CN108395376A - 2- (2- methoxyl group -5- nitro-phenoxies) acetic acid and its preparation method and application - Google Patents
2- (2- methoxyl group -5- nitro-phenoxies) acetic acid and its preparation method and application Download PDFInfo
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- CN108395376A CN108395376A CN201810438336.4A CN201810438336A CN108395376A CN 108395376 A CN108395376 A CN 108395376A CN 201810438336 A CN201810438336 A CN 201810438336A CN 108395376 A CN108395376 A CN 108395376A
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- 238000002360 preparation method Methods 0.000 title claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- -1 methoxyl group Chemical group 0.000 claims abstract description 24
- 239000005648 plant growth regulator Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000007952 growth promoter Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 9
- IVJQGBHYRPCKGH-UHFFFAOYSA-N 2-methoxy-4-nitrophenol;sodium Chemical class [Na].COC1=CC([N+]([O-])=O)=CC=C1O IVJQGBHYRPCKGH-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 241000209510 Liliopsida Species 0.000 claims description 7
- 241001233957 eudicotyledons Species 0.000 claims description 7
- 239000003966 growth inhibitor Substances 0.000 claims description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 5
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 4
- 239000003630 growth substance Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000000413 hydrolysate Substances 0.000 claims 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims 1
- 241000209140 Triticum Species 0.000 abstract description 20
- 235000021307 Triticum Nutrition 0.000 abstract description 19
- 240000004922 Vigna radiata Species 0.000 abstract description 16
- 235000010721 Vigna radiata var radiata Nutrition 0.000 abstract description 14
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 abstract description 14
- 235000017060 Arachis glabrata Nutrition 0.000 abstract description 13
- 244000105624 Arachis hypogaea Species 0.000 abstract description 13
- 235000010777 Arachis hypogaea Nutrition 0.000 abstract description 13
- 235000018262 Arachis monticola Nutrition 0.000 abstract description 13
- 235000020232 peanut Nutrition 0.000 abstract description 13
- 230000008635 plant growth Effects 0.000 abstract description 10
- 230000002401 inhibitory effect Effects 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 3
- 230000004071 biological effect Effects 0.000 abstract description 2
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical group OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035784 germination Effects 0.000 description 21
- 239000007787 solid Substances 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 230000003750 conditioning effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003375 plant hormone Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000034303 cell budding Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002373 plant growth inhibitor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000032823 cell division Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007954 growth retardant Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- KBRKFTKQRMYINW-UHFFFAOYSA-M sodium;2-methoxy-5-nitrophenolate Chemical class [Na+].COC1=CC=C([N+]([O-])=O)C=C1[O-] KBRKFTKQRMYINW-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Abstract
The present invention provides a kind of compounds of structure shown in Formulas I, are 2 (2 methoxyl group, 5 nitro-phenoxy) acetic acid, have phenoxy acetic acid class skeleton, can adjust the growth of plant.The compound has been carried out biological activity test by the present invention on monocotyledon wheat and dicotyledon mung bean and peanut respectively, the experimental results showed that for mung bean, peanut and wheat, the compound has obvious facilitation when concentration is relatively low, there is certain inhibiting effect when concentration is higher.The compound provided by the invention provides a new selection for plant growth regulator.
Description
Technical field
The present invention relates to plant growths to promote technical field more particularly to 2- (2- methoxyl group -5- nitro-phenoxies) acetic acid
And its preparation method and application.
Background technology
Plant hormone is a kind of organic substance generated by plant own metabolism, and is moved to service portion from generating unit
Just there are the micro substance of apparent physiological effect, also referred to as natural plant hormone or plant endogenous sharp in position at much lower concentrations
Element, cell division and elongation, tissue and Organ Differentiation, bloom with it is solid, ripe with aging, suspend mode with sprout and in vitro
Tissue cultures etc. regulate and control the growth and development and differentiation of plant respectively or mutually coordinated.Plant hormone is as endogenous object
Matter, content is few, extract inside plants hormone by way of realize large-scale industrial production, it is of high cost, application aspect by
Limitation is arrived.
Artificial synthesized has the chemical substance of adjustment effect to be known as plant growth regulator the growth and development of plant.Phase
For plant hormone, plant growth regulator can be obtained by artificial synthesized mode, cost relative reduction, application
It is more convenient.In the prior art, plant growth regulator can be divided into three classes according to its exercising result：Plant growth promoter, life
Long inhibitor and growth retardant.Currently, there are many research about plant growth regulator, but most researchs all concentrate on
Have the derivative of type and its compounding with insecticide, fertilizer, trace element etc., but it is more rare about plant growth regulating
The report of agent new varieties.
Invention content
The purpose of the present invention is to provide a kind of noval chemical compounds, can be used as plant growth regulator.
The present invention provides a kind of compounds and its salt compounds with structure shown in Formulas I：
Preferably, the salt compounds are the carboxylic acid sodium salt of structural compounds shown in Formulas I.
The present invention provides the preparation methods of compound described in above-mentioned technical proposal, include the following steps：
It is under the conditions of oil bath, 5- nitroguaiacol sodium salts and tetrabutylammonium bromide is soluble in water, obtain mixed solution；
Methyl chloroacetate is added drop-wise in the mixed solution, reaction system is obtained；
The reaction system is subjected to nucleophilic substitution between 75 DEG C~85 DEG C, obtains 2- (2- methoxyl group -5- nitre
Phenoxyl) methyl acetate；
The 2- (2- methoxyl group -5- nitro-phenoxies) methyl acetate is hydrolyzed with sodium hydroxide solution, adjusts hydrolysis production
The pH to 9~10 of object, into obtained alkaline hydrolysis products, dropwise addition hydrochloric acid is acidified to pH for 1~2 under condition of ice bath,
Obtain the compound of structure shown in Formulas I.
Preferably, the mass ratio of the 5- nitroguaiacol sodium salts, tetrabutylammonium bromide and water is 5.03:0.4~0.8:
60~90；
The methyl chloroacetate and the mass ratio of tetrabutylammonium bromide in mixed solution are 6：0.3~0.8.
Preferably, the temperature of the oil bath is 75 DEG C~90 DEG C.
Preferably, the rate of the dropwise addition is 1s/ drops~5s/ drops.
Preferably, further include after the acidification：It is dried in vacuo after obtained acid system is filtered, the vacuum drying
To dry under vacuum, the temperature of the drying is 30 DEG C~50 DEG C.
The present invention also provides compounds described in above-mentioned technical proposal and its salt compounds as plant growth regulator
Application.
Preferably, the application as monocotyledon or dicotyledon.
Preferably, the growth regulator is growth promoter, is structural compounds or its esters compound shown in Formulas I
Aqueous solution, the mass concentration of the aqueous solution is [0.0075%, 0.06%].
Preferably, the growth regulator is growth inhibitor, is structural compounds or its esters compound shown in Formulas I
Aqueous solution, the mass concentration ＞ 0.06% of the aqueous solution.
The present invention provides a kind of new compounds, 2- (2- methoxyl group -5- nitro-phenoxies) acetic acid, have benzene oxygen second
Acids skeleton can adjust the growth of plant.The present invention is small in monocotyledon respectively by the compound and its salt compounds
Biological activity test is carried out on wheat and dicotyledon mung bean and peanut, the experimental results showed that for mung bean, peanut and small
Wheat, the compound have obvious facilitation when concentration is relatively low, there is certain inhibiting effect when concentration is higher.
The compound provided by the invention provides a new selection for plant growth regulator.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram that embodiment prepares product；
Mung bean germination when Fig. 2 is a concentration of 0.0075%；
Mung bean germination when Fig. 3 is a concentration of 0.03%；
Mung bean germination when Fig. 4 is a concentration of 0.06%；
Wheat germination situation when Fig. 5 is a concentration of 0.01%
Wheat germination situation when Fig. 6 is a concentration of 0.03%；
Wheat germination situation when Fig. 7 is a concentration of 0.06%；
Peanut germination when Fig. 8 is a concentration of 0.03%；
Peanut germination when Fig. 9 is a concentration of 0.06%；
Wheat root compares figure when Figure 10 is a concentration of 0.03%；
Maize seedling stem and root system compare figure when Figure 11 is a concentration of 0.03%.
Specific implementation mode
The present invention provides a kind of compounds and its salt compounds with structure shown in Formulas I：
In the present invention, the compound of structure shown in the Formulas I is 2- (2- methoxyl group -5- nitro-phenoxies) acetic acid, tool
There is phenoxy acetic acid skeleton, taking root and growing for monocotyledon and dicotyledon can be adjusted, in different concentration ranges,
Have the function of promotion (low concentration) or inhibits (high concentration) plant growth.
The present invention provides the preparation methods of compound described in above-mentioned technical proposal, include the following steps：
It is under the conditions of oil bath, 5- nitroguaiacol sodium salts and tetrabutylammonium bromide is soluble in water, obtain mixed solution；
Methyl chloroacetate is added drop-wise in the mixed solution, reaction system is obtained；
The reaction system is subjected to nucleophilic substitution between 75 DEG C~85 DEG C, obtains 2- (2- methoxyl group -5- nitre
Phenoxyl) methyl acetate；
The 2- (2- methoxyl group -5- nitro-phenoxies) methyl acetate is hydrolyzed with sodium hydroxide solution, adjusts hydrolysis production
The pH to 9~10 of object, it is 1~2 that concentrated hydrochloric acid, which is added dropwise, to pH into obtained alkaline hydrolysis products under condition of ice bath, obtains Formulas I
The compound of shown structure.
The present invention preferably first mixes 5- nitroguaiacol sodium salts with tetrabutylammonium bromide with water, then oil bath heating makes
Material dissolution.5- nitroguaiacol sodium salts, tetrabutylammonium bromide and water is added in the present invention in the reaction vessel, specifically, in reality
It tests reaction vessel described in room and four-hole boiling flask may be selected, stirred equipped with thermometer, constant pressure funnel, reflux condensing tube and machinery
Mix stick.In the present invention, the mass ratio of 5- nitroguaiacol sodium salts, tetrabutylammonium bromide and water is preferably 5.03:0.4~
0.8:60~90, more preferably 5.03:0.45~0.6:80~90；In an embodiment of the present invention, the 5- nitros guaiaci lignum
The mass ratio of phenol sodium, tetrabutylammonium bromide and water can be specially 5.03:0.4:90,5.03:0.45:80 or 5.03:0.6:90.
In the present invention, the dissolving preferably carries out under stirring conditions；The rate of the stirring is preferably 200 revs/min；
In the present invention, the temperature of the oil bath is preferably 75 DEG C~90 DEG C, more preferably 80~85 DEG C；In embodiments of the present invention, institute
It can be specially 90 DEG C, 83 DEG C or 75 DEG C to state oil bath temperature.
After obtaining mixed solution, methyl chloroacetate is added drop-wise in the mixed solution by the present invention, obtains reaction system.
In the present invention, the dropwise addition preferably uses constant pressure funnel to carry out；The rate of the dropwise addition is preferably 1s/ drops~5s/
Drop, in an embodiment of the present invention, the rate of the dropwise addition can be specially 5 seconds/drop, 1 second/drop or 3s/ drops.In the present invention,
The methyl chloroacetate and the mass ratio of tetrabutylammonium bromide in mixed solution are preferably 6:0.3~0.8, concretely 6:
0.3、6:0.45、6:0.5 or 6:0.6.
After obtaining reaction system, the reaction system is warming up between 75 DEG C~85 DEG C and carries out nucleophilic displacement of fluorine by the present invention
Reaction, obtains 2- (2- methoxyl group -5- nitro-phenoxies) methyl acetate.In the present invention, the temperature of the nucleophilic substitution
Preferably 80 DEG C.
Present invention preferably employs the processes of thin-layer chromatography following response, and to judge the terminal of reaction, reaction was completed.At this
In invention, the condition TLC contact plate observing response situations of the thin-layer chromatography, reaction solution is compared with raw material, until the reaction was complete.
After completing the nucleophilic substitution, the present invention is by obtained 2- (2- methoxyl group -5- nitro-phenoxies) methyl acetate hydrogen-oxygen
Change sodium solution hydrolysis, adjusts the pH to 9~10 of hydrolysate, be added dropwise into obtained alkaline hydrolysis products under condition of ice bath
Concentrated hydrochloric acid is 1~2 to pH, obtains the compound of structure shown in Formulas I, obtains the compound of structure shown in Formulas I.In the present invention,
Preferably reaction system is cooled down before the hydrolysis, is preferably cooled to room temperature；During the cooling, analysed in reaction system
Go out solid, reaction system takes on a red color.
In the present invention, the hydrolysis preferably carries out at room temperature, and the mass concentration of sodium hydroxide solution used is preferably
10%~30%, more preferably 15%~25%, in an embodiment of the present invention, the mass concentration of the sodium hydroxide solution
Can be specially 10%, 15% or 30%.In the present invention, the time of the hydrolysis is preferably 1h.
In the present invention, the acidification preferably carries out under condition of ice bath.In the present invention, the quality of the hydrochloric acid is dense
Degree preferably 10%~36%, more preferably 15%~30%；In an embodiment of the present invention, the mass concentration of the hydrochloric acid
Can be specially 10%, 20% or 36%.In the present invention, the pH value of the acidification is preferably 1~2.In the present invention, described
Acidification is specially：Under condition of ice bath, it is added hydrochloric acid into the reaction system after cooling, the pH value of regulation system to 1~
2.In the present invention, the time of the acidification is preferably 1h~2h.During adjusting pH value, the 2- (2- in the system
Methoxyl group -5- nitro-phenoxies) sodium acetate, the color of system also becomes yellow from red, eventually becomes milky, and hydrolysis is anti-
It should terminate.
After the acidification, the present invention is dried in vacuo after preferably filtering obtained acid system, obtains structure shown in Formulas I
Compound, be white powder.In the present invention, the filtering preferably filters；The condition of the suction filtration is preferably that oil pump is taken out
Vacuum.
In the present invention, the vacuum drying is preferably dried under vacuum；The vacuum drying temperature is preferred
It is 30 DEG C~50 DEG C, more preferably 35 DEG C~45 DEG C；In an embodiment of the present invention, the vacuum drying temperature can be specific
It is 30 DEG C, 40 DEG C or 50 DEG C；The vacuum drying time is preferably 3h~5h；The vacuum drying vacuum degree preferably-
0.1MPa~0.1MPa.
In the present invention, the mechanism of above-mentioned reaction is as shown in Formula II：
In the present invention, the salt compounds are preferably the carboxylic acid sodium salt of structural compounds shown in Formulas I.
In the present invention, the preparation method of the salt compounds preferably includes following steps：
Structural compounds shown in Formulas I are mixed with water, obtain aqueous systems；
Sodium hydrate aqueous solution is added into the aqueous systems, until solid all dissolves, obtains the carboxylic acid sodium of compound
Salt.
In the present invention, the mass ratio of structural compounds and water shown in the Formulas I is preferably 1:66；The sodium hydroxide
The mass concentration of aqueous solution is preferably 10%.Obtained carboxylic acid sodium salt aqueous solution is yellow liquid.
The compound of structure shown in Formulas I provided by the invention has the function of coordinate plant growth, specifically, of the invention
Additionally provide application of the compound described in above-mentioned technical proposal as plant growth regulator.
Specifically, the compound of structure shown in the Formulas I can be as the growth tune of monocotyledon or dicotyledon
Save agent, the monocotyledon such as wheat, the dicotyledon such as mung bean and peanut.
In the present invention, the plant growth regulator can be plant growth promoter, when the compound is as plant
When object growth promoter, mass concentration of the compound in plant growth promoter preferably >=0.0075% and≤
0.06%；In an embodiment of the present invention, the mass concentration can be specially 0.0075%%, 0.03% or 0.05%；It is described
Plant growth promoter is preferably the aqueous solution of the compound or the aqueous solution of compound carboxylic acid sodium salt.For mung bean,
The mass concentration of compound shown in Formulas I as growth promoter be [0.0075%, 0.06), it is specific such as 0.0075%,
0.03% or 0.05%；For wheat, the mass concentration of compound shown in the Formulas I as growth promoter is
[0.01%, 0.06%], it is specific such as 0.01%, 0.03% or 0.06%；For peanut, the Formulas I as growth promoter
The mass concentration of shown compound is [0.03%, 0.06%], specific such as 0.03% or 0.06%.
In the present invention, the plant growth regulator can also be plant growth inhibitor, when as inhibitor,
The preferred ＞ of concentration of the compound in inhibitor 0.06%；In an embodiment of the present invention, the mass concentration can be specific
It is 0.06% or 0.1%.In an embodiment of the present invention, the plant growth inhibitor is preferably the water-soluble of the compound
Liquid.For mung bean, the mass concentration of compound shown in the Formulas I as growth inhibitor is >=0.06%, specifically such as
0.06% or 0.1%；For wheat, the mass concentration of compound shown in the Formulas I as growth inhibitor is >=0.1%,
Specific such as 0.1%；For peanut, the mass concentration of compound shown in the Formulas I as growth inhibitor is >=0.06%,
Specific such as 0.06% or 0.1%.
In order to illustrate further the present invention, with reference to embodiment to 2- provided by the invention (2- methoxyl group -5- nitre
Phenoxyl) acetic acid and its preparation method and application is described in detail, but they cannot be interpreted as protecting the present invention
The limitation of range.
In the examples below, the instrument and reagent used is as shown in Table 1 and Table 2：
1 key instrument of table
2 main agents of table
| Reagent name | Specification | Manufacturer |
| Dichloromethane | It analyzes pure | Tianjin Fu Yu Fine Chemical Co., Ltd |
| Anhydrous sodium sulfate | It analyzes pure | Chinasun Specialty Products Co., Ltd |
| Nitro piperonyl cyclonene | It analyzes pure | Tianjin Fu Yu Fine Chemical Co., Ltd |
| Sodium hydroxide | It analyzes pure | Chinasun Specialty Products Co., Ltd |
| 5- nitroguaiacol sodium salts | It analyzes pure | Henan Zhong Wei high-tech chemical inc |
| Tetrabutylammonium bromide | It analyzes pure | Shanghai Aladdin biochemical technology limited liability company |
| β-chlorotriethylamine hydrochloride | It analyzes pure | The rich Chemical Co., Ltd. of Quzhou City's riel |
| Diethyl ethylene diamine | It analyzes pure | Henan Zhong Wei high-tech chemical inc |
| Methyl chloroacetate | It analyzes pure | Shanghai Aladdin biochemical technology limited liability company |
Embodiment 1
5.03g5- nitroguaiacol sodium salts, 0.6g tetrabutylammonium bromide and 90g are sequentially added in 250ml four-hole boiling flasks
Water, then oil bath heating is to 75 DEG C, and mechanical agitation is until dissolution of raw material.6g methyl chloroacetates are taken again, use constant pressure funnel
It is slowly added into above-mentioned reaction system, drop speed is 3s/ drops.After being added dropwise to complete, control temperature is anti-between 75 DEG C to 85 DEG C
It answers, until the reaction is complete using thin-layered chromatography following response process.
Reaction solution is cooled to room temperature, after slow precipitation solid, system takes on a red color；Mass concentration is used at ambient temperature
The pH value that 30% sodium hydroxide adjusts red system reaches 9 or 10, stirring hydrolysis 1h；
Hydrolysis liquid is cooled to room temperature, after slow precipitation solid, system takes on a red color；With hydrochloric acid tune under condition of ice bath
The pH value of the red system of section reaches 1 or 2 and is acidified, and solid is persistently precipitated in system of observing, and system color is by red change
Huang, eventually becomes milky, and suction filtration obtains white solid；White solid is positioned in vacuum drying chamber and is dried at 50 DEG C,
Obtain white powder.
Obtained white powder is carried out nuclear magnetic resonance spectroscopy detection by the present invention, and the results are shown in Figure 1, can be seen by Fig. 1
Go out,1H-NMR(500MHZ,CH3OD,TMS)：δ 8.03 (1H, m), δ 7.75 (1H, d), δ 7.11 (1H, d), δ 4.75 (2H, s),
δ 4.01 (3H, s), the results show that the product that the present embodiment is prepared has structure shown in Formulas I.
The present invention weighs to obtained white powder, quality 5.0g, calculated yield 83.7%.
Embodiment 2
5.03g5- nitroguaiacol sodium salts, 0.4g tetrabutylammonium bromide and 90g are sequentially added in 250ml four-hole boiling flasks
Water, then oil bath heating is to 80 DEG C, and mechanical agitation is until dissolution of raw material.6g methyl chloroacetates are taken again, use constant pressure funnel
It is slowly added into above-mentioned reaction system, drop speed is 5s/ drops.After being added dropwise to complete, control temperature is anti-between 75 DEG C to 85 DEG C
It answers, until the reaction is complete using thin-layered chromatography following response process.
Reaction solution is cooled to room temperature, after slow precipitation solid, system takes on a red color；At ambient temperature with 30% hydroxide
The pH value that sodium adjusts red system reaches 9 or 10, stirring hydrolysis 1h.
Then hydrolysis liquid is cooled to room temperature, after slow precipitation solid, system takes on a red color；Salt is used under condition of ice bath
The pH value of the red system of acid adjusting reaches 1 or 2 and is acidified, and solid is persistently precipitated in system of observing, and system color is by red
Turn yellow, eventually become milky, suction filtration obtains white solid；White solid is positioned in vacuum drying chamber and is dried at 50 DEG C
It is dry, obtain white powder 4.7g, yield 78.7%.
Obtained white powder is carried out nuclear magnetic resonance spectroscopy detection by the present invention, the results show that the present embodiment is prepared
Product have Formulas I shown in structure.
Embodiment 3
Sequentially added in 250ml four-hole boiling flasks 5.03g5- nitroguaiacol sodium salts, 0.45g tetrabutylammonium bromide and
80g water, then oil bath heating is to 80 DEG C, and mechanical agitation is until dissolution of raw material.6g methyl chloroacetates are taken again, use constant pressure addition
Funnel is slowly added into above-mentioned reaction system, and drop speed is 1s/ drops.After being added dropwise to complete, control temperature is between 75 DEG C to 85 DEG C
Reaction, until the reaction is complete using thin-layered chromatography following response process.
Reaction solution is cooled to room temperature, after slow precipitation solid, system takes on a red color；At ambient temperature with 10% hydroxide
The pH value that sodium adjusts red system reaches 9 or 10, stirring hydrolysis 1h.
Then hydrolysis liquid is cooled to room temperature, after slow precipitation solid, system takes on a red color；Salt is used under condition of ice bath
The pH value that acid adjusts red system reaches 1 or 2 acidifications, and solid is persistently precipitated in system of observing, and system color is by red change
Huang, eventually becomes milky, and suction filtration obtains white solid；White solid is positioned in vacuum drying chamber and is dried at 50 DEG C,
Obtain white powder 4.9g, yield 82%.
Obtained white powder is carried out nuclear magnetic resonance spectroscopy detection by the present invention, the results show that the present embodiment is prepared
Product have Formulas I shown in structure.
Application examples 1
By 2- (2- methoxyl group -5- nitro-phenoxies) peracetic acid formulation of synthesis at aqua：1.5% carboxylic acid sodium salt aqua
(yellow liquid), preparation method are：100g water is added in 1.5g2- (2- methoxyl group -5- nitro-phenoxies) acetic acid, to obtained body
The sodium hydrate aqueous solution that mass concentration is 10% is added dropwise in system until all solids dissolving, becomes yellow liquid, obtain quality
A concentration of 1.5% carboxylic acid sodium salt aqua.It reuses aquae destillata and is diluted to various concentration, a concentration of 0.0075%, 0.01%,
0.03%, 0.05%, 0.06%, 0.1% aqueous solution is spare.It (is arranged according to serial number 2 and 4 in attached drawing, No. 2 represent 2- (2-
Methoxyl group -5- nitro-phenoxies) acetic acid aqua, No. 4 be clear water as a contrast.)
This experiment is all (about 28-29 DEG C) progress at room temperature.The uniform full experiment of Seed size is selected first
Then seed is impregnated with corresponding target substance aqua, takes clean culture dish, be put into the seed of immersion, then the filter with wetting
In paper covering, while seed is impregnated as a contrast with clear water.Observation statistics germination after 12h.
Experimentation has used two ways：Conditioning agent observation germination is sprayed within n hours again and is taken root first, seed first impregnates
Situation, second is that observing germination and situation of taking root after directly impregnating seed n hours with aqua.The experimental results showed that both
Influence of the mode to bud ratio is little, and following statistical results are counted according to the second situation.
The uniform full seed of Seed size is chosen, 40 wheats, 40 mung bean seeds and 20 flowers are chosen in every group of experiment
Non-hibernating eggs, it is spare to be averagely put into two different vessel after being sterilized with hypochlorite solution.Uniform discharge on the paper bed of moistening,
The plant growth regulator solution for spraying various concentration respectively impregnates the 4h times, No. 1 aqua for Formulas I structural compounds, No. 4
It is impregnated using clear water, carries out germination treatment, germination is observed after 12h and is photographed to record.After statistics, calculate separately each
Germination promotion rate of the germination percentage and dilution of dilute solution relative to clear water.As a result as shown in Fig. 2~11 and table 3~4.
Table 32- (2- methoxyl group -5- nitro-phenoxies) alphatic acid sodium aqueous is adjusting mung bean budding situation statistics
Mung bean is when concentration 0.0075% is relatively low it can be seen from Fig. 2~4 and table 3, the carboxylic acid sodium aqueous of compound of formula I
Effect be stratification；A concentration of 0.03%, the budding promotion rate of conditioning agent is far better than clear water.Reach in concentration
0.06% and 0.1%, conditioning agent has certain inhibiting effect instead substantially without facilitation；This shows in very low concentrations
When, the facilitation effect unobvious of conditioning agent have the effect for being obviously promoted germination in low concentration, inhibiting effect when high concentration
Obviously.
The case where wheat germination, is as shown in Fig. 5~7 and table 4
Table 42- (2- methoxyl group -5- nitro-phenoxies) acetic acid aqueous solutions are adjusting mung bean budding situation statistics
| Compound | Concentration (%) | Sprout number | Bud ratio (%) | Promotion rate of sprouting (%) |
| Formulas I | 0.01 | 13 | 65 | 225 |
| Clear water | 0 | 4 | 20 | - |
| Formulas I | 0.03 | 15 | 75 | 87.5 |
| Clear water | 8 | 40 | - | |
| Formulas I | 0.06 | 18 | 90 | 12.5 |
| Clear water | 16 | 80 | - |
For wheat in concentration 0.01% and 0.03%, conditioning agent takes root to wheat it can be seen from Fig. 5~7 and table 4
There is apparent facilitation effect with germination.In concentration 0.06%, also there is certain facilitation, but promote degree
Decline；This explanation, conditioning agent facilitation effect in low concentration is apparent, but life of the conditioning agent for wheat in higher concentration
Long germination has apparent inhibiting effect.
Peanut germination is as shown in Fig. 8~9, and peanut is in concentration 0.03% and 0.06% it can be seen from Fig. 8~9
When, conditioning agent has an apparent facilitation effect to the germination of peanut, and effect when specific concentration 0.03% in concentration 0.06%
More preferably.
The growing state of wheat seedling is as shown in Figure 10, as seen from Figure 10, by it is left-to-right be a concentration of 0.03% respectively
Formulas I aqua and No. 4 clear water, left side wheat seedling is more apparent than the root system of right side wheat seedling elongated to become close；
The growing state of maize seedling is as shown in figure 11, and as seen from Figure 11, concentration is all 0.03%, (a concentration of from a left side
0.03% Formulas I aqua) to right (clear water), the sturdy degree of stem is obviously better than No. 4, and root system is also more flourishing.
As can be seen from the above embodiments, the Formulas I of synthesis has for the adjustment effect of monocotyledon and dicotyledon
Institute is different, and same concentration has bigger difference, influence of the various concentration to same plant for unifacial leaf and dicotyledon
It is very different.Compound shown in Formulas I in low concentration to the facilitation of mung bean clearly, when concentration is high inhibit make
With also all apparent；Effect for peanut, concentration (concentration that inhibiting effect has been played for wheat and mung bean) when higher
Still there is certain facilitation, but the Formulas I generally speaking synthesized in low concentration all plays certain facilitation,
Formulas I has inhibiting effect to different plants respectively when concentration is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. compound and its salt compounds with structure shown in Formulas I：
2. the preparation method of compound described in claim 1, includes the following steps：
It is under the conditions of oil bath, 5- nitroguaiacol sodium salts and tetrabutylammonium bromide is soluble in water, obtain mixed solution；
Methyl chloroacetate is added drop-wise in the mixed solution, reaction system is obtained；
The reaction system is subjected to nucleophilic substitution between 75 DEG C~85 DEG C, obtains 2- (2- methoxyl group -5- nitrobenzene oxygen
Base) methyl acetate；
The 2- (2- methoxyl group -5- nitro-phenoxies) methyl acetate is hydrolyzed with sodium hydroxide solution, adjusts hydrolysate
PH to 9~10, into obtained alkaline hydrolysis products, dropwise addition hydrochloric acid is acidified to pH for 1~2 under condition of ice bath, obtains formula
The compound of structure shown in I.
3. preparation method according to claim 2, which is characterized in that the 5- nitroguaiacol sodium salts, tetrabutyl phosphonium bromide
The mass ratio of ammonium and water is 5.03:0.4~0.8:60~90；
The methyl chloroacetate and the mass ratio of tetrabutylammonium bromide in mixed solution are 6:0.3~0.8.
4. preparation method according to claim 2 or 3, which is characterized in that the temperature of the oil bath is 75 DEG C~90 DEG C.
5. preparation method according to claim 2 or 3, which is characterized in that the rate of the dropwise addition is 1s/ drops~5s/ drops.
6. preparation method according to claim 2, which is characterized in that further include after the acidification：The acidification body that will be obtained
It is dried in vacuo after system's filtering, to dry under vacuum, the temperature of the drying is 30 DEG C~50 DEG C for the vacuum drying.
7. the application of compound and its salt compounds as plant growth regulator described in claim 1.
8. application according to claim 7, which is characterized in that the application as monocotyledon or dicotyledon.
9. application according to claim 8, which is characterized in that the growth regulator is growth promoter, is shown in Formulas I
The mass concentration of the aqueous solution of structural compounds or its esters compound, the aqueous solution is [0.0075%, 0.06%].
10. application according to claim 8, which is characterized in that the growth regulator is growth inhibitor, for Formulas I institute
Show structural compounds or the aqueous solution of its esters compound, the mass concentration ＞ 0.06% of the aqueous solution.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261795A (en) * | 1997-07-03 | 2000-08-02 | 史密丝克莱恩比彻姆公司 | Compounds and methods |
| CN105622396A (en) * | 2014-10-27 | 2016-06-01 | 浙江新安化工集团股份有限公司 | 2,4-dichlorophenoxyacetic acid preparation method |
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2018
- 2018-05-09 CN CN201810438336.4A patent/CN108395376A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261795A (en) * | 1997-07-03 | 2000-08-02 | 史密丝克莱恩比彻姆公司 | Compounds and methods |
| CN105622396A (en) * | 2014-10-27 | 2016-06-01 | 浙江新安化工集团股份有限公司 | 2,4-dichlorophenoxyacetic acid preparation method |
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| BERTI, G.等: "Nitro derivatives of 2-hydroxyphenylhydroxyacetic acid", 《FARMACO, EDIZIONE SCIENTIFICA》 * |
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| JACOBS, WALTER A.等: "Nitro- and aminophenoxyacetic acids", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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