (Via) a) Synthesis of dimercapto 5-(bromoindolyl)-2,3-pyridinedicarboxylic acid (Va) (50% conversion) ) 144469.doc -19· 201021702

Br2

The compound dissolved in 1139.0邑1,2-diethanol (218.4§ (1.0 mol) of compound (Va) and 160.0 g of water was fed and heated to 72 ° C (about 1-2 ° below reflux) C) 14.4 g (0.075 mol) 2,2'-azobis(2-mercaptobutyronitrile) (Vazo 67) added to 160.0 g EDC at 72 ° C for 2 hours. After 30 minutes, 2 In an hour, 143.8 g (0-9 mol) of bromine was added, and the pH (pH 5-7) was controlled in an amount of about 375.0 g of aqueous sodium hydroxide (15%). The mixture was stirred for 1 hour to complete the reaction (HPLC analysis). After 40 ° C, separate the phases. b) Synthesis of [(5,6-dicarboxy-3-pyridyl)methyl]trimethylammonium bromide, dimercaptoether (Vila)

Feeding a mixture of 288.1 g (1.0 mol) of compound (Ilia) and a di- and tribrominated by-product in 3359.0 g EDC (organic phase in step a, unreacted compound (Ila) and higher bromination by-product). The mixture was heated to 30 ° C and the vessel was evacuated to 200 mbar. 70.9 g (1.2 mol) of tridecylamine (TMA) was added to the gas phase (closed system) at 40 ° C for 2 hours. The mixture was stirred for an additional 1 hour (HPLC conversion detection: compound (IIIa) <0_l ° / 〇) in solution. 144469.doc -20- 201021702 Distilled excess TMA along with EDC (mass: 40% EDC mass at 50-55 ° C (370-250 mbar) was transferred to step 2 (1344 g)). The pH of the distillate was <9. 630.0 g of water was sprayed onto the wall to dissolve the solids and transfer the mixture to the next container. The mixture was then stirred for 0.25 hours and the bottom organic phase was separated at 40 °C. Add 320.4 g EDC. The mixture was stirred and the bottom organic phase was separated at 40 °C. The back extraction was repeated at 40 ° C with 320.4 g EDC. The two organic stripping phases were combined with the first organic phase and recycled to the next bromination batch (after addition of 50% fresh compound (Ila) for further circulation). Repeat steps a) and b) six times. In the last cycle, compound (IIa) was not added in step a) and 0.8 mol TMA was added in step b). The total conversion of the compound (Ila) was 96.6%. The yield of the compound (la) (in 7 cycles) was 77.4%, and the purity was 95% (determined by HPLC). Bromide (IIa) (0.41 mol) containing about 40% by weight of water was dissolved in decyl alcohol. Aqueous NaOH solution was added over 30 minutes at 35 ° C and the mixture was stirred for another 15 minutes. A solution of NaOCH3 in methanol was added at 45 ° C for 20 minutes. The reaction mixture was transferred to a Parr pressure reactor and heated to the reaction temperature (80 to 100 ° C). The reactor was shut down at about 60 ° C, whereby the pressure accumulated to about 40 to 45 Psi at the reaction temperature. No external pressure is applied. After 6 to 8 hours, the reaction mixture was cooled to room temperature, treated with sulfuric acid to adjust the pH to a value of 1.5 to 2, and filtered to obtain a solid. The solid was washed with water and dried in a vacuum oven to give a white solid (mp 161 to 162. 144469.doc -21- 201021702 c) Synthesis of diacids (VI)

Br(CH3)3N

OOCH, (Vila) N^^COOCH3 1. MeOH/Base 2. H+ *

COOH COOH [5,6-Dicarboxy-3-pyridyl)methyl]trimethylammonium bromide didecyl ester (0.41 mol) containing about 40% by weight of water was dissolved in decyl alcohol. At 35 ° C, an aqueous NaOH solution was added over 30 minutes and stirred for another 15 minutes. Methanol containing NaOCH3 was added at 45 ° C for 20 minutes. The reaction mixture was transferred to a Parr pressure reactor and heated to the reaction temperature (80 to 100 ° C). At about 60 ° C, the reactor was shut down and the reaction temperature reached a rise pressure of 40 to 45 Psi. No external pressure is applied. After 6 to 8 hours, the reaction mixture was cooled to room temperature, treated with sulfuric acid to adjust pH to 1.5 to 2 and stirred to give a solid. The solid was washed with water and dried in a vacuum drying oven to obtain a white solid (mp 161 to 16 ° C) whose purity was more than 99% by HPLC. 144469.doc 22-

Claims (1)

201021702 VII. Patent application scope: 1. A 2-((1-cyanopropyl)aminoindenyl]-5-nonyloxymethylnicotinic acid of formula (I) Z is hydrogen or _; z1 is hydrogen, halogen, cyano or nitro; R1 is (^-(:4 alkyl; R2 is CVC4 alkyl, Cs-C6 cycloalkyl, or when R1 and R2 are etc. When the bonded atoms are bonded together, it represents a c3-c6 cycloalkyl group which is optionally substituted by a methyl group, and ▲ R3 is a hydrogen or a cation. ❹ 2. The compound of claim 1, wherein Z and Z1 are H. 3. The compound of claim 1 or 2, wherein R1 is CH(CH3)2 and R2 is CH3. 4. The compound of claim 1 or 2, wherein Z and Z1 are hydrazine; R1 is CH(CH3)2; R2 is CH3 and 144469.doc 201021702 R3 System. 5. A 2-[(1-cyanopropyl)aminoindenyl]-5-methoxy group of formula (I) as claimed in claim 1 or 2曱 Based on an acid test method, which comprises the steps of: (0) reacting 5-methoxymethyl acridine-2,3-dicarboxylic anhydride of formula (II) with 2-aminoalkonitrile (IIUHzN-CRiRiCISKIII) , wherein Ri&R2 is as defined in the formula (I) of claim 1 or 2, ζ 〇 Wherein Z and Z1 are as defined in formula (I). 6. The method of claim 5, wherein the ratio of the anhydride (II) to the amino nitrile (ΙΠ) is 1:0.8-1.2. 7. The method of claim 5, which is carried out in a solvent selected from the group consisting of aromatics, gasified aromatic hydrocarbons, vaporized aliphatic hydrocarbons, acetic acid, and mixtures thereof. 8. The method of claim 5, wherein the acetic acid solvent or 5 to 10 equivalents of acetic acid (based on (II)) is added to the solvent. 9. The method of claim 5, wherein the reaction is between 40 and 120. 10. The method of claim 5, wherein the reaction mixture is substantially free of specific components, such as the method of claim 5, comprising the following steps: : (1_1) under pressure in a closed vessel and at a temperature of about 75 to 110 ° C, 144469.doc 201021702 is a sterol containing at least 20% by weight of water based on the total amount of water and bromide (VII) / Water mixture, reacting a compound of formula (VII) with a base containing MOCH3 and/or hydrazine, wherein the lanthanide metal or alkaline earth metal, Wherein Q is a tertiary aliphatic or cyclic, saturated, partially unsaturated or aromatic amine; lanthanum or dentate; Ζ1 Η, halogen, CN or Ν〇2; Υ1 and Υ2 are each independently 〇Ri, NRir2, or when combined, YW2 is -Ο-, -S- or -NR3-; R1 and R2 are each independently Η; as required c^c:4 Alkoxy-substituted Ci_C4 alkyl or, if desired, one to three (: 丨-(: 4 alkyl, C!-C4 alkoxy or halogen substituted phenyl; or optionally one to three Ci_C4 alkyl) , Ci-C: a 4-alkoxy or a halogen-substituted phenyl group; and an R 3 -alkyl group; (1-2) in a base and selected from decyl-tert-butyl ether, diisopropyl ether, cyclopentyl 144469.doc 201021702 The reaction (VI) formed in the step ("" is reacted with a dehydrating agent to obtain an acid anhydride (H) Z in the presence of a solvent of methyl ether and a mixture thereof. Its t Z is hydrazine or halogen; Z1 is hydrazine, _ 素, CN or ν 〇 2, and (1 3) reacts the anhydride j (11) with the 2-amino carbonitrile (10) H2N_cRlR2 cN(m), wherein r1 & R2 is as defined in formula (I). 12. A method of producing a guanamine of formula (V), 2 Wherein Z, 2:1, R1, R, R are as defined in the formula (I) of claim 1 or 2, which comprises the following steps: 13. (1) Hydrolyzing the nitrile of formula (1) to obtain a guanamine of formula (V) . Method for preparing herbicidal sodium salivin compound of formula (IV), 144469.doc 201021702 z Wherein Z, zi, Rl, r2, r3 are as defined in the claim (1), which comprises the steps of: (1) hydrolyzing the nitrile of formula (1) according to any one of claims 1 to 4 to obtain a request The compound (V) of the formula (V), and (π) reacts the compound (V) with MOH/CHsOH (wherein the lanthanide metal, preferably Na or ruthenium), followed by acidification as needed to form the herbicidal imidazolidinone ( IV). 14. The method of claim 13, comprising the steps of: (i-Ι) preparing by reacting an acid anhydride of formula (11) as claimed in claim 5 with an amine group (10) as claimed in claim 5; Or a compound of the formula (I), and (i-2) hydrolyzing the compound of the formula (1) thus obtained to give a guanamine compound of the formula (V) as claimed in Claim 2. 144469.doc 201021702 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: z 144469.doc