KR950004700B1 - N-substituted phengl-1,2,3,6-tetrahydropthalimide derivatives - Google Patents

Abstract

The carbonyl derivatives at m-position of phenyl of phenyl-1,2,3,6-tetrahydro phthal imide (I) for herbicide is prepared by (1) reacting alpha-carbonyl compounds and N-(2-fluoro-4-chloro- 5-hydroxyphenyl) -1,2,3,6-tetrahydro phthalimide (IV) from 1,2,3,6-tetrahydro phthalate and 2-fluoro- 4-chloro- 5-hydroxy aniline to get N-fluoro-4-chloro- 5-O-[1-(2,4-dichlorophenyl0 ethane-1-on-2-yl - 1,2,3,6-tetrahydro phthalimide (VI) which has carbonyl group, (2) reacting (VI) and hydroxyl amines to get (I). (I) as herbicide is useful for tomato, wheat, soybean, corn and rice.

Description

N-substituted phenyl-1,2,3,6-tetrahydro phthalimide derivative

The present invention provides a novel herbicidal N-substituted phenyl-1,2,3,6-tetrahydro phthalimide derivative of the general formula (I) and a method for preparing the same and using the compound as a herbicide or plant growth inhibitor It's about things.

[Formula 1]

Wherein R ¹ is phenyl or fluoro substituted by halogen of chloro, bromo or iodine, R ² is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ Haloalkenyl, C ₃ -C ₆ alkynyl, or C ₂ -C ₄ cyanoalkyl group.

N-substituted phenyl tetrahydro phthalimide derivatives have been reported to have herbicidal action. For example, US Pat. No. 4,736,068 discloses general formula (a).

[Formula 2]

It is reported that such substances have herbicidal action. Where X is chlorine or bromine, R ₄ is alkenyl, C ₃ ~C, a C ₃ ~C ₄ alkyl.

The present invention is similar to the general formula (a) (X is fixed with chlorine), but in particular, R has an oxime ether type chain rather than a simple carbon chain. Has selectivity.

Hereinafter, the present invention will be described in detail.

The present invention relates to a herbicidal N-substituted phenyl-1,2,3,6-tetrahydro phthalimide derivative represented by the general formula (I).

A particularly preferred compound in the general formula (Ⅰ) of the present invention is when R ¹ is a phenyl group substituted by a phenyl or chloro, R ² is hydrogen, an alkynyl group of ethyl, C ³ alkenyl, or C ³ of the.

Moreover, it is more preferable when it is a compound of the following general formula (I-a), (I-b), (I-c), or (I-d) specifically among the compound of the said general formula (I).

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

The novel compound of general formula (I) according to the present invention has excellent herbicidal activity and thus is useful as a herbicide or a plant growth inhibitor. A pesticide composition showing such a production or plant growth inhibitory effect may be prepared and used according to a conventional method. Can be.

On the other hand, looking at the method for producing a novel compound of the general formula (I) according to the present invention, can be prepared through the process of the following reaction formula (A). That is, by reacting 1,2,3,6-tetrahydro phthalic anhydride represented by the following general formula (II) with 2-fluoro-4-chloro-5-hydroxy aniline represented by the following general formula (III) Next, a compound of the following formula (IV) is prepared and then refluxed with an α-halocarbonyl compound of the following formula (V) under an inorganic base to prepare a compound represented by the following formula (VI), wherein By reacting the hydroxylamine hydrochloride to prepare a compound represented by the following general formula (VII) and then reacting the compound of the following general formula (VII) it is possible to obtain a new compound represented by the general formula (I).

Scheme 1

In the formulas, R ¹ and R ² are as defined in the general formula (I), respectively, and X represents chloro, bromo or iodine as leaving group.

According to the present invention, 1,2,3,6-tetrahydro phthalic anhydride of formula (II) and 2-fluoro-4-chloro-5-hydroxy aniline of formula (III) are used as glacial acetic acid as a solvent. Dissolve and reflux under anhydrous conditions for 5-7 hours and cool to room temperature. Pour this reaction solution into vigorously stirred cold water to obtain the target compound of the general formula (IV), and the compound and the α-halocarbonyl compound of the general formula (V) are prepared by using an inorganic base in an organic solvent. It is refluxed for about a time and separated by a conventional method to obtain the compound of formula (VI).

As the organic solvent, acetone, dimethylformamide, and the like are used, and acetone is usually used. As the base, alkali metals such as sodium and potassium carbonate are mainly used.

Subsequently, the compound of Formula (VI) and hydroxylamine hydrochloride are suspended in a mixed solvent of distilled water and a lower alcohol (usually ethyl alcohol), and then a base is added thereto, followed by reacting at room temperature for 2 to 24 hours. The alcohol solvent is blown off under reduced pressure, and then the reaction solution is diluted with cold water to obtain a solid, which is purified by a conventional method to obtain a novel intermediate compound of the general formula (VII).

Here, methyl alcohol or ethyl alcohol is used as the lower alcohol, and pyridine or alkali metal carbonate is used as the base.

Compound represented by the general formula (I) is obtained by the intermediate of the general formula (III) and the compound of the general formula (VII) having a suitable leaving group (X) with a base in an organic solvent for 3 to 18 hours Obtained by reflux. The organic solvent and base used at this time may use the same thing as mentioned above.

The novel compound represented by the general formula (I) according to the present invention has a strong herbicidal action.

In addition, there is a wide range of selectivity between crops and weeds, particularly useful for removing weeds during the cultivation of corn, soybean, cotton, wheat or sorghum, especially in pre-germination and post-germination treatments. Outstanding

In addition, it shows excellent herbicidal action and selectivity in freshwater conditions, especially the selectivity to the blood weed problem during rice cultivation is very useful for weed removal during rice cultivation.

Exemplary compounds of the general formula (I) according to the present invention as shown in Table 1 below.

[Formula 7]

TABLE 1

Hereinafter, the present invention will be described in detail based on the Examples according to the preparation of the representative compounds, but the present invention is not limited by the Examples.

Example 1

Preparation of N- (2-fluoro-4-chloro-5-hydroxyphenyl) -1,2,3,6-tetrahydro phthalimide (IV)

To 35 ml of glacial acetic acid of 1,2,3,6-tetrahydro phthalic anhydride (II) (4.68 g, 30 mmol) and 2-fluoro-4-chloro-5-hydroxy aniline (4.96 g, 30 mmol) for 7 hours It was refluxed. The reaction solution was cooled to room temperature and poured into 100 ml of cold water to obtain a light brown solid. The solid was separated by suction filtration, dried, and separated by a column packed with silica gel to obtain the desired product.

Yield: 8.5 g (93%)

m.p: 128-131 ° C

Mass spectrometry (EIMS, 70 eV) m / z 111 (50), 134 (100), 149 (39), 169 (39), 295 (M ⁺ , 10)

Example 2

Preparation of Phthalimide (VI, R ¹ = 2,4-Cl ₂ C ₆ H ₃ )

Compound (IV) synthesized in Example 1, N- (2-fluoro-4-chloro-5-hydroxyphenyl) -1,2,3,6-tetrahydro phthalimide (1.77 g, 6 mmol) And 2-bromo-2 ', 4'-dichloroacetophenone (1.60 g, 6 mmol) were dissolved in 30 ml of anhydrous acetone, and then 1.0 g of potassium iodide and anhydrous potassium carbonate (0.42 g, 6 mmol) were added and refluxed for 15 hours.

The reaction solution is poured into 150 ml of cold water and extracted with ethyl ether (2 x 100 ml).

The combined organic layers are washed once with cold water, dried over MgSO ₄ , and the solvent is blown off under reduced pressure. The oil thus obtained was separated by a column packed with silica gel to obtain a target product in the form of a yellow solid.

Yield: 1.01 g (35%)

Example 3

Preparation of phthalimide (VII, R ¹ = 2,4-Cl ₂ C ₆ H ₃ ) (Compound 1).

Compound 25 (VI, R ¹ = 2,4-Cl ₂ C ₆ H ₃ ) (1.01 g, 2.1 mmol) and hydroxyl amine hydrochloride (0.19 g, 2.73 mmol) synthesized in Example 2 was added to 25 ml of ethyl alcohol. After suspension, pyridine (0.22 g, 2.73 mmol) and 4-dimethyl aminopyridine (10 mg) were added as a catalyst, followed by stirring at room temperature for 5 hours.

The reaction was poured into cold water to give a solid, which was collected by suction filtration, and then dried to give the desired product as a pale yellow solid.

Yield: 0.95 g (91%)

m.p: 150 to 152 ° C

¹ H NMR (dimethylsulfoxide-d ₆ ) δ 1.75 (s, 4H), 5.26 (s, 2H), 7.27 to 7.70 (m, 5H), 12.08 (s, 1H)

Example 4

Preparation of Phthalimide (Compound 2).

Compound 1 and allyl bromide synthesized in Example 3 were synthesized according to a conventional method.

Yield: 94%

m.p: 109-111 ° C

¹ H NMR (Chloroform-d ₃ ) δ 1.80 (s, 4H), 2.40 (s, 4H), 4.50 to 4.75 (m, 5H), 5.00 to 5.50 (m, 2H), 5.25 (s, 2H), 5.80 -6.20 (m, 1H), 6.75-7.70 (m, 5H)

Example 5

Preparation of Phthalimide (Compound 3).

Compound 1 and chloro acetonitrile synthesized in Example 3 were synthesized according to a conventional method.

Yield: 90%

m.p: 96-99 ° C

¹ H NMR (chloroform-d ₃ ) δ 1.80 (s, 4H), 2.45 (s, 4H), 4.90 (s, 2H), 5.25 (s, 2H), 6.70 ~ 7.50 (m, 5H)

Example 6

Preparation of Phthalimide (Compound 2).

It synthesize | combined according to the conventional method using the compound 1 and iodoethane synthesize | combined in the said Example 3.

Yield: 92%

m.p: 38-41 ° C

¹ H NMR (chloroform-d ₃ ) δ 1.31 (t, J = 7.1 Hz, 3H), 1.80 (s, 4H), 2.40 (s, 4H), 4.26 (q, J = 7.1 Hz, 2H), 5.20 ( s, 2H), 6.70 to 7.40 (m, 5H)

Example 7

Preparation of Phthalimide (Compound 5).

Compound 1 and 2-chloropropionitrile synthesized in Example 3 were synthesized according to a conventional method.

Yield: 78%

m.p: 95-98 ° C

¹ H NMR (chloroform-d ₃ ) δ 1.73 (d, 3H), 1.82 (s, 4H), 2.44 (s, 4H), 5.06 (q, 1H), 5.23 (m, 2H), 6.63-7.46 ( m, 5H)

Example 8

Preparation of Phthalimide (Compound 6).

Using Compound 1 synthesized in Example 3 and propazyl bromide were synthesized according to a conventional method.

Yield: 95%

m.p: 154 to 156 ° C

¹ H NMR (Chloroform-d ₃ ) δ 1.84 (s, 4H), 2.44 (s, 4H), 2.50 (t, 1H), 4.80 (d, 2H), 5.20 (s, 2H), 6.75-7.40 (m , 5H)

Next, Examples 9-18 and the like were all synthesized in the same manner as in the previous examples.

Example 9

Preparation of Compound 7

m.p: 105 to 110 ° C

Mass spectrometry (EIMS, 70 eV) m / z 77 (65), 79 (62), 103 (100), 393 (70), 428 (M ⁺ , 2)

Example 10

Preparation of Compound 8

¹ H NMR (Chloroform-d ₃ ) δ 1.79 (s, 4H), 2.41 (s, 4H), 2.59 (s, 1H), 4.81 (s, 2H), 5.26 (s, 2H), 6.94 to 7.75 ( m, 7H)

Example 11

Preparation of Compound 9

¹ H NMR (chloroform-d ₃ ) δ 1.79 (s, 4H), 2.40 (s, 4H), 4.71 (m, 2H), 5.15-5.47 (m, 2H), 5.28 (s, 2H), 5.93-6.07 (m, 7H)

Example 12

Preparation of Compound 10

¹ H NMR (chloroform-d ₃ ) δ 1.75 (s, 4H), 2.37 (s, 4H), 5.31 (s, 2H), 7.33-7.73 (m, 6H), 12.14 (s, 1H)

Example 13

Preparation of Compound 11

¹ H NMR (Chloroform-d ₃ ) δ 1.29 (t, 3H), 1.80 (s, 4H), 2.40 (s, 4H), 4.25 (q, 2H), 5.20 (s, 2H), 6.60-8.10 (m , 6H)

Example 14

Preparation of Compound 12

m.p: 48-52 degreeC

¹ H NMR (chloroform-d ₃ ) δ 1.80 (s, 4H), 2.40 (s, 4H), 4.50-4.75 (m, 2H), 5.25 (s, 2H), 5.00-5.50 (m, 2H), 5.90 6.10 (m, 1H), 6.70 to 8.00 (m, 6H)

Example 15

Preparation of Compound 13

m.p: 66-70 ° C

¹ H NMR (Chloroform-d ₃ ) δ 1.80 (s, 4H), 2.40 (s, 4H), 4.90 (s, 2H), 5.20 (s, 2H), 6.70-7.80 (m, 6H)

Example 16

Preparation of Compound 14

m.p: 105 ~ 108 ℃

¹ H NMR (chloroform-d ₃ ) δ 1.80 (s, 4H), 2.42 (s, 4H), 2.55-3.15 (m, 1H), 4.80 (s, 2H), 5.20 (s, 2H), 6.70 ~ 7.70 (m, 6H)

Example 17

Preparation of Compound 15

¹ H NMR (chloroform-d ₃ ) δ 1.70 (d, 3H), 1.80 (s, 4H), 2.40 (s, 4H), 5.00-5.10 (q, 1H), 5.15-5.20 (m, 2H), 6.80 7.7 (m, 6H)

Example 18

Preparation of Compound 16

m.p: 118 to 120 ° C

¹ H NMR (chloroform-d ₃ ) δ 1.79 (s, 4H), 2.41 (s, 4H), 4.74 (s, 2H), 5.25 (s, 2H), 5.46 (s, 2H), 6.78-7.7.6 ( m, 6H)

In using the compound of this invention represented by the said General formula (I), it can be used as it is, or it can also be used in manufacturing forms, such as a hydrating agent, an emulsion, a granule, a liquid, or a powder. Solid carriers or liquid carriers can be used to make the preparations described below.

Solid carriers include inorganic powders (kaolin, bentonite, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, synthetic silicon hydroxide), and edible powders (soybean flour, flour, sawdust, tobacco powder). , Starch powder, crystalline cellulose), polymer materials (petroleum resin, vinyl chloride resin, ketone resin), alumina and beeswax can be used.

Liquid carriers include alcohols (methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, methylnaphthalene), halogenated hydrocarbons (chloroform, carbon tetrachloride, chlorobenzene), ethers (dioxane, tetrahydrofuran ), Ketones (acetone, methyl ethyl ketone, cyclohexanone), esters (ethyl acetate, butyl acetate, ethylene glycol acetate), amides (dimethylformamide), nitriles (acetonitrile), ether alcohols (ethylene glycol, Ethyl ether) and water.

Nonionic, anionic, cationic, or amphoteric substances may be used as the surfactant used in the emulsification or dispersion. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene oxypropylene resins, polyoxyethylene alkyl phosphates, fatty acid salts, alkyl sulfates, alkylsulfonates, alkylarylsulfonates , Alkyl phosphates, polyoxyethylene alkyl sulfates, quaternary ammonium salts and the like. However, the surfactants that can be used are not limited to these. If necessary, glue, casein, starch, agar, polyvinyl alcohol, lignin sulfonic acid may be used as a supplement.

When preparing as a herbicide, the content of the substance represented by the general formula (I) can be used in a weight ratio of about 1 to 95%, preferably 3 to 80% by weight.

The compound (I) may be used together with other kinds of preparations to improve the herbicidal effect, and in some cases, synergy may be expected.

Compound (I) may be used together with insecticides, nematicides, fungicides, plant growth regulators or fertilizers as necessary.

The dosage of the compound (I) depends on the type of compound, the type of crop, the treatment method and the like. Generally, the dosage is about 8 g to 1 kg per 3000 pyeong, preferably 15 g to 250 g.

The herbicidal activity evaluation of the novel compounds of the present invention as described above is illustrated in the following test examples.

Test Example: Biological Evaluation Test

The appropriate amount of fertilizer sterilized sandy loam mixed and then the test pot (field conditions: 348cm ^2, paddy conditions: 115cm ²⁾ and put on. The number of pots used at this time is 2 pots of field conditions and 1 pot of paddy conditions per compound. Then, as field crops and weeds, tomatoes (L. esculentum), wheat (T. aes tiuum), soybean (G. max), corn (z. Mays), orchard grass (D. glomerata), sesame (A. uridis), D. sanguinalis, R. japonicus, A. indica, P. hydropiper, C. japonica, S. bicolor, D. grass, S. viridis, Seeds or subterranean seeds of P. dichotomiflorum, S. nigrum, A. avicennae, X. thium, etc. in pots of field conditions and as crops and weeds sativa, E. oryzieola, C. difforis, M. vaginalis, S. juncoides, C. serotinus and S. olmi (S.) Seeds, such as pygmaea, are sown in pots of non-condition, and then poured into fine soil and placed in a greenhouse. The test compound (field condition: 14 mg / pot, paddy condition: 4 mg / pot) of 4 kg / ha level was dissolved using acetone as a solvent, and then the same amount was mixed with water to which a nonionic surfactant (Tween 20) was added. Spray 14 ml per pot for 4 ml per pot for non-conditioning. The amount used below 4kg / ha is diluted and sprayed in an appropriate amount according to the ratio.

Soil treatment before germination is treated with preparations on day 1 after sowing, and transverse transverse treatment on germination 9-14 days after sowing. After treatment, grow in the greenhouse for 2-3 weeks, and herbicide effect is investigated by morphology and physiological evidence. In other words, 0% means no herbicidal effect, 10-30% slightly herbicidal effect, 40-60% moderate effect, 70-90% severe effect, and 100% means full herbicidal effect.

The herbicidal effect before germination and the herbicidal effect after germination of the representative compounds of the general formula (I) of the present invention are as shown in Tables II and III.

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

Test Example 2: Freshwater Condition Test

The search for rice herbicides in freshwater conditions is O. sativa, E. oryzieola, tadpole, s. Juncoides, M. vaginalis, C. serotinus, Olme (S. pygmaea) and the like. The herbicide effect was searched 2 days after the treatment as in the case of dry herbicide search, and the results are summarized in Table IV.

TABLE 12

Claims (15)

N-substituted phenyl-1,2,3,6-tetrahydro phthalimide derivative represented by the following general formula (I). Wherein R ¹ is phenyl or fluoro substituted by halogen of chloro, bromo or iodine, R ² is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ Haloalkenyl, C ₃ -C ₆ alkynyl, or C ₂ -C ₄ cyanoalkyl group. The compound according to claim 1, wherein R ¹ is phenyl or phenyl substituted with chloro. The compound of claim 2, wherein R ² is hydrogen, ethyl, C ₃ alkenyl or C ₃ alkynyl group. The compound of claim 1, wherein the general formula (I) is represented by the following general formula (I-a). The compound according to claim 1, wherein the general formula (I) is represented by the following general formula (I-b). The compound of claim 1, wherein the general formula (I) is represented by the following general formula (I-c). The compound according to claim 3, wherein the general formula (I) is represented by the following general formula (I-d). A herbicide containing N-substituted phenyl-1,2,3,6-tetrahydro phthalimide derivative represented by the following general formula (I) as an active ingredient. Wherein R ¹ and R ² are each as defined in formula (I) of claim 1 above. The herbicide according to claim 8, which is used in corn, soybean, cotton, wheat, sorghum in pre-germination treatment. 10. The herbicide of Claim 9 used in corn cultivation. The herbicide according to claim 8, which is used in corn, soybean, cotton, wheat, sorghum in post-germination treatment. The herbicide according to claim 11, which is used in corn cultivation. The herbicide of Claim 8 used in fresh water conditions. The herbicide according to claim 13, which is used for selective control of blood in rice cultivation. To prepare a compound represented by the general formula (VI), wherein the hydroxylamine hydrochloride is reacted to produce a compound represented by the following general formula (VII), and then react the compound of the following general formula (VII) A method for producing an N-substituted phenyl-1,2,3,6-tetrahydro phthalimide derivative represented by (I). In the formulas, R ¹ and R ² are as defined in general formula (I) of claim 1, respectively, and X represents chloro, bromo or iodine as leaving group.