CN111072548A - 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-dione compounds and herbicidal activity - Google Patents

Abstract

The invention relates to herbicidal activity of 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-dione compounds. Wherein R is¹：CH₃、H；R²：CH₃、CH₂CH₃、CH₂＝CHCH₂；R³：H、Cl；R⁴：H、Cl；R⁵，R⁶：H、CH₃. The compound (I) has certain herbicidal activity on barnyard grass under the conditions of soil treatment and application rate of 187.5 g per hectare.

Description

2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-dione compounds and herbicidal activity

Technical Field

The invention relates to 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-diketone compounds and herbicidal activity.

Background

The triketone herbicide starts after the Jielikang company discovers that the broadleaf weed herbicide sulcotrione is removed after the seedling of the high-efficiency triketone corn field in 1982, the field is widely concerned, the research on the compound is greatly developed, a plurality of similar commercial varieties are applied, and the structural characteristics of the compound are as follows.

Wherein Ar is respectively substituted phenyl, substituted benzo heterocycle and the like, and the partial structure is as follows:

simple substituted benzene rings are successfully modified into benzo heterocyclic formyl cyclohexanedione derivatives, and a plurality of compounds with good herbicidal activity are found.

Although the former work describes different 2-benzoheterocycloyl-1, 3-cyclohexanediones, nothing is specifically said about the 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-dione compounds mentioned in this patent, and even more specifically about the herbicidal activity of these compounds.

Disclosure of Invention

The invention aims to provide a 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-diketone compound and a preparation method and application thereof. The compound of the invention has good herbicidal activity to barnyard grass.

The invention is a compound of the following general formula (I):

wherein the content of the first and second substances,

R¹：CH₃、H；

R²：CH₃、CH₂CH₃、CH₂＝CHCH₂；

R³：H、Cl；

R⁴：H、Cl；

R⁵：H、CH₃；

R⁶：H、CH₃。

the 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-diketone compound provided by the invention has an effect of preventing and removing weeds. The compounds of the present invention have herbicidal activity against barnyard grass at a dose of 187.5 g/ha.

Detailed Description

The essential features of the invention can be seen from the following examples, which should not be construed as limiting the invention in any way.

Example 1: synthesis of Compound I-1

40 mmoles of II (R)¹＝H；R²＝CH₃；R³＝H；R⁴＝Cl；R⁵＝H；R⁶H)40 mmol of triethylamine and 5 mmol of trimethylsilylcyanide in 50 ml of benzene, stirring and reacting at 50 ℃, tracking by thin layer chromatography until the reaction is finished, cooling to room temperature, washing with water and drying, and removing the solvent under reduced pressure to obtain the crude product of the target compound. The target compound is obtained through column chromatography, the yield is 66%, and the melting point is 128.6-130.4 ℃.

Example 2: synthesis of Compound I-5

40 mmoles of II (R)¹＝H；R²＝CH₂＝CHCH₂；R³＝H；R⁴＝Cl；R⁵＝H；R⁶H)20 mmol of triethylamine and 8 mmol of triazole, stirring in 40 ml of acetonitrile at room temperature for reaction, tracking by thin-layer chromatography until the reaction is finished, washing with water and drying, and removing the solvent under reduced pressure to obtain a crude product of the target compound. The target compound is obtained by column chromatography, the yield is 56 percent, and the melting point is 119.8-121.8 ℃.

Example 3: synthesis of Compound I-17

40 mmoles of II (R)¹＝H；R²＝CH₂＝CHCH₂；R³＝Cl；R⁴＝H；R⁵＝CH₃；R⁶＝CH₃) Stirring 30 mmol triethylamine and 15 mmol triazole in 30 ml diethyl ether at room temperature for reaction, tracking by thin layer chromatography until the reaction is finished, washing with water, drying, and removing solvent under reduced pressure to obtain crude product of the target compound. The yellow solid target compound is obtained by column chromatography, the yield is 63 percent, and the melting point is 241.9-243.9 ℃.

Example 4: synthesis of Compound I-22

40 mmoles of II (R)¹＝H；R²＝CH₂＝CHCH₂；R³＝Cl；R⁴＝H；R⁵＝H；R⁶H)40 mmol of triethylamine and 10 mmol of triazole, stirring in 50 ml of diethyl ether at room temperature for reaction, tracking by thin layer chromatography until the reaction is finished, washing with water and drying, and removing the solvent under reduced pressure to obtain a crude product of the target compound. The yellow solid target compound is obtained by column chromatography, the yield is 63 percent, and the melting point is 241.9-243.9 ℃.

Compound (I) was synthesized in a similar manner, with the physical parameters of the compound shown in table 1.

TABLE 1 physical Property parameters of Compound (I)

Example 4 Primary Screen assay for herbicidal Activity

Potting method (stem and leaf treatment): putting a certain amount of soil into a plastic small cup with the diameter of 8cm, adding a certain amount of water, covering soil with a certain thickness after sowing, culturing in a greenhouse, and covering seedlings with plastic before emergence. After emergence, a certain amount of clear water was added every day to maintain normal growth. When the seedling grows to a certain period, the stem and leaf spray treatment is carried out. The treatment dose was 187.5 g/ha. The results of the investigation after 21 days of treatment were measured for the fresh weight of the aerial parts, and the drug effect was expressed as the percentage of the fresh weight inhibition. The herbicidal activity data of compound (I) are shown in table 2.

Activity grading index: ++++: more than or equal to 80 percent; +++: 60-79%; ++: 40-59%; +: less than 39%.

Table 2: inhibition (%) of barnyard grass by the foliage treatment of Compound (I) (dose 187.5 g/ha)

Compound (I)	Inhibition rate	Compound (I)	Inhibition rate	Compound (I)	Inhibition rate
						I-1	++	I-9	+	I-17	+
I-2	+	I-10	+	I-18	++++
						I-3	+	I-11	+	I-19	++++
I-4	+	I-12	+	I-20	++++
						I-5	+	I-13	++++	I-21	++
I-6	+	I-14	++	I-22	+++
						I-7	+	I-15	++++	I-23	+
I-8	+	I-16	++

Claims (2)

1. A 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-dione compound, characterized in that it is a compound of general formula (I):

wherein the content of the first and second substances,

R¹：CH₃、H；

R²：CH₃、CH₂CH₃、CH₂＝CHCH₂；

R³：H、Cl；

R⁴：H、Cl；

R⁵：H、CH₃；

R⁶：H、CH₃。

2. use of 2- (2,3,4, 9-tetrahydro-1H-carbazole-6-carbonyl) cyclohexane-1, 3-diones as claimed in claim 1, characterized by herbicidal activity against barnyard grass.