CN102718722B - The novel fragrant phenoxy ramification of carboxylic esters preparations and applicatio research that a kind of water oil is double molten - Google Patents
The novel fragrant phenoxy ramification of carboxylic esters preparations and applicatio research that a kind of water oil is double molten Download PDFInfo
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- CN102718722B CN102718722B CN201210235509.5A CN201210235509A CN102718722B CN 102718722 B CN102718722 B CN 102718722B CN 201210235509 A CN201210235509 A CN 201210235509A CN 102718722 B CN102718722 B CN 102718722B
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- 238000011160 research Methods 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 title description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- -1 bisulfate ion Chemical class 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 4
- 229940068372 acetyl salicylate Drugs 0.000 claims abstract description 4
- 229940001468 citrate Drugs 0.000 claims abstract description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229960001860 salicylate Drugs 0.000 claims abstract description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 12
- 241000196324 Embryophyta Species 0.000 claims description 9
- 230000002363 herbicidal effect Effects 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000001963 growth medium Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 241000380130 Ehrharta erecta Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000009333 weeding Methods 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 125000002769 thiazolinyl group Chemical group 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229940079593 drug Drugs 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 0 CCOC(C(C)Oc(cc1)ccc1O*)=O Chemical compound CCOC(C(C)Oc(cc1)ccc1O*)=O 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CWHJIJJSDGEHNS-MYLFLSLOSA-N Senegenin Chemical compound C1[C@H](O)[C@H](O)[C@@](C)(C(O)=O)[C@@H]2CC[C@@]3(C)C(CC[C@]4(CCC(C[C@H]44)(C)C)C(O)=O)=C4[C@@H](CCl)C[C@@H]3[C@]21C CWHJIJJSDGEHNS-MYLFLSLOSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000012136 culture method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000009871 tenuigenin Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- FAFQSSXABFWMBC-UHFFFAOYSA-M CC(C(Cl)=O)Oc(cc1)ccc1O[AlH2] Chemical compound CC(C(Cl)=O)Oc(cc1)ccc1O[AlH2] FAFQSSXABFWMBC-UHFFFAOYSA-M 0.000 description 1
- RFOKRDOWYKTWKG-UHFFFAOYSA-M CC(C(O)=O)Oc(cc1)ccc1O[AlH2] Chemical compound CC(C(O)=O)Oc(cc1)ccc1O[AlH2] RFOKRDOWYKTWKG-UHFFFAOYSA-M 0.000 description 1
- TYIYMOAHACZAMQ-CQSZACIVSA-N Cyhalofop-butyl Chemical group C1=CC(O[C@H](C)C(=O)OCCCC)=CC=C1OC1=CC=C(C#N)C=C1F TYIYMOAHACZAMQ-CQSZACIVSA-N 0.000 description 1
- 239000005502 Cyhalofop-butyl Substances 0.000 description 1
- 241000192043 Echinochloa Species 0.000 description 1
- 241000209510 Liliopsida Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000005614 Quizalofop-P-ethyl Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126540 compound 41 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RENRQMCACQEWFC-UGKGYDQZSA-N lnp023 Chemical compound C1([C@H]2N(CC=3C=4C=CNC=4C(C)=CC=3OC)CC[C@@H](C2)OCC)=CC=C(C(O)=O)C=C1 RENRQMCACQEWFC-UGKGYDQZSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- OSUHJPCHFDQAIT-GFCCVEGCSA-N quizalofop-P-ethyl Chemical group C1=CC(O[C@H](C)C(=O)OCC)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 OSUHJPCHFDQAIT-GFCCVEGCSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The profit with weeding activity is held concurrently the compounds process for production thereof of molten fragrant phenoxy carboxylic-acid and salt thereof and an applied research, as shown in general formula (I, II):
wherein: n=0,1,2,3,4,5 ... or (CH
2)
nrepresent the alkyl with side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; R
2represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; Or R
1, R
2be selected from following structure:
ar is selected from one of following group:
Description
Technical field:
The present invention relates to the double molten novel fragrant phenoxy ramification of carboxylic esters preparation of a kind of water oil and weeding activity.。
Background technology:
Traditional Agricultural pharmaceutically dosage form is with missible oil, wettable powder, pulvis and granule are main, along with the manufacture and exploit of pesticides new formulation, following meeting is towards aqua, the future development such as aqueous emulsion and microemulsion, from this development trend, this just has higher requirement to the novel pesticide molecule being about to succeed in developing, not only want efficient, low toxicity, safety and and environmental friendliness, also wish that drug molecule has certain water-soluble simultaneously, directly use if drug molecule has the good water-soluble aqua that just can be made into, so not only can reduce production cost but also can reduce when drug molecule is made into certain preparation needs to add a large amount of solvent, tensio-active agent, the environmental pollution that auxiliary agent and permeate agent etc. bring.From this respect, good water-soluble of drug molecule has very important significance.Meanwhile, having necessarily water-soluble and fat-soluble drug molecule, is also that medicine is effectively necessary through microbial film.
No matter medicine is that epidermal absorption or other approach absorb, and all needs with the form of molecule through barrier membranes.First medicine need dissolve, and if medicine has desirable biopharmaceutical properties, its region from the regional diffusion of high density to lower concentration, strides across cytolemma and enters into the recycle system.All microbial films contain lipid as major ingredient.In biofilm structure, active molecule all has the end structure containing phosphatic high polarity, and, in most of the cases, the hydrocarbon chain of two very hydrophobic.Microbial film has bilayer structure, and hydrophilic chain end structure is towards the aqueous regions of both sides.Very hydrophilic medicine cannot stop wherein as a biomembranous part because of the similar reason mixed by very hydrophobic medicine through biomembranous lipid layer, thus effectively can not enter inner tenuigenin.
Patent documentation CN1927843A, WO2006/125337A1 report some fragrant phenoxy carboxylic acid ester compound and have good herbicidal activity, wherein typical compound, and as quizalofopPethyl, cyhalofop-butyl is commercial varieties important in this compounds.But they exist preparation processing difficulty in application process, generally can only be processed into the missible oil of low levels, and need to add a large amount of auxiliary agents, to improve its sticking power on crop, improve its bioavailability.
The object of the invention is by regulating the water-soluble and fat-soluble of several fragrant phenoxy ramification of carboxylic esters, making them can reach a well balance, reducing the loss of in vitro, thus improve the utilization ratio of medicine.The fragrant phenoxy ramification of carboxylic esters of new design and synthesis has two identical constructional features: they have part (oil soluble part) and the one-level that protonated form exists under physiology PH condition of a close ester, secondary, or tertiary amine group (water-soluble portion).Water-soluble-oily molten balance is like this that medicine is effectively through microbial film institute necessary [SusanMilosovich, etal.J.Pharm.Sci., 82,227 (1993)].Amino with positive charge considerably increases the solubleness of medicine.This point can be able to be seen from experimental implementation: in product aftertreatment, does not become the compound of positive ion to be dissolved in sherwood oil and water insoluble, and after becoming quaternary amine, compound is present in water layer, and is insoluble to sherwood oil.As a rule, the solubleness of medicine is step that is the slowest in absorption process and maximum speed limit.When these novel cpds make medicament, in its molecule, amino understands the phosphate end group bonding with cytolemma.Therefore, the partial concn of medicine outside microbial film is very high thus contribute to these medicines by the region of area with high mercury to lower concentration.After these drug molecules enter into microbial film, hydrophilic parts can promote the tenuigenin that medicine enters into the concentrated aqueous solution of semi liquid state.
Summary of the invention:
The object of this invention is to provide the fragrant phenoxy ramification of carboxylic esters of a class formation novelty and the compound of salt thereof and synthetic method, this compounds has excellent weeding activity.
The invention provides a kind of fragrant phenoxy carboxylic acid esters of novel structure and the compound of salt thereof, as shown in general formula (I, II):
Wherein:
N=0,1,2,3,4,5 ... or (CH
2)
nrepresent the alkyl with side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; R
2represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; Or R
1, R
2be selected from following structure:
Ar is selected from one of following group:
The comparatively preferred compound of the present invention is:
N=1 ~ 4, Y is acid ion, R
1, R
2be selected from H, C
1-C
4alkyl or R
1=R
2be selected from following structure:
Ar is selected from Ar1, Ar2
In the present invention, more preferred structural formula of compound is as follows:
In formula, the carbon atom of mark * is R type.
The following method preparation of general formula compound (I, II) of the present invention:
Raw material (III can be buied by market) is dissolved in suitable solvent, with in alkaline aqueous solution, temperature reacts 1-24 hour under being 0 DEG C to boiling point, then through hydrochloric acid or sulfuric acid acidation, obtained intermediate acid (III-1).Suitable solvent is selected from dioxane, benzene, toluene, ethyl acetate, THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride; Suitable alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus.
Intermediate acid (III-1) and SOCl
2, PCl
3or oxalyl chloride is dissolved in suitable solvent, such as dioxane, benzene, toluene, ethyl acetate, THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride, with organic bases as pyridine, triethylamine take DMF as catalyzer, and temperature is react 1-24 hour obtained acyl chlorides (III-2) under 0 DEG C to boiling point.
Acyl chlorides (III-2) and (n+1)-(dialkyl group) amino-1-alcohol (preparing), in suitable solvent, temperature is react 1-24 hour obtained product (I) under 0 DEG C to boiling point.Solvent can be dioxane, benzene, toluene, ethyl acetate, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.Add alkaline matter, as pyridine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus etc. are favourable to reaction.
Product (I) and diluted acid YH, product (I) can be dissolved in suitable solvent, add diluted acid YH, temperature is react 1-24 hour obtained product (II) under 0 DEG C to boiling point.Solvent can be dioxane, benzene, toluene, ethyl acetate, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.
Table 1: the compounds of this invention of part as shown in general formula I
Table 2: the compounds of this invention of part as shown in general formula I I
Part of compounds in table
1hNMR data are as follows:
Compound 13:(CDCl
3) 8.683 (s, 1H), 8.057 (s, 1H), 7.682-7.705 (d, 1H), (7.602-7.624 d, 1H), 7.189-7.211 (d, 2H), 6.954-6.976 (d, 2H), 4.767-4.817 (q, 1H), 4.213-4.333 (q, 2H), 3.684-3.705 (t, 4H), 2.341-2.402 (m, 6H), 1.814-1.882 (m, 2H), 1.665-1.682 (d, 3H)
Compound 41:(CDCl
3) 7.442-7.472 (q, 1H), 6.984-7.007 (d, 2H), 6.901-6.917 (d, 2H), 6.860-6.894 (d, 1H), (4.711-4.762 q, 1H), 4.176-4.299 (q, 2H), 3.678-3.702 (t, 4H), (2.313-2.389 m, 6H), 1.782-1.852 (m, 2H), 1.630-1.647 (d, 3H)
Compound 13-H:(D
2o) δ 8.52 (s, 1H), 7.15 (m, 1H), 7.11 (d, 4H), 6.82 (m, 2H), 4.89 (q, 1H), 4.05 (t, 2H), 3.89 (t, 4H), 3.41 (t, 4H), (3.08 t, 2H), 2.04 (m, 2H), 1.62 (d, 3H).
Compound 41-H:(D
2o) δ 7.61 (dd, 1H), 7.38 (dd, 1H), 7.35-7.28 (m, 2H), 7.16 (dd, 1H), 6.99-6.91 (m, 2H), 4.89 (q, 1H), 4.04 (t, 2H), 3.87 (t, 4H), 3.12 (t, 2H), 2.83 (t, 4H), 1.91 (p, 2H), 1.62 (d, 3H).
General formula (I, II) compound of the present invention has weeding activity, uses the growth that can control gramineous weeds well after seedling.Compare with existing similar compound, such compounds exhibit goes out better weeding activity and broad spectrum.
It is the herbicidal composition of active ingredient that the present invention also comprises with general formula (I, II) compound.In this herbicidal, the weight percentage of active ingredient is 1-99%.Agriculturally acceptable carrier is also comprised in this herbicidal composition.
General formula (I of the present invention, II) compound and the herbicidal composition as active ingredient thereof can make several formulations use, especially general formula (II), directly can be made into aqua to use, both decreased with an organic solvent to the pollution of environment, be more conducive to again absorption and the conduction of plant.In these compositions, also can add liquid or solid carrier, and add appropriate tensio-active agent and carry out compounding application.
Other embodiment of the present invention is the method for control gramineous weeds, and the method comprises and compound of the present invention and composition thereof is applied on the surface of described weeds or its growth medium.Amount of application is generally per hectare 6 grams to 500 grams, and preferably having effective amount is per hectare 30 grams to 300 grams.In addition, also can add one or more other weedicide in compound of the present invention and in active composition, can produce more efficient thus, the effect of wide spectrum.
General formula (I, II) compound of the present invention both can be used alone as weedicide and other known sterilant, sterilant, plant-growth regulator or fertilizer also can be coordinated to mix together.
It is clear that within the scope of the claims in the present invention, should can carry out various change and conversion as required.
Embodiment
The following example and raw test-results of surveying can be used for weeding activity of the present invention is described further, but do not mean that restriction the present invention.
Synthesis example
The synthesis of compound 1:
1.
III (R type is added in 250ml reaction flask, 18.64g, 0.05mol, market is buied) and 40mlTHF, be stirred to entirely molten, drip the 40ml aqueous solution of 2.2g sodium hydroxide, stirring at room temperature 4 hours, stop stirring, suction filtration elimination insolubles, decompression removing THF, aqueous solution dilute hydrochloric acid acidifying, obtains white solid (III-1) 16.3g.
2.
In 50ml reaction flask, add III-1 (1.72g, 0.005mol) and 15ml methylene dichloride, under stirring, add thionyl chloride (1.18g, 0.01mol), 2 DMF, reflux 5 hours, precipitation obtains yellow oil (III-2) 1.70g.
3.
III-2 (1.70g is added in 50ml reaction flask, 0.0047mol), adding the stirring of 10ml methylene dichloride makes molten, morpholine propyl alcohol (0.70g) is dripped under ice-water bath, the mixed solution of triethylamine (0.50g) and 5ml methylene dichloride, half an hour dropwises, and removes ice bath, stirred at ambient temperature 5h.The hydrochloride of suction filtration removing triethylamine after completion of the reaction, filtrate is washed twice with saturated common salt, one time is being washed, organic phase anhydrous magnesium sulfate drying, precipitation with saturated sodium bicarbonate solution, obtain clear yellow viscous thing 2,10g, column chromatography purifies (PE: EA=3: 1, add a small amount of TEA), finally obtain 1.70g pale yellow oil, this is compound 1.
The synthesis of compound 3:
Compound 1 compound 3
Compound 1 (1.70g) is dissolved in the dichloromethane solution of 20ml drying, solution is proceeded in 50ml two-mouth bottle, pass into dry HCl gas (to be added drop-wise in concentrated hydrochloric acid by the vitriol oil and to produce HCl gas, and obtained by vitriol oil drying), the time of passing into is 5-30min, precipitation obtains white solid 1.83g, and this is compound 3.
Table 1,2 other compounds all obtain by similar approach.
Raw survey example
Adopt and respectively Preliminary activation test has been carried out to the compounds of this invention to the cauline leaf process in the pot-culture method of mechanism of action sensitivity.
Pot-culture method (cauline leaf process): put into a certain amount of soil in the plastic cassettes of diameter 8cm, add a certain amount of water, after planting cover certain thickness soil, cultivate in greenhouse, cover with plastic film before coming up.After emerging, every day, in addition quantitative clear water was to keep normal growth.Cauline leaf spraying process is carried out when seedling grows to the certain period.Locate 27 days " Invest, Then Investigate " results, measure overground part fresh weight, suppress percentage ratio to represent drug effect with fresh weight.Compare with the examination material not by compound treatment, examination material is monocotyledon weed barnyard grass and lady's-grass.
Part is as follows in compound of Formula I test result:
Part is as follows in Compounds of formula II test result:
Claims (5)
1. a compound for fragrant phenoxy carboxylic acid esters salt, as shown in general formula (II):
Wherein:
N=0,1,2,3,4,5; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, R
1represent the alkoxyl group of the alkyl of 1-6 carbon atom, a 1-6 carbon atom; R
2represent the alkoxyl group of the alkyl of 1-6 carbon atom, a 1-6 carbon atom, wherein R
1, R
2it is not methyl; Or be selected from following concrete structure:
Ar is selected from one of following group:
。
2. compound as claimed in claim 1, is characterized in that, in general formula (II):
N=1 ~ 4; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, R
1, R
2be selected from C
1-C
4alkyl, wherein R
1, R
2it is not methyl.
3. compound according to claim 1 or its composition are for controlling annual and perennial grass herbaceous weed and woody weeds purposes.
4. a herbicidal composition, containing, for example compound according to claim 1 and agriculturally acceptable carrier, in composition, the weight percentage of active ingredient is 1-99%.
5. control a method for weeds, it is characterized in that: the herbicidal composition as claimed in claim 4 using herbicidally effective amount on the growth medium or place of weeds or weeds.
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| CN106631895A (en) * | 2016-11-29 | 2017-05-10 | 江苏富鼎化学有限公司 | Phenoxyphenoxylpropargyl propionate compound as well as preparation method and application thereof |
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| CN111825625B (en) * | 2020-08-21 | 2023-05-05 | 山东京博农化科技股份有限公司 | Purification method of R-quizalofop-p-ethyl |
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| JPS62161762A (en) * | 1986-01-10 | 1987-07-17 | Aguro Kanesho Kk | Hydroxyacetic acid amide derivative |
| JPH03251570A (en) * | 1990-02-28 | 1991-11-11 | Mitsubishi Petrochem Co Ltd | Phenozypropionic ester derivative and herbicide containing same as active ingredient |
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| EP0023785B1 (en) * | 1979-07-17 | 1985-04-03 | Ici Australia Limited | Quinoxalinyloxyphenoxyalkane carboxylic acid derivatives, their preparation and their use as herbicides |
| CN1552693A (en) * | 2003-05-27 | 2004-12-08 | 沈阳化工研究院 | Benzoylcyclohexanone amine compounds with herbicidal activity |
| CN1603299A (en) * | 2003-09-29 | 2005-04-06 | 沈阳化工研究院 | Novel carboxylate herbicides |
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Cited By (2)
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| CN106631895A (en) * | 2016-11-29 | 2017-05-10 | 江苏富鼎化学有限公司 | Phenoxyphenoxylpropargyl propionate compound as well as preparation method and application thereof |
| CN106631895B (en) * | 2016-11-29 | 2019-03-29 | 江苏富鼎化学有限公司 | Phenoxy phenoxy base propionic acid propargyl ester compound and its preparation method and application |
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