CN1289494C - Esters compound of dibenzanthracene-1,3-dioxa-cyclooctane-2-amine carboxylic acid of possessing weeding activity - Google Patents
Esters compound of dibenzanthracene-1,3-dioxa-cyclooctane-2-amine carboxylic acid of possessing weeding activity Download PDFInfo
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- CN1289494C CN1289494C CN 200310119042 CN200310119042A CN1289494C CN 1289494 C CN1289494 C CN 1289494C CN 200310119042 CN200310119042 CN 200310119042 CN 200310119042 A CN200310119042 A CN 200310119042A CN 1289494 C CN1289494 C CN 1289494C
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- alkyl
- compound
- cyclooctane
- halo
- carboxylic acid
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention relates to an ester compound of dibenzanthracene-1, 3-dioxa-cyclooctane-2-amine carboxylic acid with weeding activity, which is shown as the general formula (I), wherein R1 is H, halogen, C1 to C4 alkyl or halogenating C1 to C4 alkyl; R2 and R3 are H, halogen, CN, NO2, CO2H, NH2, C1 to C4 alkyl, halogenating C1 to C4 alkyl, C1 to C4 alkoxyl groups, phenoxy groups, C1 to C4 alkylthio, C1 to C3 alkyl carbonyl, C1 to C3 carbalkoxy, C1 to C4 dialkyl amino groups or C1 to C4 alkyl sulfonyl; R4 and R5 are H, halogen, C1 to C4 alkyl or halogenating C1 to C5 alkyl; or R4 and R5 can form -CH2CH2- or -CH2CH2CH2-ring; R6 is H, C1 to C6 alkyl, or halogenating C1 to C6 alkyl; R7 is C1 to C10 alkyl, halogenating C1 to C10 alkyl, C3 to C10 cycloalkyl, C2 to C6 alkenyl or C3 to C6 alkynyl, m=0 to 4, and n=0 to 4.
Description
Technical field
The invention belongs to the weedicide field.
Background technology
Because weedicide or its composition are in use for some time, weeds can produce resistance to it, therefore, need constantly invention novel with improved herbicidal compound and composition.In addition, consider the factor of aspects such as energy economy ﹠ environment, the invention weedicide different with existing herbicide action mechanism also is very important.
Some dibenzo-1,3-two oxa-s-cyclooctane-2-carboxylic acid ester compound are as medicine (J.Medicinal Chemistry, 15,1273-1278 (1972)), and weedicide (US 4938790 and US 4976770) is existing to be reported.Chinese patent application CN1336371A discloses some and has had the dibenzo-1 of weeding activity, 3-two oxa-s-cyclooctane-2-oximino carboxylate compound.But in above-mentioned patent, do not see open as amine ester compound shown in the present.
Summary of the invention
The invention provides a kind of dibenzo-1 of novel structure, 3-two oxa-s-cyclooctane-2-carboxylic acid amine ester compound, shown in general formula (I):
Wherein:
R
1Be H, halogen, C
1-C
4Alkyl or halo C
1-C
4Alkyl;
R
2, R
3Be respectively H, halogen, CN, NO
2, CO
2H, NH
2, C
1-C
4Alkyl, halo C
1-C
4Alkyl, C
1-C
4Alkoxyl group, phenoxy group, C
1-C
4Alkylthio, C
1-C
3Alkyl-carbonyl, C
1-C
3Carbalkoxy, C
1-C
4Dialkyl amido or C
1-C
4Alkyl sulphonyl;
R
4, R
5Be respectively H, halogen, C
1-C
4Alkyl or halo C
1-C
5Alkyl; Or R
4, R
5Can form-CH
2CH
2-or-CH
2CH
2CH
2-ring;
R
6Be H, C
1-C
6Alkyl or halo C
1-C
6Alkyl;
R
7Be C
1-C
10Alkyl, halo C
1-C
10Alkyl, C
3-C
10Cycloalkyl, C
2-C
6Thiazolinyl or C
3-C
6Alkynyl;
m＝0-4；
n＝0-4。
Comparatively preferred compound is among the present invention:
R
1Be H;
R
2, R
3Be respectively H, halogen, C
1-C
4Alkyl, halo C
1-C
4Alkyl or C
1-C
4Alkoxyl group;
R
4, R
5Be respectively H, C
1-C
4Alkyl or halo C
1-C
5Alkyl; Or R
4, R
5Can form-CH
2CH
2-ring;
R
6Be H, C
1-C
6Alkyl or halo C
1-C
6Alkyl;
R
7Be C
1-C
10Alkyl, halo C
1-C
10Alkyl, C
3-C
10Cycloalkyl, C
2-C
6Thiazolinyl or C
3-C
6Alkynyl;
m＝0-4；
n＝0-4。
More preferred compound is among the present invention:
R
1, R
2, R
3Be H;
R
4, R
5Be respectively H or C
1-C
4Alkyl;
R
6Be H or C
1-C
6Alkyl;
R
7Be C
1-C
10Alkyl;
m＝1；
n＝1。
So-called alkyl is meant the straight or branched form, for example groups such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl.Cycloalkyl is meant and comprises the closed chain form, for example groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group.Alkylhalide group is meant the group that alkyl is replaced by one or more halogen atoms.
So-called thiazolinyl is meant the straight or branched form, the group of 1 to 2 carbon-carbon double bond is arranged, for example vinyl, propenyl, allyl group etc.
So-called alkynyl is meant the straight or branched form, and 1 to 2 carbon carbon triple-linked group, for example ethynyl, proyl, propargyl etc. are arranged.
So-called alkoxyl group is meant the straight or branched form, and end is connected with the group of Sauerstoffatom, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, tert-butoxy etc.
So-called alkylthio is meant the straight or branched form, and end is connected with the group of sulphur atom, for example methylthio group, ethylmercapto group etc.
So-called halogen is meant fluorine, chlorine, bromine, iodine.
General formula compound of the present invention (I) can be prepared by following method:
Fortified phenol (IV) (can be by buying on the market or can being made by currently known methods, referring to J.Org.Chem.USSR (Engl.Transl.), 11,1985,2403-2407) and α, α-dihalo carboxylic acid or its ester are dissolved in the The suitable solvent, chloroform for example, methylene dichloride, tetracol phenixin, normal hexane, benzene, toluene, ethyl acetate, DMF, THF, dioxane, ethanol or Virahol, and at alkali such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, cesium carbonate or sodium hydride exist down, and temperature is reacted down to boiling point and to be made acid, i.e. compound (III) in 0.5-100 hour for-10 ℃.
Compound (III) and SOCl
2, oxalyl chloride or PCl
3Be dissolved in The suitable solvent, chloroform for example, methylene dichloride, tetracol phenixin, normal hexane, benzene, toluene, ethyl acetate, THF, or dioxane, and at organic bases such as triethylamine, under pyridine or the DMF condition as catalyzer, temperature made acyl chlorides, i.e. compound (II) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.
Compound (II) and azanol (can by buying on the market) be in The suitable solvent, and temperature is reacted down to boiling point and to be made compound (I) in 0.5-48 hour for-10 ℃.Solvent can be chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.Add alkaloids, as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonates etc. are to reacting favourable.
The The compounds of this invention of table 1 part shown in general formula I
| Compound | R 4 | R 5 | R 6 | R 7 | mp(℃) |
| 1 | H | H | CH 3 | CH 3 | Oil |
| 2 | H | H | C 2H 5 | C 2H 5 | Oil |
| 3 | H | H | C 3H 7 | C 3H 7 | |
| 4 | H | H | CH 3 | C 2H 5 | |
| 5 | CH 3 | H | CH 3 | CH 3 | |
| 6 | CH 3 | H | C 2H 5 | C 2H 5 | |
| 7 | -CH 2CH 2- | CH 3 | CH 3 | ||
| 8 | -CH 2CH 2- | C 2H 5 | C 2H 5 | ||
Part of compounds in the table
1H NMR (CDCl
3) data are as follows:
Compound 1:
7.4-7.0(m，8H)，5.08(s，1H)，4.60(d，1H)，3.50(d，1H)，2.94(s，6H)
Compound 2:
7.5-7.0(m，8H)，5.15(s，1H)，4.62(d，1H)，3.50(d，1H)，3.10(q，4H)，1.28(t，6H)
General formula of the present invention (I) dibenzo-1,3-two oxa-s-cyclooctane-2-carboxylic acid amine ester cpds has weeding activity, uses behind Miao Qianmiao and can effectively control single broadleaf weed.
The present invention comprises that also with general formula (I) compound be the herbicidal composition of active ingredient.The weight percentage of active ingredient is between 1-99% in this herbicidal composition.Comprise also in this herbicidal composition that agricultural goes up acceptable carrier.
Compound of the present invention can preparation form be administered on soil or the blade face.This compound is dissolved in the carrier usually or is mixed with preparation so that be easier to disperse when using as weedicide.For example: these chemicals can be made into wettable powder or missible oil.In these compositions, add a kind of liquid or solid carrier at least, and when needing, can mix suitable tensio-active agent.
Other embodiments of the present invention are method of controlling weeds, and this method comprises herbicidal composition of the present invention is imposed on the surface of growth medium of the places of described weeds or described weeds or described weeds.Usually the comparatively suitable significant quantity of selecting is that per hectare 10 restrains 5000 grams, and preferred significant quantity is that per hectare 100 restrains 2000 grams.
Use for some, can in herbicidal composition of the present invention, add one or more other weedicide, can produce additional advantage and effect thus.
Compound of the present invention both can use separately also can be mixed together use with other known sterilant, sterilant, plant-growth regulator or fertilizer etc.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
The following example, living test are tested the result and be can be used to further specify the present invention, but do not mean that restriction the present invention.
Synthetic example
Synthesizing of compound 1:
Under the ice-water bath condition, oxalyl chloride (2.6 grams, 21 millis rub) is joined acid (A) (3.0 grams, 13 millis rub) and CH
2Cl
2In the mixture of (20 milliliters), drip a DMF then.After reaction mixture at room temperature stirs and spends the night, remove target compound (B) 3.2 grams that desolvate and obtain faint yellow solid by underpressure distillation.
Under the ice-water bath condition will on go on foot the CH that product (B) (0.2 gram) joins azanol (0.1 gram) and triethylamine (0.2 restrains)
2Cl
2In (10 milliliters) solution.Reaction soln at room temperature stirred 3 hours, evaporate to dryness, and residuum extracts with ethyl acetate (100 milliliters), organic layer water, 1%NaHCO
3Anhydrous MgSO is used in the aqueous solution and saturated common salt washing
4Dry.Obtain buttery 0.15 after the underpressure distillation and digest compound 1.
Other compounds in the table 1 can make by above similar method.
Give birth to and survey example
With the former medicine of acetone solution, by design dosage, join in the certain water gaging that contains tensio-active agent, make certain density preparation.Spray with mobile belt atomizer.The examination material is put in spraying rolling in the cupboard and is with, and mobile shower nozzle is sprayed onto medicament on the examination material with the covering of the fan Sprayable through examination material top, identical on nozzle and the common field spray device.Roll band and will try material and shift out outside the cupboard, place loft drier dry.
Test before the seedling: after planting carry out, test compound sparges soil surface, handles and is placed on the greenhouse, waters then; Test behind the seedling, seed germination also grew 10-21 days, made the examination material that has a series of growing stages before the processing, selected size, the consistent examination material of growing stage then, handled, and handled to be placed on the greenhouse and to water.The examination material with compound treatment does not compare.The examination material is broadleaf weed youth-and-old-age, piemarker and Cassia tora; Monocotyledon weed barnyard grass grass, dog tail and lady's-grass.
Examination material after the spraying drying places the greenhouse.Test is from the top water spray before the seedling, and test is poured water from the bottom and kept 48 hours so that water does not touch the blade face behind the seedling.
Handling the back investigated in 4 weeks.Inhibiting rate is total effect of various infringements such as chlorosis, withered spot, retarded growth or the calcination of leaf angle, obtains the result with blank after relatively.Partial test the results are shown in Table 2.
Table 2: the weeding activity of compound in the part general formula I
[before the seedling behind (1200 gram/hectare)/seedling (1200 gram/hectare)]
| Compound | The barnyard grass grass | The dog tail | Piemarker |
| 1 | 40/90 | 30/50 | 20/95 |
| 2 | 80/85 | 70/85 | 20/90 |
Claims (5)
1, a kind of dibenzo-1,3-two oxa-s-cyclooctane-2-carboxylic acid amine ester compound, shown in general formula (I):
Wherein:
R
1Be H;
R
2, R
3Be respectively H, halogen, C
1-C
4Alkyl, halo C
1-C
4Alkyl or C
1-C
4Alkoxyl group;
R
4, R
5Be respectively H, C
1-C
4Alkyl or halo C
1-C
5Alkyl; Or R
4, R
5Can form-CH
2CH
2-ring;
R
6Be H, C
1-C
6Alkyl or halo C
1-C
6Alkyl;
R
7Be C
1-C
10Alkyl, halo C
1-C
10Alkyl, C
3-C
10Cycloalkyl, C
2-C
6Thiazolinyl or C
3-C
6Alkynyl;
m＝0-4；
n＝0-4。
2, the compound shown in claim 1 is characterized in that, in the general formula (I):
R
1, R
2, R
3Be H;
R
4, R
5Be respectively H or C
1-C
4Alkyl;
R
6Be H or C
1-C
6Alkyl;
R
7Be C
1-C
10Alkyl;
m＝1；
n＝1。
3, the described compound of claim 1 is used to control the purposes of single broadleaf weed.
4, a kind of herbicidal composition is characterized in that: said composition comprises that described compound of claim 1 and agricultural go up acceptable carrier, and wherein the weight content of active ingredient is 1-99%.
5, a kind of control method for weed is characterized in that: this method comprises the herbicidal composition as claimed in claim 4 of using herbicidally effective amount on growth medium of these weeds or these weeds or place.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310119042 CN1289494C (en) | 2003-12-12 | 2003-12-12 | Esters compound of dibenzanthracene-1,3-dioxa-cyclooctane-2-amine carboxylic acid of possessing weeding activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310119042 CN1289494C (en) | 2003-12-12 | 2003-12-12 | Esters compound of dibenzanthracene-1,3-dioxa-cyclooctane-2-amine carboxylic acid of possessing weeding activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1626529A CN1626529A (en) | 2005-06-15 |
| CN1289494C true CN1289494C (en) | 2006-12-13 |
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ID=34761285
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310119042 Expired - Fee Related CN1289494C (en) | 2003-12-12 | 2003-12-12 | Esters compound of dibenzanthracene-1,3-dioxa-cyclooctane-2-amine carboxylic acid of possessing weeding activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1289494C (en) |
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2003
- 2003-12-12 CN CN 200310119042 patent/CN1289494C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1626529A (en) | 2005-06-15 |
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Effective date of registration: 20080711 Address after: F6-F12, middle block, Kai Chen World Trade Centre, 28 Fuxing Man Street, Xicheng District, Beijing, China. Zip code: 100031 Co-patentee after: Shenyang Institute of Chemical Engineering Patentee after: China Sinochem Group Corp Address before: No 8, Shen Liaodong Road, Tiexi District, Liaoning, Shenyang: 110021 Patentee before: Shenyang Institute of Chemical Engineering |
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Address after: 28, Fuxing Man Street, Xicheng District, Beijing, China. Zip code: 100031 Co-patentee after: Shenyang Research Institute of Chemical Industry Patentee after: China Sinochem Group Corp Address before: 28, Fuxing Man Street, Xicheng District, Beijing, China. Zip code: 100031 Co-patentee before: Shenyang Institute of Chemical Engineering Patentee before: China Sinochem Group Corp |
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Owner name: CHINA SINOCHEM CO., LTD. Free format text: FORMER OWNER: SINOPEC CORPORATION Effective date: 20100108 |
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Effective date of registration: 20100108 Address after: 28, Fuxing Man Street, Xicheng District, Beijing, China. Zip code: 100031 Co-patentee after: Shenyang Research Institute of Chemical Industry Patentee after: China sinochemical Limited by Share Ltd Address before: 28, Fuxing Man Street, Xicheng District, Beijing, China. Zip code: 100031 Co-patentee before: Shenyang Research Institute of Chemical Industry Patentee before: China Sinochem Group Corp |
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Granted publication date: 20061213 Termination date: 20131212 |