CN1060480C - Substituted phenoxyl acetyloxy hydrocarbyl phosphonate with phytocidal activity and its preparation - Google Patents
Substituted phenoxyl acetyloxy hydrocarbyl phosphonate with phytocidal activity and its preparation Download PDFInfo
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Abstract
The present invention relates to substituted phenoxyl acetoxy hydrocarbyl phosphonate ester (phosphonate) which has the general formula disclosed in the specification and has weed removal activity. In the formula, R<1> and R<2> represent alkoxyl with C1 to C3, OH or OM(M is Na, K, NH4, etc.) and are identical or different; R<3> represents heterocyclic radicals such as H, alkyl with C1 to C4, substituted alkyl, substituted phenyl (the substituting group is halogen, NO2, CH3 or OCH3), furyl, etc.; R<4> represents H or alkyl with C1 to C4; X and Y represent H, Cl, Br, NO2 or CH3 and are identical or different. The compound has an obvious inhibiting effect on the growth of single-cotyledon plants or dicotyledonous plants, and the compound can be used as herbicide; parts of the compounds also have a growth regulation function to plants.
Description
The present invention relates to have the substituted phenoxyl acetyloxy hydrocarbyl phosphonate of weeding activity or salt compound and preparation method thereof, and it is as the biological activity of weedicide, plant-growth regulator.
Because it is simple that the phosphorus agent has preparation, the characteristics that raw material is easy to get, after phosphonic acid based weedicide commercializations such as glyphosate, two propylamine phosphines, have many again about the report of phosphonate derivative as weedicide, the following compd A that contains phosphonate bond and carboxylic acid ester bond was once disclosed as German Patent Ger offen 3702921 (1988), Tarasova, RT and Boxhkova, N etc. have also reported carbamoyloxy alkyl phosphonate compounds (Zh such as Tarasova R.T respectively, obsheh, khim, 1,981 51 (11) 2413-17; Borhkona.N etc., Toxicol Bavivon, chem1989,20-21,267-71), these phosphonate derivatives all can be used as weedicide or plant-growth regulator is used for the farmland.
The inventor also has been developed into following a few phosphonate derivative, category-B (Central China Normal University's journal 1996,30 (1) 53-57 such as Xu Liang, He Hongwu in recent years; Hubei chemical industry 1996 supplementary issue P47-49), C class (SCI 1996 Vol17 such as Hu Limin He Hong force, No12 P1869-1873), D class (chemical reagent 1996 such as He Hongwu, 18 (2) 70-72), E class (Central China Normal University's journal 19994,28 (1) P71-76 such as He Hongwu; And find that they are all showing weeding activity or plant growth regulating activity preferably in varying degrees applied chemistry 1994,11 (4) P21-24).
When X, Y are 2-Cl, 4-Cl, then R is H, Me (methyl), Et (ethyl), Pr (propyl group), Ph (phenyl)
X, Y are H, 4-Cl, and then R is H, Me, Et, Pr, Ph, CCl
3
X, Y are H, 4-methyl, and R is CCl
3
The objective of the invention is to explore the better compound of weeding activity, provide a class to have weeding activity and with the novel phosphonate ester derivative and the synthetic method of plant growth regulating activity.
The present invention is on above-mentioned E compounds research basis, enlarge the structural pattern of above-claimed cpd, proposed a class and E class and different novel phosphonate derivative-substituted phenoxyl acetyloxy hydrocarbyl phosphonate or the salt of above-mentioned existing classes of compounds structure, its general structure is as follows
In the formula: R
1, R
2Show not C
1-C
3Alkoxyl group, OH, ONa, OK, ONH
4Group
R
1With R
2It is identical or inequality,
R
3Expression H, C
1-C
4Alkyl or CCl
3, phenyl, substituting group are halogen, NO
2, CH
3, OCH
3Substituted-phenyl, furyl,
R
4Expression H, C
1-C
4Alkyl,
X, Y represent H, Cl, Br, NO
2, CH
3, its X is identical with Y or inequality,
But the qualifications of logical formula I is as follows:
R in logical formula I
1, R
2Be oxyethyl group, R
4During for H,
If X, Y are 2-Cl, 4-Cl, then R
3Be CCl
3, substituting group is halogen, NO
2, CH
3, OCH
3Substituted-phenyl, furyl,
If X, Y are H, 4-Cl, then R
3For substituting group is halogen, NO
2, CH
3, OCH
3Substituted-phenyl,
If X, Y are H, 4-methyl, then R
3Be to remove CCl
3The structural changes scope of above-mentioned defined in addition.
Having the range of structures of the logical formula I compound of the present invention and the constitutional features difference of above-mentioned E compounds is: the E compounds has only been represented and has been worked as R
1, R
2Be oxyethyl group, R
4During for hydrogen atom, X, Y are 2,4-dichloro, R
3The expression hydrogen atom, methyl, ethyl, propyl group, phenyl, when X, Y are 4-chlorine, hydrogen atom, R
3Be hydrogen atom, methyl, ethyl, propyl group, phenyl, trichloromethyl, when X, Y are 4-four bases, hydrogen atom, R
3Be 12 compounds of trichloromethyl, and on behalf of its structure, general structure proposed by the invention (I) be different from the novel phosphonate derivative of the compound of above-mentioned E class.
The compound that belongs to formula I of the present invention comprises with the represented substituted phenoxyl acetyloxy hydrocarbyl phosphonate of following general formula (I-1), with the substituted phenoxy acetoxyl alkyl phosphonic acids of general formula (I-2) expression, with the substituted phenoxy acetoxyl alkyl of general formula (I-3) expression
(1-1), R, R in (1-2), (1-3) formula
5Be C
1-C
3Alkyl, R and R
5Identical or inequality, R
3, R
4, in X, Y and the formula I definition identical, M is Na, K, NH
4
The compound of above-mentioned formula I provided by the invention has remarkable restraining effect to unifacial leaf or dicotyledons growth, thereby can be used as the effective ingredient of weedicide.
The compound that formula I is represented has the growth regulating effect to plant, can be used as the effective ingredient of plant-growth regulator.
With the preparation method of the substituted phenoxyl acetyloxy hydrocarbyl phosphonate of general formula (I-1) expression, be to make the logical represented compound of formula II
The compound represented with following logical formula III
React (A method)
In (II), (III), (I-1) formula, R and R
5Be C
1-C
3Alkyl, R and R
5Identical or inequality, R
3, R
4, in X, Y and the formula I definition identical.
Alpha-hydroxy alkyl phosphonate (II) is 1: 1～1.1 mol ratios with the reaction ratio of aroyl acetyl chlorine (III) in the above-mentioned reaction, reaction solvent adopts multiple organic solvents such as chloroform, methylene dichloride, ethylene dichloride, benzene, acetone, ethyl acetate, in the presence of basic catalyst pyridine or tertiary amine, 0 ℃-80 ℃ reactions 6-8 hour, can obtain yield preferably.
The preparation method of the substituted benzene oxygen acetoxy phosphine alkyl acid esters that general formula (I-1) is represented utilizes logical represented compound and the represented compound (R in the formula of following logical formula IV of formula II
4With defined identical in the logical formula I) react, obtain the compound of general formula, R and R in (V) formula for (V)
5Be C
1-C
3Alkyl, R and R
5Can be identical or inequality, R
3, R
4Identical with definition in the formula I, react with compound (defined identical in X, Y and the logical formula I in the formula, M is Na, K) that logical formula VI is represented again and prepare (B method)
During this law (B method) preparation (I-1) compound, Alpha-hydroxy phosphonic acid ester (II) and chloroacetyl chloride (IV), in the presence of organic solvent, adopting weak organic bases is acid binding agent, 0 ℃-50 ℃ reactions 2-5 hour, can be converted into alpha-chloro acetoxyl alkyl phosphonic acid ester (V) smoothly, its yield＞90%.Organic solvent can adopt multiple organic solvents such as chloroform, methylene dichloride, ethylene dichloride, ethyl acetate, acid binding agent adopts tertiary amine or pyridine usually, during by (V) and phenol (salt) (VI) prepared in reaction target compound (I-1), reactant ratio such as uses excessive slightly at mol ratio or phenol.In various polarity organic solvents such as acetone, dimethyl formamide, ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, at K
2CO
3Or react under the existence of mineral alkalis such as NaOH, KOH.If adding catalyzer such as the KI of 0.5～1.0 mmole or ammonium salt can achieve good results.
Substituted phenoxy acetoxyl alkyl phosphinic acid compounds general formula in the logical represented compound of formula I is preparation method's (C method) of (I-2), the dialkyl substituted phenoxyl acetyloxy hydrocarbyl phosphonate of representing for (I-1) with the general formula of preceding method system of OO-is a raw material, at reagent (CH
3)
3SiI or (CH
3)
3Under the effect of SiBr, be converted into corresponding OO-two (trimethyl silicon based) phosphonic acid ester earlier, further alcoholysis generates corresponding substituted phenoxy acetoxyl alkyl phosphonic acids again
R in the formula
3, R
4, in X, Y and the logical formula I definition identical.
When adopting this law (C method) preparation (I-2) compound, various polarity organic solvents such as solvent employing acetone in intermediate (VI) preparation feedback or ethyl acetate, acetonitrile, dimethyl formamide, temperature of reaction is 0 ℃～80 ℃, and is better in the time of 10～40 ℃, compound (I-1) and (CH
3)
3SiI or (CH
3)
3The reaction ratio of SiBr is 1: 1～2.5 mol ratios, reaction times is 1-2.5 hour, slough solvent after having reacted, can obtain intermediate (VI), again (VI) behind the precipitation is dissolved in methyl alcohol or ethanol, the propyl alcohol, after stirring 0.5～1.0 hour under≤40 ℃, backflow 1-3 hour, can obtain the crude product of (I-2), handle purifying more according to a conventional method and can obtain (I-2) pure product.
Substituted phenoxy acetoxyl alkyl phosphonate in the logical represented compound of formula I of the present invention is with preparation method's (D method) of the compound of general formula (I-3) expression.Substituted phenoxy acetoxyl alkyl phosphonic acids with general formula (I-2) expression of preceding method preparation, in the presence of salt of wormwood or yellow soda ash, sodium hydroxide, potassium hydroxide, sodium alkoxide, ammonia and various amine, can select that one or more organic solvents are reaction solvent in benzene, acetone, ethyl acetate, the hydrochloric ether, reacted 0.5-2.5 hour in room temperature or reflux conditions, just can obtain corresponding salt, compound in the reaction (I-2) is 1: 1～2.5 mol ratios with the proportioning of alkali.
R in the formula
3, R
4, X, Y be identical with the definition in the logical formula I.
Be described more specifically the compound of (I) of the present invention formula below by embodiment, and the preparation method of compound in (I-1), (I-2), (I-3) formula, only the present invention will be described for these embodiment, rather than limit the invention.
Embodiment 1
O with 0.01 mole, O-dimethyl-Alpha-hydroxy methylphosphonate is dissolved in 10 milliliters of chloroforms, add 0.8 milliliter of triethylamine again,, add 0.011 mole 2 below 15 ℃, 10 milliliters of chloroformic solutions of 4-Dichlorophenoxy Acetyl Chloride 98Min., stirring reaction is 4 hours in the time of 35 ℃, and then is raised to 50 ℃ of reactions 2 hours, adopts 1%NaOH solution, saturated NaCl solution that reaction solution is washed 2-3 time after having reacted respectively, tell organic layer, use anhydrous Na
2SO
4Drying, precipitation, it is that developing agent carries out Thin-layer separation that crude product adopts ethyl acetate and sherwood oil, gets yellow oily liquid, yield＞75.8% behind the purifying.n
20=1.5448 ultimate analyses: measured value C%38.14%H%3.65%
Calculated value C%38.49%H%3.79%
IR(cm
-1)：3020(γPh-H)1760(C=O) 1220(P=O)
1180(C-O) 1050(P-O-C) 810(C-Cl)
1HNMR(δppm)3．8-3．9(d6H，20CH3)，4．3(d，2H，-CH2P)
4．75(S，2H，-OCH2)，6．8-7．5(m，3H，-C6H3)
Embodiment 2
O with 0.01 mole, O-dimethyl-Alpha-hydroxy is dissolved in 10 milliliters of ethyl acetate the methyl-benzyl phosphonic acid ester, add 0.8 milliliter of pyridine again,, add 0.01 mole 2 below 20 ℃, 10 milliliters of ethyl acetate solutions of 4-Dichlorophenoxy Acetyl Chloride 98Min., 40 ℃ of stirring reactions 5 hours, and then be warmed up to 60 ℃ of reactions after 2 hours, adopt the method for example 1 to handle, get yellow oily liquid behind the purifying, yield is 59.2%.n
D 20=1.5929 ultimate analysis measured value C% 50.02% H% 4.50%
Calculated value C% 49.89% H% 4.38%
IR(cm
-1)：3018(Ph-H) 1750(C=O) 1262(P=O)
1189(C-0) 1036(P-0-C) 804(C-Cl)
1HNMR(δppm)2．3(S，3H，-CH3)，3．62-3．85(d，6H，20CH3)
4．7(S，2H，-OCH2-)，5．0，6．2(d，1 H，-CHP-)
6．77-7．42(m，7H，C6H4+C6H3)
Embodiment 3
O with 0.01 mole, O-di-Alpha-hydroxy ethyl phosphonate is dissolved in 20 milliliters of ethylene dichloride, add 0.8 milliliter of triethylamine again, under 20 ℃, add 0.011 mole 2,20 milliliters of dichloroethane solutions of 4-dichlorophenoxy propionyl chloride, stirring reaction is 4 hours in the time of 45 ℃, reacts 2 hours in the time of 55 ℃ then, by embodiment 1 same post processing mode reaction solution is carried out aftertreatment again, get pale yellow oily liquid body, n after the separation and purification
D 20=1.4783, its yield is 60%.
IR(cm
-1)：3074(Ph-H) 1763(C=O) 1244(P=O)
1103(C-O) 1060(P-O-C) 819(C-Cl)
738(P-C)
1HNMR(δppm) 0．95(t，6H，2CH3)1．44(m，3H，CH3)
1．38(m，4H，2CH2) 1．67(d，3H，CH3)
3．98(m，4H，2OCH2) 4．75(m，1H，OCH)
5．29(m，1H，CHP) 6，6-7．4(m，3H，C6H3)
MS(m／z)：426(M
+)
Embodiment 4
O with 0.01 mole, O-dimethyl-Alpha-hydroxy butyl phosphine acid esters is dissolved in 15 milliliters of ethyl acetate, the Trimethylamine 99 that adds 0.8 milliliter again is at 15 milliliters of ethyl acetate solutions that add 0.01 mole of 2-(2,4 dichloro benzene oxygen base) propionyl chloride below 15 ℃, 40 ℃ of stirring reactions 4.5 hours, and then be raised to 50 ℃ the reaction 2.5 hours, by embodiment 1 same post processing mode reaction solution is carried out aftertreatment then, separation and purification just pure product, be the pale yellow oily liquid body, yield is 68%.n
20=1．4896
1HNMR(δppm)0．95(t，3H，CH3)，1．50(m，4H，CH2CH2)
1．68(d，3H，CH3)3．71(m，6H，2OCH3)
4．78(q，1H，OCH)，5．28(q，1H，CHP)
6．6-7．6(m，3H，C6H3)；
IR(cm
-1)：3068(Ph-H) 1763(C=O) 1262(P=O)
1098(C-O) 1032(P-O-C) 821(C-Cl)
738(P-C)
MS(m／z)：398(M
+)
Embodiment 5
With 0.01 mole O, a pair of benzyl chloride base of O-diethyl-Alpha-hydroxy phosphonic acid ester is dissolved in 15 milliliters of CHCl
2, add 0.011 mole pyridine again, at 5 milliliters of CH that drip 0.011 mole of chloroacetyl chloride below 15 ℃
2Cl
2Solution, reaction is 1 hour under this temperature, places at normal temperatures and spends the night, and washes reaction solution with water, the organic phase anhydrous Na
2SO
4Dry precipitation obtains
With the 0.01 mole of O that makes, the O-diethyl-α-a pair of benzyl chloride base of chloroethene acyloxy phosphonic acid ester is dissolved in 30 milliliters of acetone, adds 0.11 mole 2,4 dichloro phenol and 0.006 mole K
2CO
3Solid, the KI that adds catalytic amount again refluxed 2 hours, and cooling adopts the method for example 1 to handle, and will be yellow oily liquid behind the product purification, and yield is 57%.n
20=1.5065 ultimate analysis measured value C% 47.54% H% 4.35%
Calculated value C% 47.37% H% 4.16%
IR(cm
-1)：3073(Ph-H) 1774(C=O) 1259(P=O)
1175(C-O) 1025(P-O-C) 804(C-C1)
1HNMR(δppm)1．25-1．4(m，6H，2CH3)，3．9-4．2(m，4H，2OCH3)
4．8(S，2H，-OCH2)，6．7(d，1H，-CHP)
6．8-7．5(m，7H，C6H4，C6H3)
Embodiment 6
O with 0.02 mole, O-diethyl-Alpha-hydroxy-benzylphosphonic acid ester is dissolved in 15 milliliters of chloroforms, the Trimethylamine 99 that adds 0.022 mole again, at 5 milliliters of chloroformic solutions that drip 0.022 mole of chloroacetyl chloride below 20 ℃, reaction is 1 hour under this temperature, places at normal temperatures and spends the night, pressing the method for embodiment 5 again handles, can obtain O, the crude product of O-diethyl-alpha-chloro acetoxyl group benzylphosphonic acid ester, yield 85%.
0.01 mole of the above-mentioned crude product that makes is dissolved in 30 milliliters of acetone, adds 0.11 mole 4-chlorophenol sodium salt, refluxed 2.5 hours, cooling adopts the method for embodiment 1 to handle, and is yellow oily liquid behind the product purification, and yield is 65%, n
20=1.5934 ultimate analysis measured value C% 51.22% H% 4.60%
Calculated value C% 51.02% H% 4.70%
IR(cm
-1)：3017(Ph-H) 2778(C-H) (R) 1773(C=O)
1258(P=O) 1170(C-O) 1023(P-O-C)
755(C-C1) 738(P-C)
1HNMR(δppm)1．3(m，6H，2CH3)，4．0(m，4H，2OCH3)
4．7(S，2H，-OCH2CO)，6．2(d，1H，OCHP)
6．8-7．3(m，8H，2C6H4)
Embodiment 7
Method by embodiment 5 makes O earlier, O-diethyl-alpha-chloro acetoxyl group p-chlorobenzyl phosphonic acid ester, this compound of 0.01 mole that will make again is dissolved in 30 milliliters of acetone, the Na2CO3 solid that adds 0.11 mole of p-NP and 0.006 mole, the KI that adds 0.5 mmole again refluxed 2.5 hours, and cooling is pressed the method for embodiment 1 and handled, be the yellowish brown oily liquids behind its product purification, yield is 60%.
n
D 20=1．5490 M．S：(m／z)：457M
+
IR(cm
-1)：3018(Ph-H) 3000(C-H)R 1761(C=O)
1225(P=O) 1178(C-O) 1022(P-O-C)
804(C-C1) 721(P-C) 1350(Ph-NO2)
1HNMR(δppm)1．3(m，6H，2CH3)，4．1(m，4H，2OCH2)
4．8(S，2H，-OCH2CO)，6．2(d，1H，OCHP)
6．9-7．4(m，8H，2C6H4)
Embodiment 8
Method by embodiment 1 makes O earlier, O-dimethyl-2,4-Dichlorophenoxy acetoxy-methyl phosphonic acid ester, then stir and 10 ℃ condition under, in being dissolved with 25 milliliters of CH3CN solution of 0.035 mole of this compound, add 40 milliliters of CH3CN that are dissolved in 0.07 mole of Me3SiI, insulation reaction is after 1 hour in the time of 10 ℃, CH3CN is removed in underpressure distillation, can obtain brown oily liquids, again this brown oily liquids is dissolved in 50 ml methanol, at room temperature stirred 0.5 hour, refluxed then 1 hour, remove methyl alcohol through underpressure distillation, obtain colourless dope, (eluent: propyl alcohol: sherwood oil 2: 5) just can obtain target product, yield is 51% after chromatographic separation.
Ultimate analysis: measured value C% 34.1% H% 2.65%
C％ 34．32％ H％ 2．85％
IR(cm
-1)：3360(Ph-H) 2976(R-H) 2120～2384，
2644～2788(P-OH) 1762(C=O) 1204(P=O)
1582，1476(C=C) 1180(C-O) 1050(P-O-C)
1HNMR(δppm) 4．65(s，2H，OCH2)，4．35(d，2H，-CH2P)
6．68-7．50(m，3H，-C6H3) 9．0-10．0(s，2H，2OH)
Embodiment 9
Method by embodiment 1 makes O earlier, O-dimethyl-2,4-Dichlorophenoxy acetoxyl group ethyl phosphonate, again this compound of 0.035 mole is dissolved in 25 milliliters of ethyl acetate solutions, in the time of 15 ℃, add 40 milliliters the ethyl acetate that is dissolved with 0.07 mole of Me3SiBr, insulation reaction was sloughed ethyl acetate after 1.5 hours in the time of 15 ℃, can obtain the oily liquids of light brown, again this brown oily liquids is dissolved in 50 ml methanol, at room temperature stirred 45 minutes, refluxed then 1 hour, remove methyl alcohol through underpressure distillation, obtain colourless dope, (eluent: propyl alcohol: sherwood oil 2: 5) just can obtain target product, yield is 65% after chromatographic separation.Ultimate analysis: measured value C% 36.40% H% 3.44% C% 36.51% H% 3.34%IR (cm
-1): 3360 (Ph-H) 2926 (R-H) 1762 (C=O)
1204(P=O) 1582，1476(C=C)
2120～2384，2644～2788(P-OH)
1HNMR(δppm) 1．36-1．64(m，3H，CH3) 4．62(s，2H，OCH2)
5．16-5．48(m，H，-PCH) 6．68-7．40(m，3H，C6H3-)
9．0-10．0(s，2H，2OH)
Embodiment 10
Add the K2CO3 of 20 milliliters of ethyl acetate and 0.04 mole in the product (0.02 mole) that the foregoing description 9 is obtained, left standstill after the stirring 24 hours, suction filtration is white crystals with the solid that obtains with the dehydrated alcohol recrystallization, can obtain corresponding phosphonic acids sylvite
Adopt above-mentioned similar method, can prepare other compound equally, see Table 1, listedly in the table 1 be synthetic part of compounds of the present invention
The implication of ellipsis in the table: Me-methyl Et-ethyl Pr-propyl group Ph-phenyl Bu-butyl
Furyl-furyl n-pr-n-propyl n-Bu-normal-butyl
P-Meph-p-methylphenyl p-Clph-rubigan
Bromophenyl between o-Clph-Chloro-O-Phenyl m-Brph-
| NO R 1 R 2 R 3 R 4 X Y |
| 1 OMe OMe H H 2-Cl 4-Cl 2 OMe OMe Me H 2-Cl 4-Cl 3 OMe OMe Et H 2-Cl 4-Cl 4 OMe OMe n-Pr H 2-Cl 4-Cl 5 OMe OMe n-Bu H 2-Cl 4-Cl 6 OMe OMe Ph H 2-Cl 4-Cl 7 OMe OMe p-MePh H 2-Cl 4-Cl 8 OMe OMe p-ClPh H 2-Cl 4-Cl 9 OMe OMe o-ClPh H 2-Cl 4-Cl 10 OMe OMe m-BrPh H 2-Cl 4-Cl ll OMe OMe 2-Furyl H 2-Cl 4-Cl 12 OMe OMe CC13 H 2-Cl 4-C1 13 OEt OEt p-MePh H 2-Cl 4-Cl 14 OEt OEt p-ClPh H 2-Cl 4-Cl 15 OEt OEt o-ClPh H 2-Cl 4-Cl l6 OMe OMe H Me 2-Cl 4-Cl 17 OMe OMe Me Me 2-Cl 4-Cl 18 OMe OMe Et Me 2-Cl 4-Cl l9 OMe OMe n-Pr Me 2-Cl 4-Cl 20 OMe OMe Ph Me 2-Cl 4-Cl 21 OEt OEt Ph Me 2-Cl 4-Cl 22 OEt OEt Me Me 2-Cl 4-Cl 23 OPr-n OPr-n Me Me 2-Cl 4-Cl 24 OMe OMe 4-NO2Ph Me 2-Cl 4-Cl 25 OMe OMe 2-ClPh Me 2-Cl 4-Cl 26 OMe OMe 2-NO2Ph Me 2-Cl 4-Cl 27 OPr-n OPr-n n-Pr Me 2-Cl 4-Cl 28 OMe OMe H H H 4-NO2 29 OMe OMe Me H H 4-NO2 30 OMe OMe Me H 2-NO2 H 3l HO HO H H Cl Cl 32 HO HO CH3 H Cl Cl 33 HO HO Et H Cl Cl 34 HO HO Pr H Cl Cl 35 KO KO H H Cl Cl 36 KO KO CH3 H Cl Cl 37 OMe HO H H Cl Cl 38 OMe OMe H H H 4-Br |
From following test example as can be seen, the compound of formula I of the present invention has very strong inhibition activity to various plants and weeds.
Embodiment 11 IC
50Measure (to the inhibition activity of cucumber growth)
Cucumber seeds (No. one, commercial summer Shen) behind presoaking and germinating, is selected consistent seed, put in the culture dish of the different concns soup that the people prepared (10 centimetres of Φ), 10 in every ware is established three and is repeated and blank, inserts in the growth cabinet.Temperature is controlled at 25 ± 2 ℃, and photo-irradiation treatment is illumination 10 hours every days, 14 hours dark processing, and it is long to take out the mensuration root after 6 days, and stem is long, calculates inhibiting rate, adopts method of least squares to carry out result's statistics, asks IC
50, as the IC of table 2 part (I) formula compound
50Value.
Table 2 IC
50Measurement result
| The N0 compound | R 1 | R 2 | R 3 | R 4 | X | Y | IC 50(ppm) | |
| Root is long | Stem is long | |||||||
| 1 2 3 4 6 9 10 11 l2 l3 l5 | OMe OMe OMe OMe OMe OMe OMe OMe OMe Ogt 0Me | OMe OMe OMe OMe OMe OMe OMe OMe OMe Ogt 0Me | H Me gt n-Pr Ph o-ClPh m-BrPh 2-Furyl CCl 2 p-MePh o-Clph | H H H H H H H H H H H | 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl 2-Cl | 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl 4-Cl | 0.0198 0.0009 0.1215 0.0029 0.0353 0.0218 0.0271 0.0485 0.0748 0.7856 0.17174 | 2.6704 2.6981 5.1771 3.5947 3.7487 3.5718 2.7275 7.4362 2.2402 6.9361 10.1485 |
Under the situation of compound of the present invention as the weedicide use, compound of the present invention and other can be used for the use that combines of the active compound of having of gardening farm, the compound that compound of the present invention and other have herbicide effect and even the plant growth regulation use that combines.
Under the situation that compound of the present invention uses as weedicide, carrier or the mixing diluents that allows on compound of the present invention and the gardening can be modulated into it normally used various formulation whereby, as be modulated into and play the part of agent.Granula, hydrating agents, emulsion, but the water solvent flowing agent waits and uses.Also can succeed with other agricultural chemicals, sterilization. sterilant. miticide, weedicide, plant growth regulating chaste tree, fertilizer and soil improvement agent etc. mix use or also use simultaneously.
Embodiment 12, the weeding activity inhibition test
(1) active culture ware method:
Get the 10ppm of 10 milliliters of formulas (1) compound, 100ppm solution is put into respectively and is lined with two filter paper, diameter is in 10 centimetres the culture dish, wheat that again will be after vernalization, barnyard grass grass, common vetch, radish, each 20 culture dish of putting into different concns respectively of Semen Brassicae campestris, culture dish is inserted (25 ℃) in the thermostat container, illumination/dark processing (8/16 hour) is after 96 hours, measure the long and clear water contrast of root length, stem of plant, calculate different medicine samples, different concns, the root length of different examination materials, the long percentage that suppresses of stem respectively.
The measurement result of part formula I compound sees Table 3
Table 3
| Chemical combination No | Concentration (PPm) | Wheat | The barnyard grass grass | Common vetch | Radish | Rape | |||||
| Root suppresses % | Stem suppresses % | Root suppresses % | Stem suppresses % | Root suppresses % | Stem suppresses % | Root suppresses % | Stem suppresses % | Root suppresses % | Stem suppresses % | ||
| 6 | 10 100 | 95．94 100 | 49．41 91．57 | 80．94 95．29 | 36．36 63．64 | 100 100 | 100 100 | 94．44 100 | 83．33 100 | 92．11 100 | 86．00 99．00 |
| 7 | 10 100 | 89．86 100 | 27．49 57．84 | 80．94 95．29 | 36．36 63．64 | 100 100 | 100 100 | 94．44 100 | 76．67 83．33 | 92．44 100 | 80．11 85．00 |
| 9 | 10 100 | 10．75 73．02 | -11．29 0 | 24．71 71．76 | -9．09 | 50．00 75．00 | 12．0 50．0 | 69．44 86．11 | 6．67 37．33 | 67．11 85．10 | 10．66 38．33 |
| 8 | 10 100 | 84．79 100 | 32．55 74．70 | 82．35 95．29 | 27．27 43．09 | 100 100 | 100 100 | 86．11 94．44 | 67．67 66．67 | 85．11 95．00 | 71．22 68．00 |
| 2 | 10 100 | 80．00 92．95 | 40．05 75．00 | 30．00 70．00 | 10．11 20．10 | 95．5 100 | 94．00 96．55 | 85．55 95．00 | 60．65 68．11 | 98．2 100 | 96．6 99．4 |
| 3 | 10 100 | 98．17 100 | 47．67 53．49 | 100 100 | 49．02 62．52 | 100 100 | 100 100 | 96．06 100 | 85．31 88．34 | 94．19 100 | 89．13 89．13 |
| 2．4- D | 10 100 | 100 100 | 47．67 53．49 | 100 100 | 89．13 89．13 | ||||||
(2) pot-culture method:
The loam of quantitatively packing into and sieving with the potted plant box of 30 * 20 * 5.5 centimetres plastics, elder generation's water is drenched, sprout rape on the kind, common vetch, radish, wheat, each two row of barnyard grass grass, 10 of every row, cover 0.6 centimetre of the fine earth of sieving, adopt every mu 150 gram of compound (1) to broadcast back seedling pre-treatment and seedling aftertreatment immediately, the seedling aftertreatment is generally the 2-3 leaf phase, and two kinds of processing are all handled with emulsion spray, other establishes the clear water contrast, give out light according to glass room about 15 days, temperature is 25 ℃, cuts over-ground part after the processing, claim fresh weight, ask fresh weight, ask fresh weight to compare, calculate and suppress percentage with contrast (CK).
Partly (I) formula compound is given birth to survey and be the results are shown in Table 4.
Compound (I) is to the inhibition percentage % 150g/ mu of plant
| Compound N o | The seedling pre-treatment | The seedling aftertreatment | ||||
| Rape % | Radish % | Common vetch % taraxacum | Rape % | Radish % | Common vetch % taraxacum | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 | 100 92.54 100 99.54 99.54 100 54.71 18.83 100 100 100 100 100 100 100 | 100 100 100 98.99 98.9 100 76.08 52.42 100 100 100 100 100 100 100 | (100) (98.99 (100) 100 100 100 62.5 37.5 100 (100) (100) 100 (83.33 (100) 100 | 100 100 100 100 100 100 100 33.33 100 100 100 100 100 100 100 | 100 100 100 100 100 100 100 45.59 100 100 100 100 100 100 100 | (100) (100) (100) 100 100 100 100 25.74 100 (100) (100) 100 (100) (100) 100 |
Embodiment 13 plant growth regulating activities are measured wheat bud scale elongation test method
Be taken at the wheat bud scale of cultivating in the dark 3 days, downcut 3 millimeters sections as the examination material with cutting the bud scale cutter after discarding vertical 2 millimeters, sample to be tested with 0.01 milliliter phosphoric acid---citric acid solution (PH=5) is diluted to 100ppm and 10ppm, get 3 milliliters of liquid to be measured in the culture dish of φ=6 centimetre (putting a filter paper in the ware), put into 10 of the wheat bud scale sections (operating in the darkroom carries out) that cut in each culture dish, placed under 26 ℃ of constant temperature dark culturing 24 hours, survey per 10 staple fiber ppd, calculate the effect percentage.
Table 5 wheat bud scale elongation test measurement result
| Compound N o | Wheat bud scale method | Compound N o | Wheat bud scale method | ||||
| 100ppm | 10ppm | 5ppm | 100ppm | 100ppm | 5ppm | ||
| Effect % | Effect % | Effect % | Effect % | Effect % | Effect % | ||
| 1 2 3 4 5 6 7 8 9 10 | -30 -25.4 -30 -25.4 -25.4 -14.3 -1.8 -10.7 -30 -25 | 3.5 3.3 19.3 5.3 3.3 16.4 28.8 25 7.0 9.6 | 25 26.3 25.0 32.7 | 11 12 15 IAA 2.4- D | -23.1 -19.2 -9.6 30.2 -30 | 12.5 17.3 11.5 25 19.3 | 26.9 5.8 21.2 21.0 |
Claims (6)
1, logical represented substituted phenoxyl acetyloxy hydrocarbyl phosphonate or the salt of formula I, in the formula:
R
1, R
2Expression C
1-C
3Alkoxyl group, OH, ONa, OK, ONH
4Group
R
1With R
2It is identical or inequality,
R
3Expression H, C
1-C
4Alkyl or CCl
3, phenyl, substituting group are halogen, NO
2, CH
3, OCH
3Substituted-phenyl, furyl,
R
4Expression H, C
1-C
4Alkyl,
X, Y represent H, Cl, Br, NO
2, CH
3, its X is identical with Y or inequality,
But the qualifications of logical formula I is as follows:
R in logical formula I
1, R
2Be oxyethyl group, R
4During for H,
If X, Y are 2-Cl, 4-Cl, then R
3Be CCl
3, substituting group is halogen, NO
2, CH
3, OCH
3Substituted-phenyl, furyl,
If X, Y are H, 4-Cl, then R
3For substituting group is halogen, NO
2, CH
3, OCH
3Substituted-phenyl, furyl,
If X, Y are H, 4-methyl, then R
3For removing CCl
3The structural changes scope of above-mentioned defined in addition.
2, the substituted phenoxyl acetyloxy hydrocarbyl phosphonate general formula (I-1) in the described compound of representing by logical formula I of claim 1
Preparation method's (B method), it is characterized in that making the logical represented compound of formula II
The compound represented with following logical formula IV,
React, the gained general formula is (V) represented intermediate.
Represented with following logical formula VI again compound
React R, R in (I-1), (II), (IV), (V), (VI) formula
5Expression C
1-C
3Alkyl, R and R
5Can be identical or inequality, R
3, R
4, X, Y be identical with the definition in the claim 1, M is Na, K.
3, with the represented substituted phenoxy acetoxyl alkyl phosphonic preparation method of general formula (I-2)
R in the formula
3And R
4, X, Y be identical with the definition in the claim 1, it is characterized in that utilizing claim 2 or 3 described methods to prepare O, the dialkyl substituted phenoxyl acetyloxy hydrocarbyl phosphonate of O-is a raw material, at reagent (CH
3)
3SiI or (CH
3)
3Be converted into corresponding O under the effect of SiBr, O-two (trimethyl silicon based) phosphonic acid ester, further alcoholysis generates corresponding substituted phenoxy acetoxyl alkyl phosphonic acids again.
4, with the preparation method of the represented substituted phenoxy acetoxyl alkyl phosphonate of general formula (I-3)
M is Na, K, NH in the formula
4, R
3And R
4, X, Y be identical with the definition in the claim 1, it is characterized in that with make in the claim 4 with the represented substituted phenoxy acetoxyl alkyl phosphonic acids of general formula (I-2), under the effect of alkali, change into corresponding substituted phenoxy acetoxyl alkyl phosphonate.
5, the application of the substituted oxy acetoxyl group phosphonate compound of representing with logical formula I as claimed in claim 1 is characterized in that the effective ingredient as weedicide.
6, the application of the substituted oxy acetoxyl alkyl phosphonate compound of representing with logical formula I as claimed in claim 1 is characterized in that the effective ingredient as plant-growth regulator.
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| US9029542B2 (en) | 2011-09-06 | 2015-05-12 | Central China Normal University | Substituted phenoxyethyl (isopropyl) acyloxyalkyl phosphonate comprising phosphorusheterocyclic ring and having herbicidal activity, and preparation therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100382697C (en) * | 2003-10-14 | 2008-04-23 | 华中师范大学 | Weeding composition containing herbicide O,O-dimethyl-1-(2,4-dichlorophenoxy acetoxy) ethyl phosphonate |
| CN100412078C (en) * | 2004-02-26 | 2008-08-20 | 华中师范大学 | Fluorine substituted phenoxy acetyl oxide alkyl phosphonate ester and salt with weeding active and preparation process thereof |
| CN1319449C (en) * | 2005-04-14 | 2007-06-06 | 华中师范大学 | Substituted phenoxy acetyl oxy alkyl phospho acid and phosphonate ester possessing bactericidal insecticidal activity |
| CN100375748C (en) * | 2005-04-26 | 2008-03-19 | 华中师范大学 | Substituted phenoxy-acetoxy-aromatic heterocyclic radical-alkyl ester phisphinic acid possessing bactericidal and herbicidal activity, and preparation |
| CN101323628B (en) * | 2008-07-04 | 2011-11-30 | 华中师范大学 | 1-(2,4-disubstituted phenoxyl acetoxy) alkyl phosphonate having herbicide activity and preparation thereof |
| CN102771509A (en) * | 2012-07-23 | 2012-11-14 | 河南金田地农化有限责任公司 | Herbicide composition containing clacyfos |
| CN103588814A (en) * | 2012-08-13 | 2014-02-19 | 华中师范大学 | Optically active isomer of substituted phenoxyl acetyloxy (amino) hydrocarbyl phosphonate with herbicidal activity and preparation thereof |
| CN104098603B (en) * | 2013-04-02 | 2016-08-17 | 华中师范大学 | There is the O of activity of weeding, O-dialkyl group-α-(substituted benzene oxygen butyryl acyloxy) alkyl phosphonate and preparation method |
| CN105985374B (en) * | 2015-02-15 | 2020-08-28 | 华中师范大学 | Preparation method of oxalyl phosphine chloride and production equipment thereof |
| CN108218919A (en) * | 2016-12-14 | 2018-06-29 | 华中师范大学 | Compound and its purposes as herbicide |
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| GB2037771A (en) * | 1978-11-10 | 1980-07-16 | Sandoz Ltd | ???-substituted benzyl phosphonic acid ester derivatives |
| EP0016310A1 (en) * | 1979-02-13 | 1980-10-01 | Symphar S.A. | Monophosphonate compounds, process for their preparation and pharmaceutical compositions containing them |
| US4231781A (en) * | 1978-08-31 | 1980-11-04 | Gaf Corporation | Halophenoxy-alkoxy phosphonates and thiophosphonates |
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1997
- 1997-04-30 CN CN97109095A patent/CN1060480C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4231781A (en) * | 1978-08-31 | 1980-11-04 | Gaf Corporation | Halophenoxy-alkoxy phosphonates and thiophosphonates |
| GB2037771A (en) * | 1978-11-10 | 1980-07-16 | Sandoz Ltd | ???-substituted benzyl phosphonic acid ester derivatives |
| EP0016310A1 (en) * | 1979-02-13 | 1980-10-01 | Symphar S.A. | Monophosphonate compounds, process for their preparation and pharmaceutical compositions containing them |
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|---|---|---|---|---|
| US9029542B2 (en) | 2011-09-06 | 2015-05-12 | Central China Normal University | Substituted phenoxyethyl (isopropyl) acyloxyalkyl phosphonate comprising phosphorusheterocyclic ring and having herbicidal activity, and preparation therefor |
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