CN105348315A - Tributyltin o-phenyl dioxy acetate, preparation method therefor and applications - Google Patents
Tributyltin o-phenyl dioxy acetate, preparation method therefor and applications Download PDFInfo
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- CN105348315A CN105348315A CN201510753322.8A CN201510753322A CN105348315A CN 105348315 A CN105348315 A CN 105348315A CN 201510753322 A CN201510753322 A CN 201510753322A CN 105348315 A CN105348315 A CN 105348315A
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- China
- Prior art keywords
- adjacent benzene
- acetic ester
- tributyl tin
- preparation
- dioxy acetic
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- 241000790917 Dioxys <bee> Species 0.000 title claims abstract description 52
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title abstract 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 147
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 130
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 61
- 235000019439 ethyl acetate Nutrition 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims description 27
- 240000001592 Amaranthus caudatus Species 0.000 claims description 19
- 235000009328 Amaranthus caudatus Nutrition 0.000 claims description 19
- 239000004178 amaranth Substances 0.000 claims description 19
- 235000012735 amaranth Nutrition 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 11
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 244000237956 Amaranthus retroflexus Species 0.000 claims description 9
- 235000013479 Amaranthus retroflexus Nutrition 0.000 claims description 9
- 244000234609 Portulaca oleracea Species 0.000 claims description 9
- 235000001855 Portulaca oleracea Nutrition 0.000 claims description 9
- 241000219793 Trifolium Species 0.000 claims description 9
- 210000000582 semen Anatomy 0.000 claims description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 8
- 241000196324 Embryophyta Species 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 230000008635 plant growth Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- 238000009333 weeding Methods 0.000 abstract description 18
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 8
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 239000005648 plant growth regulator Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- -1 ester group triadimefon compound Chemical class 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 230000004071 biological effect Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 2
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 description 2
- 240000006122 Chenopodium album Species 0.000 description 2
- 235000009344 Chenopodium album Nutrition 0.000 description 2
- 244000058871 Echinochloa crus-galli Species 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 244000178993 Brassica juncea Species 0.000 description 1
- 235000005855 Brassica juncea var. subintegrifolia Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000008853 Datura stramonium Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- DWMUPKFIPHJSMZ-UHFFFAOYSA-N O(C1=CC=CC=C1)CC(=O)O.[Sn] Chemical compound O(C1=CC=CC=C1)CC(=O)O.[Sn] DWMUPKFIPHJSMZ-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 235000000208 Solanum incanum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- GXZYJGUCMMVAQW-UHFFFAOYSA-N dicyclohexyl(methyl)tin Chemical compound C1CCCCC1[Sn](C)C1CCCCC1 GXZYJGUCMMVAQW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 244000230342 green foxtail Species 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- RNVJQUPAEIQUTC-UHFFFAOYSA-N tricyclohexyltin Chemical compound C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 RNVJQUPAEIQUTC-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses tributyltin o-phenyl dioxy acetate. Tributyltin o-phenyl dioxy acetate is a complex with a structural formula (I) shown in the specification, wherein Bu is n-butyl. The invention also discloses a preparation method for the complex and applications in biological weeding activity.
Description
Technical field
The present invention relates to a kind of tributyl tin adjacent benzene dioxy acetic ester and preparation method thereof, and the application of the adjacent benzene dioxy acetic ester of this tributyl tin in plant growth regulating.
Background technology
In agriculture weeding, use a kind of weedicide or its composition for a long time, in a large number, weeds can develop immunity to drugs, and therefore, weedicide needs continuous innovation.People are in order to find the good herbicidal compound of high reactivity, highly selective and Environmental compatibility, and one of fruitful approach utilizes the activated compound of tool for guide's developing new drug thing.As everyone knows, since discovery 2,4-dichlorphenoxyacetic acid has efficiently, after the weeding of highly selective and biological regulation effect, phenoxy carboxylic acid herbicides is because structure is simple, activity is high, cost is low, is the class weedicide that output is maximum, usable floor area is the widest always.
Phenoxy acetic acid is not only widely used, and structure is special, different from general phenylformic acid, lipid acid, its alkoxyl group with rigidity phenyl ring, flexibility and the carboxyl of strong coordination, there is the feature of the organometallic complex of the coordination mode flexible and changeable with metal and the changeable formation different structure of sterie configuration, the new compound with novel structure and property can be constructed.
Organotin and derivative thereof not only have good biological activity, are used as desinsection, sterilization and cancer therapy drug, and antifouling paint, wood preservation etc.Some organo-tin compounds, also have the weeding activity being better than or being equivalent to 2,4 dichlorophenoxyacetic acid.Their low phytotoxicities, general low to the toxicity of non-target tissues, in environment under light, heat and biological action, easily can be transformed into the less compound of toxicity quickly, finally be degraded into nontoxic tindioxide residue, have desinsection, the multiple effect of sterilization concurrently as weedicide, demonstrate good Development volue.Therefore, with phenoxy acetic acid and organo-tin compound for precursor, organotin phenoxy acetic acid ester is formed with the key effect that becomes of tin by carboxyl, or form title complex by the coordination of carbonyl and tin, the compounds two classes with weeding activity is integrated, seek that drug effect is better, selectivity be better, the weedicide new variety of use safety, significant.
Document (Chinese Journal of Inorganic Chemistry, 2006,22:656-660) is reported, the synthetic method of dialkyl tin Chlorlacetic Acid ester.
Document (organic chemistry, 2006,11:1571-1575) report, series of new is containing aryloxyacetic acid ester group triadimefon compound, the weeding activity test result of this series compound shows, substituting groups different on phenyl ring has obvious impact to weeding activity.
Document (chemical journal, 1995,53:1034-1040) report, the synthetic method of mixed trialkylated tin derivative methyldicyclohexyl tin (replacement) phenoxy acetic acid ester and biological activity, research shows, these compounds, except there being good acaricidal activity, also have certain sterilization, weeding and Plant Hormone Action.
Document (Chinese Journal of Inorganic Chemistry, 2010,26:1507-1510) is reported, the synthetic method of tri-n-butyl tin 2,4 dichlorophenoxyacetic acid ester and its structure.
Document (chemical research and application, 2010,22:926-929) is reported, the synthetic method of siliceous dialkyl tin phenoxy acetic acid title complex.
Document (organic chemistry, 1991,11:82-87) is reported, the synthetic method of Tricyclohexyltin aromatoxyacetate and kill mite and the effect to plant-growth regulator.
Document (JournalofOrganometallicChemistry, 2014,758:19-24) is reported, the synthetic method of di-n-butyl tin isophthalic dioxy acetic ester.
Document (SCI, 1991,12:1186-1189) is reported, the synthesis of tributyl tin hydrocarbon fluoroacetate and weeding activity, and the weeding activity of this compounds is better than or close to weedicide 2,4 dichlorophenoxyacetic acid.
Document (chemical journal, 1995,53:721-728) is reported, mixing tributyl tin carboxylicesters is to the weeding activity of the test materialss such as oat, barnyard grass, lady's-grass, rape, clover, three-coloured amaranth, and part of compounds has good inhibition.
Mixed trialkylated tin derivative pesticide disclosed in Chinese patent CN1097546A has very strong sterilization, desinsection, kills the two or more biological activity such as mite and weeding.
US Patent No. 3723089 discloses the plant growth regulation of a kind of organo-tin compound to plant such as leaf mustard, lamb's-quarters, lady's-grass, corn, wheat, cotton, peas.
US Patent No. 4260552 discloses the weeding activity of a series of polysubstituted organo-tin compound to plant such as lamb's-quarters, thorn apple, morning glory, lady's-grass, paddy green bristlegrass and barnyard grasses, and the growth inhibition ratio of most compounds to tested plant reaches 100%.
The experiment proved that material plant to growth regulating effect based on trialkylated tin aryloxyacetic acid ester compound, the present invention selects the organotin of tributyltin oxide, adjacent benzene two fluoroacetic acid is part, react under certain condition, synthesis obtains the compound stronger to the growth regulating effect of purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clover, provides new approach for developing new plant-growth regulator.
Summary of the invention
The first object of the present invention there is provided a kind of tributyl tin adjacent benzene dioxy acetic ester.
The second object of the present invention is to provide the preparation method of above-mentioned tributyl tin adjacent benzene dioxy acetic ester.
The third object of the present invention is to provide the application of the adjacent benzene dioxy acetic ester of above-mentioned tributyl tin in plant-growth regulator.
As a kind of tributyl tin adjacent benzene dioxy acetic ester of first aspect present invention, the compound for following structural formula (I):
Wherein Bu represents normal-butyl.
Tributyl tin of the present invention adjacent benzene dioxy acetic ester is through ultimate analysis, Infrared spectroscopy and nuclear magnetic resonance spectrum structural analysis, and result is as follows:
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
As the preparation method of a kind of tributyl tin adjacent benzene dioxy acetic ester of second aspect present invention, be in the reaction vessel having nitrogen protection, add adjacent benzene two fluoroacetic acid, tributyltin oxide and reaction solvent in order successively, under stirring and refluxing, react 4 ~ 18h; Cooling, filters; At pressure 0.004 ~ 0.01MPa, temperature is under 30 ~ 55 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white crystal, be tributyl tin adjacent benzene dioxy acetic ester.
In a preferred embodiment of the invention, described adjacent benzene two fluoroacetic acid and the amount of substance of tributyltin oxide are than being 1:1 ~ 1:1.2.
In a preferred embodiment of the invention, the consumption of described reaction solvent is that adjacent benzene two fluoroacetic acid of every mmole adds 12 ~ 25 milliliters.
In a preferred embodiment of the invention, described reaction solvent is dehydrated alcohol or anhydrous methanol or dry-out benzene.
In a preferred embodiment of the invention, in described methylene chloride-methanol mixed solvent, the volume ratio of methylene dichloride and methyl alcohol is 1:4 ~ 1:20.
As the application of the adjacent benzene dioxy acetic ester of a kind of tributyl tin in plant-growth regulator of third aspect present invention.
Applicant has carried out plant growth regulating activity to above-mentioned tributyl tin adjacent benzene dioxy acetic ester and has confirmed research, confirm that compound has plant growth regulation, that is the purposes of above-claimed cpd is the application in plant growth regulating, is exactly specifically the application in preparation purslane or Amaranthus retroflexus or Semen Cassiae or thorn amaranth or red roundleaf three-coloured amaranth or alfalfa plant growth regulator.
Tributyl tin of the present invention adjacent benzene dioxy acetic ester demonstrates good Developing restraint effect to purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clover etc., the features such as tributyl tin of the present invention adjacent benzene dioxy acetic ester weeding activity is high, cost is low, preparation method is simple, provide new way for developing new weedicide.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of tributyl tin adjacent benzene dioxy acetic ester.
Fig. 2 is tributyl tin adjacent benzene dioxy acetic ester
1hNMR spectrogram.
Fig. 3 is tributyl tin adjacent benzene dioxy acetic ester
13cNMR spectrogram.
Embodiment
Further describe the present invention by following examples, but scope of the present invention should be noted not by any restriction of these embodiments.
Embodiment 1:
The preparation of tributyl tin adjacent benzene dioxy acetic ester:
50mL has in the there-necked flask of nitrogen protection, add 0.226g (1mmol) adjacent benzene two fluoroacetic acid, 0.596g (1mmol) tributyltin oxide, 20ml anhydrous methanol, stirring and refluxing 6h, after having reacted, be cooled to room temperature, filter, at pressure 0.004MPa, temperature is under 30 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, wherein the volume ratio of methylene dichloride and methyl alcohol is 1:5, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white solid, be tributyl tin of the present invention adjacent benzene dioxy acetic ester ligand polymer.Productive rate: 42.6%.Fusing point: 82 DEG C ~ 83 DEG C.
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
Embodiment 2:
The preparation of tributyl tin adjacent benzene dioxy acetic ester:
25mL has in the there-necked flask of nitrogen protection, add 0.226g (1mmol) 1, 6-naphthalene two fluoroacetic acid, 0.655g (1.1mmol) tributyltin oxide, 12ml dehydrated alcohol, stirring and refluxing 4h, after having reacted, be cooled to room temperature, filter, at pressure 0.005MPa, temperature is under 35 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, wherein the volume ratio of methylene dichloride and methyl alcohol is 1:12, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white solid, be tributyl tin of the present invention adjacent benzene dioxy acetic ester ligand polymer.Productive rate: 44.1%.Fusing point: 82 DEG C ~ 83 DEG C.
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
Embodiment 3:
The preparation of tributyl tin adjacent benzene dioxy acetic ester:
50mL has in the there-necked flask of nitrogen protection, add 0.226g (1mmol) adjacent benzene two fluoroacetic acid, 0.715g (1.2mmol) tributyltin oxide, 25ml dry-out benzene, stirring and refluxing 10h, after having reacted, be cooled to room temperature, filter, at pressure 0.01MPa, temperature is under 55 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, wherein the volume ratio of methylene dichloride and methyl alcohol is 1:20, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white solid, be tributyl tin of the present invention adjacent benzene dioxy acetic ester ligand polymer.Productive rate: 41.8%.Fusing point: 82 DEG C ~ 83 DEG C.
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
Embodiment 4:
The preparation of tributyl tin adjacent benzene dioxy acetic ester:
250mL has in the there-necked flask of nitrogen protection, add 2.260g (10mmol) adjacent benzene two fluoroacetic acid, 6.437g (10.8mmol) tributyltin oxide, 130ml dry-out benzene, stirring and refluxing 18h, after having reacted, be cooled to room temperature, filter, at pressure 0.007MPa, temperature is under 50 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, wherein the volume ratio of methylene dichloride and methyl alcohol is 1:14, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white solid, be tributyl tin of the present invention adjacent benzene dioxy acetic ester ligand polymer.Productive rate: 41.0%.Fusing point: 82 DEG C ~ 83 DEG C.
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
Embodiment 5:
The preparation of tributyl tin adjacent benzene dioxy acetic ester:
250mL has in the there-necked flask of nitrogen protection, add 2.260g (10mmol) adjacent benzene two fluoroacetic acid, 6.854g (11.5mmol) tributyltin oxide, 150ml anhydrous methanol, stirring and refluxing 8h, after having reacted, be cooled to room temperature, filter, at pressure 0.008MPa, temperature is under 38 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, wherein the volume ratio of methylene dichloride and methyl alcohol is 1:4, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white solid, be tributyl tin of the present invention adjacent benzene dioxy acetic ester ligand polymer.Productive rate: 44.9%.Fusing point: 82 DEG C ~ 83 DEG C.
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
Embodiment 6:
The preparation of tributyl tin adjacent benzene dioxy acetic ester:
250mL has in the there-necked flask of nitrogen protection, add 2.260g (10mmol) 1, 6-naphthalene two fluoroacetic acid, 6.079g (10.2mmol) tributyltin oxide, 150ml dehydrated alcohol, stirring and refluxing 14h, after having reacted, be cooled to room temperature, filter, at pressure 0.009MPa, temperature is under 45 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, wherein the volume ratio of methylene dichloride and methyl alcohol is 1:16, under 10 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white solid, be tributyl tin of the present invention adjacent benzene dioxy acetic ester ligand polymer productive rate: 42.3%.Fusing point: 82 DEG C ~ 83 DEG C.
Ultimate analysis (C
34h
62o
6sn
2): theoretical value: C50.77, H7.77; Measured value: C50.75, H7.73.
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)。
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
Test example:
Tributyl tin of the present invention adjacent benzene dioxy acetic ester, its Herbicidal is realized by Plating experimental technique.
Plating:
Plating is adopted to measure the tributyl tin adjacent benzene dioxy acetic ester of embodiment 1 preparation to the weeding activity of common weed in the farm crop such as purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clover.
Test process: weigh a certain amount of testing sample with analytical balance, adds a small amount of DMF and dissolves, and drip 1 emulsifying agent (tween-80), it is stand-by that adding distil water is diluted to desired concn respectively.
With the culture dish of diameter 9cm, built-in two layers of filter paper and 10 have exposed the seeds such as the white purslane of bud, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clover, and adding 5mL said sample solution is respectively nutrient solution, directly makes blank with distilled water as nutrient solution, incubation growth in growth cabinet is positioned over after process, keep temperature 25 DEG C, humidity 80%RH, illumination 30%, periodicity of illumination daytime/night=16/8 culture condition, cultivate 6 days, measurement result, each test parallel testing three times.
Data processing: measure the stem of plant and the length of root with ruler, get its mean value, calculates the inhibiting rate of medicament.Result is for just to illustrate that medicament is inhibited, for negative, result illustrates that medicament has promoter action.
Inhibiting rate=[(blank mean length-process mean length)/blank mean length] * 100%
As shown in table 1 with the weeding activity test result of Plating to seeds such as purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clovers, conclusion is that tributyl tin adjacent benzene dioxy acetic ester demonstrates good Developing restraint effect to purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clover etc.
The weeding activity experimental data (growth inhibition ratio %) of table 1 tributyl tin adjacent benzene dioxy acetic ester.
Tributyl tin adjacent benzene dioxy acetic ester prepared by all the other embodiments is with the same test example of weeding activity testing method of Plating to crop seeds such as purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth, clovers, and test result and table 1 are substantially identical.
Claims (10)
1. a tributyl tin adjacent benzene dioxy acetic ester, the compound for following structural formula (I):
Wherein Bu represents normal-butyl.
2. tributyl tin as claimed in claim 1 adjacent benzene dioxy acetic ester, its infrared data:
IR(KBr,cm
-1)：3024.3(w)，2960.7(w),2914.4(w)，1768.7(s)，1510.2(s)，1201.6(s)，788.8(m)，601.7(m)，520.7(w)，453.2(w)。
3. tributyl tin as claimed in claim 1 adjacent benzene dioxy acetic ester, its nuclear magnetic data:
1HNMR(CDCl
3,500MHz),δ(ppm)：0.87～1.59(m，54H，Bu-
H)，4.51(s,4H,-OC
H 2-)，6.78(d,1H,Ph-
H)，7.87(d,1H,Ph-
H)，7.15(d,1H,Ph-
H)，7.34(d,1H,Ph-
H)；
13CNMR(CDCl
3,125MHz)，δ(ppm)：173.64(-
COO)，113.01～154.17(Ph-
C)，67.40(-O
CH
2-)，13.61～27.75(Bu-
C)。
4. the preparation method of tributyl tin according to claim 1 adjacent benzene dioxy acetic ester, is in the reaction vessel having nitrogen protection, add adjacent benzene two fluoroacetic acid, tributyltin oxide and reaction solvent in order successively, under stirring and refluxing, react 4 ~ 18h; Cooling, filters; At pressure 0.004 ~ 0.01MPa, temperature is under 30 ~ 55 DEG C of conditions, with Rotary Evaporators evaporate to dryness filtrate, obtain the thick product of the adjacent benzene dioxy acetic ester of tributyl tin, with methylene chloride-methanol mixed solvent recrystallization, under 15 ~ 35 DEG C of conditions, control solvent evaporates crystallization, obtain white crystal, be tributyl tin adjacent benzene dioxy acetic ester.
5. preparation method as claimed in claim 4, is characterized in that, described adjacent benzene two fluoroacetic acid is 1:1 ~ 1:1.2 with the amount of substance ratio of tributyltin oxide.
6. preparation method as claimed in claim 4, is characterized in that, the consumption of described reaction solvent is that adjacent benzene two fluoroacetic acid of every mmole adds 12 ~ 25 milliliters.
7. the preparation method as described in claim 4 or 6, is characterized in that, described reaction solvent is dehydrated alcohol or anhydrous methanol or dry-out benzene.
8. preparation method as claimed in claim 4, it is characterized in that, in described methylene chloride-methanol mixed solvent, the volume ratio of methylene dichloride and methyl alcohol is 1:4 ~ 1:20.
9. the application of the adjacent benzene dioxy acetic ester of tributyl tin described in claim 1 or 4 in plant growth regulating.
10. application according to claim 9, wherein said plant is purslane, Amaranthus retroflexus, Semen Cassiae, thorn amaranth, red roundleaf three-coloured amaranth or clover.
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Cited By (1)
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| CN105732696A (en) * | 2016-04-07 | 2016-07-06 | 衡阳师范学院 | Tricyclohexyltin chloride 1,3,5-benzene trioxy-acetate and preparation method and application thereof |
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