Title of Invention

ALPHA - BETA - AND BETA - GAMMA - UNSATURATED-CARBOXYLATES AND THEIR USE AS HERBICIDES

Abstract

The present invention disclose the alpha-substituted-carbonyloxy-alpha-beta-and/or beta-gamma-unsaturated-carboxylates and their use as herbicides. The said compounds are represented by formulas I and II: wherein R1 is (C1-C4)alkyl;R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is aryl, or substituted aryl; The configuration of the chiral carbon atom labeled “*” is R or S, or their mixture of various ratio. The compounds of this invention possess outstanding herbicidal activity, as well as better crop safety.

Full Text

FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION(See section 10 and rule 13) 1. ALPHA- BETA- AND BETA - GAMMA - UNSATURATED - CARBOXYLATES AND THEIR USE AS HERBICIDES. 2. (A) SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY. (B) P.R. China (C) 8 Shenliaodong Road, Tiexi District, Shenyang, Liaoning 110021 P.R. China. The following specification particularly describes the invention and the manner in which it is to be performed. 1 This invention belongs to the field of herbicide. More specifically, this invention involves in the alpha-beta-and beta-gamma-unsaturated-carboxylates and their use as herbicides. BACKGROUND OF THE INVENTION The search for the novel and improved herbicidal compounds is continually needed because of the factors such as the evolution of new weed species; the emergence and rapid development of the weed resistant to the existing herbicides; the awareness and emphasis on the environmental protection related to pesticides; the growing demand for more food production with the decrease of farmland and the increase of population; and the rapid development of agricultural technology as well as the improvement of farming system. Certain of alpha-beta-and beta-gamma-unsaturated-carboxylates are disclosed as agricultural herbicides (EP 149034 A2, US 6251829), but no alpha-substituted-carbonyloxy-alpha-beta-and beta-gamma-unsaturated-carboxylates claimed in present invention are disclosed. SUMMARY OF THE INVENTION The purpose of this invention is to provide novel alpha-beta-and beta-gamma-unsaturated-carboxylates and their use as herbicides. The technical program of this invention is as follows: The present invention provides to a kind of novel alpha-substituted-carbonyloxy-alpha-beta-and beta-gamma-unsaturated-carboxylates which are represented by formulas I and II: i ii 2 wherein Ri is (C1-C4)alkyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is one of the following groups: ■W jyy J&- «K>- - Ql Q2 Q3 Q4 Q5 The configuration of the chiral carbon atom labeled "*" is R or S, or their mixture of various ratio. The preferred compounds in this invention are the compounds of the formulas I and II as above mentioned, wherein R1 is (C1-C4)alkyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is Ql, Q2, Q3, Q4, or Q5; The configuration of the chiral carbon atom labeled "*" is R. Or the preferred compounds in this invention are the compounds of the formulas I and II as above mentioned, wherein R1 is methyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is Ql; The configuration of the chiral carbon atom labeled "*" is R or S, or their mixture of various ratio. Still more preferred compounds in this invention are the compounds of the formulas I and II as above mentioned, wherein R1 is methyl; 3 R.2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is Q l; The configuration of the chiral carbon atom labeled "*" is R. The most preferred compounds in this invention are the following two compounds: XV ^oV^o- XV tXyA O /^ wherein The configuration of the chiral carbon atom labeled "*" is R. In the formulas I and II as above mentioned, the term "alkyl" includes branched or straight chain alkyl groups, the term "alkenyl" refers to an ethylenically unsaturated hydrocarbon group, straight or branched, having 1 or 2 ethylenic bonds, for example propenyl, 2-propenyl, etc., the term "alkynyl" refers to an unsaturated hydrocarbon group, s straight or branched, having 1 or 2 acetylenic bonds, for example propinyl, propargyl, etc.. The compounds of the formulas I and II as above mentioned in the present invention can be prepared by the following processes: Scheme O-VH ~"■* ^o-y o-V^ ft 0^ . Q'°Y^ ft cr° u Y v 'k.^w^OH K^ o o III III-l III-2 I 4 II The starting material III, which is commercially available, in an appropriate solvent is reacted with alkaline aqueous solution at a certain temperature between -10 °C and the boiling point of the solvent for 30 minutes to 48 hours, and then acidified with hydrochloric acid or sulfuric acid, to yield intermediate acid, compound III-1. The appropriate solvent is selected from chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, tetrahydrofuran or dioxane, etc.. The base is chosen from NaOH, KOH, Na2CO3, K2C03, or NaHC03, etc.. The intermediate III-l is reacted with SOCI2, oxalyl chloride, or PCI3 in a suitable solvent, e.g., chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, tetrahydrofuran or dioxane, etc., to yield intermediate acid chloride III-2, in the presence of the organic bases such as Et3N, pyridine or DMF, etc. as catalyst at a certain temperature between -10 °C and the boiling point of the solvent for 30 minutes to 48 hours. The intermediate acid chloride III-2 is reacted with 3-methyl-2-oxobutyrate, which is commercially available, in a suitable solvent, to yield target I, at a certain temperature between -10 °C and the boiling point of the solvent for 30minutes to 48 hours. The suitable solvent is selected from chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetone, DMF, tetrahydrofuran or dioxane, etc.. The presence of the bases such as Et3N, pyridine, NaOH, KOH, Na2C03, K2CO3, NaHCO3, etc., is favorable to the reaction. The intermediate acid chloride III-2 is reacted with 2-hydroxy-3-methylbut-3-enoate, which is commercially available, to yield target II. The reaction conditions and the selections of solvent and base are the same as those of target I. Table 1: The examples of the representative compounds of formula I (The configuration of the chiral carbon atom labeled "*" is R) Compounds No. Q R1 R2 Physical property [a]D25 (c= 1, acetone) 5 1 Qi Methyl Ethyl Light yellow oil +7.98° 3 Q2 Methyl Ethyl Light yellow oil +10.75° 5 Q5 Methyl Ethyl Light yellow oil +6.66° Table 2: The examples of the representative compounds of formula II (The configuration of the chiral carbon atom labeled "*" is R) Compounds No. Q Ri R2 Physical property [a]D25 (c= 1, acetone) 2 Qi Methyl Ethyl Light yellow oil +18.84° 4 Q2 Methyl Ethyl Light yellow oil +24.62° 6 Q5 Methyl Ethyl Light yellow oil +20.33° The 1H NMR (CDCI3, 300 MHz) data of the compounds in tables 1 and 2 are shown as following. Compound No. 1: 8.675 (s, IH), 8.049 (d, IH), 7.634 (d, IH); 7.602 (dd, IH), 7.21-7.17 (m, 2H), 7.06-7.02 (m, 2H), 4.956 (q, IH), 4.202 (q, 2H), 2.220 (d, 3H), 1.788 (d, 3H), 1.709 (d, 3H), 1.261 (t, 3H); Compound No. 2: 8.661 (s, IH), 8.028 (d, IH), 7.666 (d, IH), 7.583 (dd, IH), 7.20-7.17 (m, 2H), 7.02-6.98 (m, 2H), 5.48-5.46 (m, IH), 5.23-5.20 (m, IH), 5.15-5.13 (m, IH), 4.92-4.88 (m, IH), 4.28-4.15 (m, 2H), 1.81-1.80 (m, 3H), 1.76-1.70 (m, 3H), 1.268 (t, 3H); Compound No. 3: 7.46-7.18 (m, 5H), 7.05-7.01 (m, 2H), 4.926 (q, IH), 4.196 (q, 2H), 2.208 (s, 3H), 1.766 (d, 3H), 1.701 (s, 3H), 1.261 (t, 3H); Compound No. 4: 7.44-7.39 (m, 2H), 7.35-7.29 (m, 2H), 7.27-7.22 (m, IH), 7.02-6.97 (m, 2H), 5.46-5.44 (m, IH), 5.22-5.19 (m, IH), 5.15-5.12 (m, IH), 4.88-4.85 (m, IH), 4.28-4.19 (m, 2H), 1.80-1.79 (m, 3H), 1.74-1.68 (m, 3H), 1.269 (t, 3H); Compound No. 5: 8.242 (d, IH), 7.967 (d, IH), 7.11-7.08 (m, 2H), 7.03-7.00 (m, 2H), 4.926 (q, IH), 4.196 (q, 2H), 2.209 (s, 3H), 1.767 (d, 3H), 1.688 (s, 3H), 1.261 (t, 3H) ; Compound No. 6: 8.250 (d, IH), 7.962 (d, IH), 7.10-7.06 (m, 2H), 7.00-6.96 (m, 2H), 5.46-5.44 (m, IH), 5.22-5.18 (m, IH), 5.15-5.12 (m, IH), 4.89-4.85 (m, IH), 4.26-4.18 (m, 2H), 1.189 (s, 3H), 1.74-1.69 (m, 3H), 1.269 (t, 3H). 6 The compounds of formulas I and II possess herbicidal activity, which can control many kinds of weeds in agriculture. For example, when used post emergence the compounds can control monocot weeds effectively. The present invention also includes the herbicidal compositions in which the compounds of formulas I and II are active ingredients. The concentration of active ingredient(s) in the compositions is from 1% to 99%. There are also agronomically acceptable carriers in these herbicidal compositions. The herbicidal compositions of the present invention can be used in the form of various formulations. Usually, the compound of the present invention, the active ingredient, is diluted with an inert liquid or solid carrier to make a formulation such as a wettable powder or an emulsifiable concentrate etc., so that it can be easily dispersed as a hebercide. Therefore, in these compositions, at least a liquid or solid carrier is added, and usually suitable surfactant to be added too. Also provided by this invention is the application method of controlling weeds, which is to apply the compositions of the present invention to the weeds above mentioned, the soil where the weeds above mentioned grow in, or the surface of the growth medium. The suitably effective dose of the compounds of the present invention is usually within a range of from 1 g/ha to 1 kg/ha, preferably from 10 g/ha to 500 g/ha. For some applications, one or more other herbicides can be added in the compositions of the present invention to make additional merits and effects. The compounds of the present invention can be used .alone, and aslo in combination with an insecticide, a fungicide, a plant growth controlling agent or a fertilizer, etc.. Thealpha-substituted-carbonyloxy-alpha-beta-andbeta-gamma-unsaturated-carboxylates of this invention possess outstanding herbicidal activity, as well as better crop safety compared with the existing herbicides. Especially they provide surprisingly satisfactory safety to the monocot crops. It shall be noted that variations and changes are permitted within the scopes of the present invention. DESCRIPTION OF THE INVENTION IN DETAIL I The following synthesis examples and results of biological tests are used to further illustrate the present invention, but not to limit it. 7 Synthesis examples The synthesis of the compound No. 1: 1. 0 O To a 500 mL flask Quizalofop-P-ethyl (30.00 g, 80.40 mmol, bought from Jiangshu Fengshan Group Co., Ltd., the configuration of the chiral carbon atom labeled "*" is R, so is the configuration of the following chiral carbon atom labeled "*") and tetrahydrofuran (80 mL) were added. After Quizalofop-P-ethyl was dissolved in tetrahydrofuran entirely through stirring, the solution of NaOH (3.26 g, 80.68 mmol) in water (80 mL) was added too. The reaction mixture was stirred at room temperature for 5 h, and then was extracted with EtOAc (100 mL). The aqueous layer was acidified with hydrochloric acid, the formed solid was collected by filtration. The intermediate acid (25.00 g) was dried and obtained as white solid. 2. CIXXNT TX\°H ~ CIXXNX XX0Jyc, o o To a 250 mL flask the intermediate acid (20.00 g, 58.00 mmol) obtained above and CH2CI2 (150 mL) were added, oxalyl chloride (11.00 g, 85.74 mmol) was added slowly with stirring, and then 3 drops of DMF was added. The reaction mixture was stirred at room temperature for 4h. After that, the intermediate acid chloride (23.00 g) was obtained as yellow oil after CH2CI2 and oxalyl chloride unreacted were removed at reduce pressure. 3. o ^^ Compound No. 1 8 To a 50 mL flask ethyl 3-methyl-2-oxobutyrate (0.47 g, 3.16 mmol), Et3N (0.35 g, 3.43 mmol), and CH2CI2 (5 mL) were added, and then the solution of the intermediate acid chloride (1.25 g, 3.40 mmol) obtained above in CH2CI2 (10 mL) were added dropwise with stirring with an ice water bath, which took approximately half an hour. The mixture was stirred at room temperature for 5 h. After that, EtOAc (100 mL) and water (20 mL) were added to the reaction mixture, the combined organic layer was washed in sequence with saturated NaHC03 aqueous solution (20 mL) and brine (20 mL), and dried over MgSO4.The combined organic solvent was removed at reduce pressure. The compound No. 1 (1.28 g) was obtained as light yellow oil after purified with column chromatography on silica gel (EtOAc:Petroleum ether =1:10). • The synthesis of the compound No. 2: Compound No. 2 To a 50 mL flask ethyl 2-hydroxy-3-methylbut-3-enoate (0.50 g, 3.30 mmol), Et3N (0.35 g, 3.43 mmol), and CH2CI2 (5 mL) were added, and then the solution of the intermediate acid chloride (1.26 g, 3.43 mmol) obtained above for the synthesis of the compound No. 1 in CH2CI2 (10 mL) were added dropwise, which took approximately half an hour. The mixture was stirred at room temperature for 5 h. After that, EtOAc (100 mL) and water (20 mL) were added to the reaction mixture, the EtOAc layer seperated was washed in sequence with saturated NaHC03 aqueous solution (20 mL) and brine (20 mL), and dried over MgSO4. The solvent was removed at reduce pressure. The compound No. 2 (1.41 g) was obtained as light yellow oil after purified with column chromatography on silica gel (EtOAc: Petroleum ether =1:10). The other compounds in Tables 1 and 2 could be prepared by similar procedures as mentioned above. Biological testing examples: According to the dose designed, the compound to Be evaluated was dissolved in acetone, and added into l% Toween 80 stand water solution to make a formulation with a 9 certain concentration. A moving belt plant sprayer (maufacturer: Engineer Research Ltd. of UK) was used for spraying (spraying pressure: 1.95kg/cm2; sprying volume: 50ml/m2; belt moving speed: 30cm/s; sprying nozzle: fan-shaped). For postemergence tests, the monocot weed seeds (barnyard grass, foxtail, and crabgrass) and crop seeds (rice, wheat, maize, and soybean)were planted in the growing containers of 100 cm2 size, covered with 1 cm soil and watered. The seeds were watered growed as standard procedure in greenhouse. At the stages of 1.5 leaf of weeds and 2-3 leaf of crops of rice, wheat, maize, and soybean, the test plants with uniform size and stage of development were selected, and treated with the formulation prepared previously. The l%oToween 80 stand water solution without testing compound was used as control. The treated plants were placed in a dry and windy place for drying. The plants were then returned to the greenhouse and growed as standard procedure. The test plants were watered from the bottom of the containers in 48h in order not to wash away the test formulation. Four weeks after application, the state of the plant was evaluated visually. The inhibition effect was the combination results of various damages such as green losing, withered spot, growth block or leaf burn, and which was obtained through comparison with control. Some of the test results are shown in Table 3. Table:3 Herbicidal activity the representative compounds of formulas I and II (postemergence, 40 g a.i./ha, inhibition %) Compounds No. Barnyard grass 1 100 2 100 3 90 4 85 5 80 6 95 The compound No.2 was tested for extended herbicidal spectrum and evaluating safety to crops compared with the commercial herbicide Quizalofop-P-ethyl, which was purchased from Jiangshu Fengshan Group Co., Ltd.. The results of this test were partly given in Table 4. 10 Table 4: The comparison of herbicidal activity and safety to crops between the compound No.2 and Quizalofop-P-ethyl (postemergence, 40 g a.i./ha, inhibition %) The tested Compound No.2 Quizalofop-P-ethyl Safety to crops (inhibition %) Herbicidal activity (inhibition %) Barnyard grass Foxtail Crabgrass Rice Wheat Maize Soybean Note 1: ": Not tested. 11 We Claim: 1. An alpha-substituted-carbonyloxy-alpha-beta-and beta-gamma-unsaturated-carboxylates comprised the characteristic structure indicated by formulas I and II: Q'°Y^i ?i 9 Q'°Y^I Ri o i II wherein R1 is (C1-C4)alkyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is one of the following groups: The configuration of the chiral carbon atom labeled "*" is R or S, or their mixture of various ratio. 2. The compound according to the claim 1, characterized in that wherein: Ri is (C1-C4)alkyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is Ql, Q2, Q3, Q4, or Q5; The configuration of the chiral carbon atom labeled "*" is R. 3. The compound according to the claim 1, characterized in that wherein: Ri is methyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is Q l; 12 The configuration of the chiral carbon atom labeled "*" is R or S, or their mixture of various ratio. 4. The compound according to the claim 3, characterized in that wherein: Ri is methyl; R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is Q l; The configuration of the chiral carbon atom labeled "*" is R. 5. The compounds according to the claim 4, characterized in that are the following two compounds: wherein The configuration of the chiral carbon atom labeled "*" is R. 6. Applying the compound according to the claim 1, characterized in that is used to control monocot weeds. 7. A herbicidal composition comprising the characteristic compounds of the claim 1 and an agronomically acceptable carrier, in which the concentration of active ingredient(s) is from l% to 99%. 8. A method for controlling weeds with the composition of the claim 7 characterized in that of applying a herbicidally effective amount of the composition of claim 7 to the weeds, and the growth medium or the soil where the weeds grow in. 13 9. An alpha - beta - and beta - gamma - unsaturated - carboxylates and their use as herbicides as claimed substantially as herein described with forgoing description. Dated this 14th Day of August 2007. 17 ABSTRACT The present invention disclose the alpha-substituted-carbonyloxy-alpha-beta-and/or beta-gamma-unsaturated-carboxylates and their use as herbicides. The said compounds are represented by formulas I and II: I ii wherein Ri is (C1-C4)alkyl;R2 is hydrogen, (C1-C6)alkyl, (C3-C6)alkenyl, or (C3-C6)alkynyl; Q is aryl, or substituted aryl; The configuration of the chiral carbon atom labeled "*" is R or S, or their mixture of various ratio. The compounds of this invention possess outstanding herbicidal activity, as well as better crop safety.

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