CN102219707B - Acrylpimaric dioxime derivative as well as preparation method and application thereof - Google Patents
Acrylpimaric dioxime derivative as well as preparation method and application thereof Download PDFInfo
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- CN102219707B CN102219707B CN201110103320.6A CN201110103320A CN102219707B CN 102219707 B CN102219707 B CN 102219707B CN 201110103320 A CN201110103320 A CN 201110103320A CN 102219707 B CN102219707 B CN 102219707B
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- korean pine
- ester derivative
- methyl
- oxime
- propylene korean
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- -1 oxime compound Chemical class 0.000 claims abstract description 36
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 30
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 27
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 27
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 51
- 235000011615 Pinus koraiensis Nutrition 0.000 claims description 44
- 240000007263 Pinus koraiensis Species 0.000 claims description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 36
- 238000010992 reflux Methods 0.000 claims description 27
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 8
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 claims description 8
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 6
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 230000009435 amidation Effects 0.000 abstract 1
- 238000007112 amidation reaction Methods 0.000 abstract 1
- 150000002632 lipids Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 36
- 229910052717 sulfur Inorganic materials 0.000 description 27
- 238000004090 dissolution Methods 0.000 description 24
- 238000001035 drying Methods 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 230000006837 decompression Effects 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000001953 recrystallisation Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- ATROHALUCMTWTB-WYMLVPIESA-N (z)-n-diethoxyphosphinothioyloxybenzenecarboximidoyl cyanide Chemical compound CCOP(=S)(OCC)O\N=C(/C#N)C1=CC=CC=C1 ATROHALUCMTWTB-WYMLVPIESA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 2
- VTWKXBJHBHYJBI-SOFGYWHQSA-N (ne)-n-benzylidenehydroxylamine Chemical compound O\N=C\C1=CC=CC=C1 VTWKXBJHBHYJBI-SOFGYWHQSA-N 0.000 description 2
- XXOHMWCSTKXDLH-YFHOEESVSA-N (nz)-n-[1-(4-methoxyphenyl)ethylidene]hydroxylamine Chemical compound COC1=CC=C(C(\C)=N/O)C=C1 XXOHMWCSTKXDLH-YFHOEESVSA-N 0.000 description 2
- XAAUYUMBCPRWED-NTMALXAHSA-N (nz)-n-[1-(4-methylphenyl)ethylidene]hydroxylamine Chemical compound O/N=C(/C)C1=CC=C(C)C=C1 XAAUYUMBCPRWED-NTMALXAHSA-N 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- 0 CC(CCC1)(C(CC2)C1(C)C(ON=C(C)c(cc1)ccc1Cl)=O)C(C1)C22C=*C1CC2C(ON=C(C)c(cc1)ccc1Cl)=O Chemical compound CC(CCC1)(C(CC2)C1(C)C(ON=C(C)c(cc1)ccc1Cl)=O)C(C1)C22C=*C1CC2C(ON=C(C)c(cc1)ccc1Cl)=O 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000005916 Methomyl Substances 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- QGLZXHRNAYXIBU-WEVVVXLNSA-N aldicarb Chemical compound CNC(=O)O\N=C\C(C)(C)SC QGLZXHRNAYXIBU-WEVVVXLNSA-N 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000004141 diterpene derivatives Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 2
- FTYXDGNSLZMOQY-UHFFFAOYSA-N n-(4-phenylbutan-2-ylidene)hydroxylamine Chemical compound ON=C(C)CCC1=CC=CC=C1 FTYXDGNSLZMOQY-UHFFFAOYSA-N 0.000 description 2
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- GQKRUMZWUHSLJF-NTCAYCPXSA-N Chlorphoxim Chemical compound CCOP(=S)(OCC)O\N=C(/C#N)C1=CC=CC=C1Cl GQKRUMZWUHSLJF-NTCAYCPXSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- FZSVSABTBYGOQH-XFFZJAGNSA-N [(e)-(3,3-dimethyl-1-methylsulfanylbutan-2-ylidene)amino] n-methylcarbamate Chemical compound CNC(=O)O\N=C(C(C)(C)C)\CSC FZSVSABTBYGOQH-XFFZJAGNSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- GMAUQNJOSOMMHI-JXAWBTAJSA-N alanycarb Chemical compound CSC(\C)=N/OC(=O)N(C)SN(CCC(=O)OCC)CC1=CC=CC=C1 GMAUQNJOSOMMHI-JXAWBTAJSA-N 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 235000015097 nutrients Nutrition 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an acrylpimaric dioxime ester derivative as well as a preparation method and an application thereof. The invention discloses a preparation method of the acrylpimaric dioxime ester derivative. The method comprises the steps of carrying out amidation on raw material acrylpimaric acid to obtain acrylpimaric acyl chloride; and then reacting the acrylpimaric acyl chloride with an oxime compound; and introducing a condensed multi-alcyl structure of a rosin into the oxime compound so that the oxime ester derivative of the acrylpimaric acid is prepared, wherein the derivative has both better lipid solubility and certain bioactivity and in particular has an antibacterial effect. Because the acrylpimaric acid used in the invention comes from a modified product of natural product rosin, low cost and simple preparation method are obtained.
Description
Technical field
The invention belongs to field of natural product chemistry, relating to rosin acrylic acid is the method that the two oxime ester derivative of propylene Korean pine prepared by raw material, also relates to the antibacterial application of this analog derivative.
Background technology
Oxime Ester is owing to having extensive biological activity, and be used to sterilant, Insecticides (tech) & Herbicides (tech), antitumor and antiviral etc. at present, many kinds also have the advantage such as low toxicity, low residue.Since exploitation in 1963 first oxime ester pesticides tranid (Tranid), in succession develop the oxime carbamate insecticides such as aldicarb (Aldicard), methomyl (Methomy1), thiofanox (Tbiofanox) and alanycarb (Alanyacarb), oxime phosphoric acid ester sterilant Volaton (Phoxime), phoxiom_methyl (Phoxime-methy1) and chlorphoxim (Chlorpoxime) and there is the sterilant phosphorus Asia prestige of organophosphorus and oxime carbamate dual structure.Wherein methomyl, aldicarb and Volaton etc. have applied the many decades time, are still large pesticide species in the world at present.In the eighties in 20th century after a while except a few oxime ester pesticide, the great majority of exploitation are all weedicides.The nineties in 20th century, oximes Agrochemicals is rapid, develops large quantities of sterilant and weedicide.The molecular designing of current oxime compounds, one of synthesis and the bioactivity research focus remaining pesticides discovery.
Rosin is the thick liquid be secreted from pine tree and a kind of natural resin being distilled and obtain, and main component is the resinous acid of tricyclic diterpene structure.China is rosin production big country, and annual production ranks first in the world.Rosin acrylic acid is the diprotic acid of the luxuriant and rich with fragrance skeleton of tricyclic diterpene that rosin and vinylformic acid are obtained by reacting by Diels-Alder Diene-addition, has two active carboxyl structure.At present, the existing research applying it to coating, tackiness agent, tensio-active agent etc., but have not been reported in biological activity field.
Summary of the invention
The object of this invention is to provide two oxime ester derivative of a kind of propylene Korean pine and preparation method thereof and antibacterial application, products therefrom activity is high, and cost is low, and preparation method is simple.
The present invention adopts following technical scheme: the two oxime ester derivative of a kind of propylene Korean pine, and general structure is as follows:
Wherein R
1for any one in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, rubigan; R
2for any one in-H, methyl, phenmethyl, benzyl, or R
1and R
2cheng Huanwei cyclobutyl.
Prepare a method for the two oxime ester derivative of described propylene Korean pine, by following formula reaction,
Wherein R
1for any one in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, rubigan; R
2for any one in-H, methyl, phenmethyl, phenyl, or R
1and R
2cheng Huanwei cyclobutyl.
Described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, triphosgene; The temperature of reaction of chloride is the reflux temperature of chloride reagent; The ratio 1: 2.0 ~ 4.0 that propylene Korean pine acyl chlorides and oxime compounds press amount of substance reacts.
Described aldehydes or ketones is any one in acetaldehyde, acetone, phenyl aldehyde, methyl phenyl ketone, 1,3-dibenzyl ketone, parachloroacetophenone, 4-methoxyacetophenone, benzophenone, p-methyl aceto phenone, p-tolyl aldehyde, pimelinketone, benzyl acetone.
Described acid binding agent is any one in sodium carbonate, sodium bicarbonate, triethylamine, pyridine.
The two oxime ester derivative of described propylene Korean pine is preparing the application in sterilant.
Beneficial effect:
1. the present invention is with biomass resource rosin derivative--and rosin acrylic acid is raw material, is incorporated in oxime compounds, prepares two oxime ester derivatives of rosin acrylic acid by the greasiness ring structure that condenses of rosin.Not only increase the fat-soluble of this compounds, and improve the added value of rosin.
2. bacteriostatic activity test of the present invention adopts filter paper enzyme.Experimental result shows, the present invention synthesis compound a, b, c, d and e to colibacillary fungistatic effect higher than commercially available sterilant bromogeramine; The inhibition zone diameter of bromogeramine is 9.66mm, and the inhibition zone diameter of compound a, b, c, d and e reaches 12.17mm, 10.00mm, 10.33mm, 9.67mm and 9.67mm respectively.
Embodiment
The present invention's rosin acrylic acid used is according to the method preparation in contriver openly patent of invention " preparation method of rosin acrylic acid " (publication number: CN101591238A).Described embodiment is to citing of the present invention below, instead of limitation of the invention.
Embodiment 1
The two oxime ester derivative of a kind of propylene Korean pine, general structure is as follows:
Wherein R
1for any one in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, rubigan; R
2for any one in-H, methyl, phenmethyl, benzyl, or R
1and R
2cheng Huanwei cyclobutyl.
Prepare a method for the two oxime ester derivative of described propylene Korean pine, by following formula reaction,
Wherein R
1for any one in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, rubigan; R
2for any one in-H, methyl, phenmethyl, benzyl, or R
1and R
2cheng Huanwei cyclobutyl.When preparing propylene Korean pine acyl chlorides, operable solvent is methylene dichloride, trichloromethane, tetrahydrofuran (THF); When preparing oxime compounds, operable solvent is dehydrated alcohol, anhydrous methanol, acetone; When preparing the two oxime ester derivative of propylene Korean pine, operable solvent is the mixed solvent of methylene dichloride and triethylamine or pyridine.
Described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, triphosgene; The temperature of reaction of chloride is the reflux temperature of chloride reagent; The ratio 1: 2.0 ~ 4.0 that obtained propylene Korean pine acyl chlorides and oxime compounds press amount of substance reacts.
Described aldehydes or ketones is any one in acetaldehyde, acetone, phenyl aldehyde, methyl phenyl ketone, 1,3-dibenzyl ketone, parachloroacetophenone, 4-methoxyacetophenone, benzophenone, p-methyl aceto phenone, p-tolyl aldehyde, pimelinketone, benzyl acetone.
Described acid binding agent is any one in sodium carbonate, sodium bicarbonate, triethylamine, pyridine.
With the two oxime ester derivative of described propylene Korean pine for activeconstituents is preparing the application in sterilant.
Embodiment 2
Compound a
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol p-tolyl aldehyde, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 1.0mol sodium bicarbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain p-tolyl aldehyde oxime with ethanol-hexanaphthene recrystallization.
0.06mol p-tolyl aldehyde oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.0 ~ 5 DEG C drips aforesaid propylene Korean pine acyl chlorides, reacts 12h under dropwising rear room temperature.React complete, separating-purifying obtains compound a.Yield 78.0%, m.p.:108.9-110.3 DEG C of .IR (cm
-1): 2932,2867 (-CH
3,-CH
2); 1743 (C=O); 1607 (C=N); 812 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 8.35 (S, H ,-CH=N-); 8.26 (S, H ,-CH=N-); (7.58-7.65 m, 4H, Ar-H); (7.17-7.26 m, 4H, Ar-H); (5.40 S, H, C=CH-); 2.60 (S, H ,=CH-(CH
3)
2); 2.36-2.38 (m, H ,-CH-C=O-); 2.17 (m, 6H, CH
3-Ar); 1.82-1.85 (m, 3H ,-CH-); 1.05-1.78 (m, 14H ,-CH
2-); 0.65-1.56 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 631 (M+Na
+) .C
39h
48n
2o
4ultimate analysis (calculated value)/%:C, 76.94 (76.46); H, 7.95 (8.41); N, 4.60 (4.45).
Embodiment 3
Compound b
In the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to dissolution of solid, add 0.05mol phosphorus trichloride, after reflux 4h, leave standstill and filter.Decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol acetone, 0.15mol oxammonium hydrochloride and 150mL anhydrous methanol, be stirred to dissolution of solid.Under room temperature, add 1.0mol sodium carbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain acetoxime with ethanol-hexanaphthene recrystallization.
0.06mol acetoxime is added, 40mL methylene dichloride and 10mL pyridine in 250mL there-necked flask.-5 ~ 0 DEG C drips aforesaid propylene Korean pine acyl chlorides, reacts 24h under dropwising rear room temperature.React complete, separating-purifying obtains compound b.Yield 79.4%, m.p.:87.1-87.5 DEG C of .IR (cm
-1): 2927,2865 (-CH
3,-CH
2); 1734 (C=O); 1642 (C=N) .5.38-5.40 (m, H, C=CH-); 2.52-2.57 (m, H ,=CH-(CH
3)
2); 2.33-2.37 (m, H ,-CH-C=O-); 2.03-2.17 (S, 3H ,-CH-); 1.67-2.06 (S, 12H, N=C-(CH
3)
2); 1.03-1.57 (m, 14H ,-CH
2-); 0.61-1.14 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 485 (M+H
+) .C
29h
44n
2o
4ultimate analysis (calculated value)/%:C, 71.87 (71.79); H, 9.15 (9.46); N, 5.78 (5.48).
Embodiment 4
Compound c
In the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL trichloromethane, be stirred to dissolution of solid, add 0.05mol phosphorus pentachloride, after reflux 4h, leave standstill and filter.Decompression steams solvent, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol benzyl acetone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, drip 15mL triethylamine.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain benzyl acetone oxime with ethanol-hexanaphthene recrystallization.
0.06mol benzyl acetone oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides at 0 ~ 5 DEG C, under dropwising rear room temperature, react 12h.React complete, separating-purifying obtains compound c.Yield 85%, m.p.56.0-56.6 DEG C of .IR (cm
-1): 2927,2864 (-CH
3,-CH
2); 1750 (C=O); 1642 (C=N); 746,699 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 7.03-7.30 (m, 10H, Ar-H); 5.36 (S, H, C=CH-); 4.17 (m, 4H ,-CH
2-Ar); 2.61 (S, H ,=CH-(CH
3)
2); 2.33-2.43 (m, H ,-CH-C=O-); 1.61-1.97 (m, 3H ,-CH-); 1.55 (S, 6H, N=C-CH
3); 0.98-1.48 (m, 18H ,-CH
2-); 0.57-1.19 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s687 (M+Na
+) .C
43h
56n
2o
4ultimate analysis (calculated value)/%:C, 77.67 (77.57); H, 8.49 (8.50); N, 4.21 (4.30).
Embodiment 5
Compound d
0.02mol rosin acrylic acid and 80mL tetrahydrofuran (THF) is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol triphosgene, after reflux 4h, decompression steams solvent and excessive triphosgene, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol p-methyl aceto phenone, 0.15mol oxammonium hydrochloride and 150mL acetone, be stirred to dissolution of solid.Under room temperature, drip 15mL pyridine.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain p-methyl aceto phenone oxime with ethanol-hexanaphthene recrystallization.
0.06mol p-methyl aceto phenone oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides at 0 ~ 5 DEG C, under dropwising rear room temperature, react 24h.React complete, separating-purifying obtains compound d.Yield 85%, m.p.78.9-80.1 DEG C, IR (cm
-1): 2929,2864 (-CH
3,-CH
2); 1748 (C=O); 1602 (C=N); 815 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 7.64 (t, J=8.2Hz, 4H, Ar-H); (7.15-7.26 m, 4H, Ar-H); (5.42 S, H, C=CH-); 2.60 (S, H ,=CH-(CH
3)
2); 2.31-2.37 (m, H ,-CH-C=O-); 2.17 (m, 6H, CH
3-Ar); 1.63-1.67 (S, 3H ,-CH-); 1.58 (S, 6H, N=C-CH
3); 1.05-1.57 (m, 14H ,-CH
2-); 0.67-1.28 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 659 (M+Na
+) .C
41h
52n
2o
4ultimate analysis (calculated value)/%:C, 77.32 (77.84); H, 8.23 (8.40); N, 4.40 (4.10).
Embodiment 6
Verbindung
In the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to dissolution of solid, add 0.05mol oxalyl chloride, after reflux 4h, leave standstill and filter.Decompression steams solvent, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol pimelinketone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 0.5mol sodium carbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain cyclohexanone-oxime with ethanol-hexanaphthene recrystallization.
0.08mol cyclohexanone-oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides at 0 ~ 5 DEG C, under dropwising rear room temperature, react 12h.React complete, separating-purifying obtains Verbindung.Yield 85%, m.p.:61.9-62.1 DEG C; IR:
2861 (-CH
3,-CH
2), 1744 (C=O), 1639 (C=N) cm
-1.
1hNMR (CDCl
3, 300MHz): δ=5.37 (S, H, C=CH-), 2.47-2.66 (S, H ,=C
h-(CH
3)
2), 2.23-2.48 (m, H ,-CH-C=O-), 1.93-1.97 (S, 3H ,-CH-), 1.21-1.85 (m, 34H ,-CH
2-), 0.62-1.05 (S, 12H ,-CCH
3) ppm; MS (ESI (+)) m/s 565 (M+H
+) .C
35h
52n
2o
4ultimate analysis (calculated value)/%:C, 74.43 (73.99); H, 9.28 (9.24); N, 4.96 (4.48).
Embodiment 7
Compound f
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol acetaldehyde, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 0.5mol sodium carbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain ethylidenehydroxylamine with ethanol-hexanaphthene recrystallization.
0.06mol ethylidenehydroxylamine is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Aforesaid propylene Korean pine acyl chlorides is dripped at 0 ~ 5 DEG C.After dropwising, under room temperature, react 12h.React complete, separating-purifying obtains compound a.Yield 70.4%, m.p.175.0-176.2 DEG C of .IR (cm
-1): 2929,2861 (-CH
3,-CH
2); 1742 (C=O); 1633 (C=N).
1hNMR (CDCl
3. δ/ppm.300MHz), 8.35 (S, H ,-CH=N-); 8.29 (S, H ,-CH=N-); 5.40 (S, H, C=CH-); 2.59 (S, H ,=CH-(CH
3)
2); 2.34-2.35 (m, H ,-CH-C=O-); 1.86-1.91 (S, 3H ,-CH-); 1.73-1.77 (m, 6H, CH
3-CH=N-); 1.07-1.55 (m, 14H ,-CH
2-); 0.65-1.33 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 457 (M+H
+) .C
27h
40n
2o
4ultimate analysis (calculated value)/%:C, 71.02 (70.88); H, 8.83 (8.70); N, 6.13 (6.50).
Embodiment 8
Compound g
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol phenyl aldehyde, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 1.0mol sodium bicarbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain benzaldoxime with ethanol-hexanaphthene recrystallization.
0.08mol benzaldoxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.0 DEG C drips aforesaid propylene Korean pine acyl chlorides, reacts 24h under dropwising rear room temperature.React complete, separating-purifying obtains compound b.Yield 65.8%, m.p.:172.9-173.6 DEG C of .IR (cm
-1): 2924,2864 (-CH
3,-CH
2); 1766 (C=O); 1612 (C=N); 756,695 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 8.39 (S, H ,-CH=N-); 8.30 (S, H ,-CH=N-); (7.69-7.76 m, 4H, Ar-H); (7.26-7.47 m, 6H, Ar-H); (5.40 S, H, C=CH-); 2.60 (S, H ,=CH-(CH
3)
2); 2.37-2.47 (m, H ,-CH-C=O-); 1.83-1.97 (S, 3H ,-CH-); 1.17-1.71 (m, 14H ,-CH
2-); 0.63-1.27 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 581 (M+H
+) .C
37h
44n
2o
4ultimate analysis (calculated value)/%:C, 76.52 (76.31); H, 7.64 (8.06); N, 4.82 (4.60).
Embodiment 9
Compound h
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol phosphorus pentachloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol methyl phenyl ketone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 0.5mol pyridine in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain acetophenone oxime with ethanol-hexanaphthene recrystallization.
0.08mol acetophenone oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.-5 ~ 0 DEG C drips aforesaid propylene Korean pine acyl chlorides, reacts 24h under dropwising rear room temperature.React complete, separating-purifying obtains Verbindung.Yield 84%, m.p.167.3-168.9 DEG C of .IR (cm
-1): 2931,2869 (-CH
3,-CH
2); 1743 (C=O); 1612 (C=N); 754,689 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 7.70-7.76 (m, 4H, Ar-H); (7.36-7.49 m, 6H, Ar-H); (5.41 S, H, C=CH-); 2.55 (S, H ,=CH-(CH
3)
2); 2.36-2.47 (m, H ,-CH-C=O-); 1.83-1.99 (S, 3H ,-CH-); 1.56 (S, 6H, N=C-CH
3); 0.97-1.53 (m, 14H ,-CH
2-); 0.99-1.44 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 609 (M+H
+) .C
27h
40n
2o
4ultimate analysis (calculated value)/%:C, 76.94 (77.26); H, 7.95 (7.68); N, 4.60 (4.65).
Embodiment 10
Compound i
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol phosphorus trichloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol1,3-dibenzyl acetone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, drip 20mL pyridine.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, with obtained 1, the 3-dibenzyl acetoxime of ethanol-hexanaphthene recrystallization.
0.06mol1 is added, 3-dibenzyl acetoxime, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides at 0 ~ 5 DEG C, under dropwising rear room temperature, react 24h.React complete, separating-purifying obtains compound g.Yield 60%, IR (cm
-1): 2926,2864 (-CH
3,-CH
2); 1748 (C=O); 1634 (C=N); 752,699 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 7.19-7.29 (m, 20H, Ar-H); 5.38 (S, H, C=CH-); 2.88 (m, 8H ,-CH
2-Ar); 2.83-2.95 (m, H ,=CH-(CH
3)
2); 2.61-2.73 (m, H ,-CH-C=O-); 2.28-2.40 (S, 3H ,-CH-); 1.06-1.99 (m, 14H ,-CH
2-); 0.62-1.17 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 811 (M+Na
+) .C
53h
60n
2o
4ultimate analysis (calculated value)/%:C, 80.67 (80.55); H, 7.66 (7.59); N, 3.55 (3.60).
Embodiment 11
Compound j
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol parachloroacetophenone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 0.5mol triethylamine in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain parachloroacetophenone oxime with ethanol-hexanaphthene recrystallization.
0.08mol parachloroacetophenone oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides under 5 DEG C of conditions, under dropwising rear room temperature, react 24h.React complete, separating-purifying obtains compound j.Yield 65.8%, m.p.85.7-86.6 DEG C, Yield:65.8%.IR (cm
-1): 2929,2865 (-CH
3,-CH
2); 1753 (C=O); 1614 (C=N); 829 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 7.66-7.72 (m, 4H, Ar-H); (7.32-7.39 m, 4H, Ar-H); (5.42 S, H, C=CH-); 2.54 (S, H ,=CH-(CH
3)
2); 2.42-2.49 (m, H ,-CH-C=O-); 2.31-2.36 (S, 3H ,-CH-); 1.54 (S, 6H, N=C-CH
3); 1.05-1.50 (m, 14H ,-CH
2-); 0.67-1.29 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 699 (M+Na
+) .C
39h
46cl
2n
2o
4ultimate analysis (calculated value)/%:C, 69.12; H, 6.84; N, 4.13.Found:C, 68.80; H, 6.92; N, 3.89.
Embodiment 12
Compound k
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol benzophenone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 0.5mol sodium carbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain diphenylketoxime with ethanol-hexanaphthene recrystallization.
0.06mol diphenylketoxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides at 0 ~ 5 DEG C, under dropwising rear room temperature, react 12h.React complete, separating-purifying obtains compound 1.Yield 85%, m.p.71.8-72.1 DEG C, Yield:65.8%.IR (cm
-1): 2928,2863 (-CH
3,-CH
2); 1754 (C=O); 1667 (C=N); 775,695 (Ar-H) .7.46-7.57 (m, 8H, Ar-H); (7.25-7.40 m, 12H, Ar-H); (5.29 S, H, C=CH-); 2.50 (S, H ,=CH-(CH
3)
2); 2.31-2.40 (m, H ,-CH-C=O-); 2.16 (S, 3H ,-CH-); 0.96-1.54 (m, 14H ,-CH
2-); 0.48-1.32 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 733 (M+H
+) .C
49h
52n
2o
4ultimate analysis (calculated value)/%:C, 80.30 (79.98); H, 7.15 (7.26); N, 3.82 (4.05).
Embodiment 13
Compound 1
0.02mol rosin acrylic acid and 80mL methylene dichloride is added in the there-necked flask of 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess thionyl chloride, obtained propylene Korean pine acyl chlorides.
In 500mL there-necked flask, add 0.1mol p-methoxy-acetophenone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to dissolution of solid.Under room temperature, add 0.5mol sodium carbonate in batches, add complete in 30 minutes.TLC monitors reaction process.React complete, filter, filtrate is dropped in frozen water, separates out solid.Filtration, drying, obtain p-methoxy-acetophenone oxime with ethanol-hexanaphthene recrystallization.
0.06mol p-methoxy-acetophenone oxime is added, 40mL methylene dichloride and 10mL triethylamine in 250mL there-necked flask.Drip aforesaid propylene Korean pine acyl chlorides at 0 ~ 5 DEG C, under dropwising rear room temperature, react 24h.React complete, separating-purifying obtains compound i.Yield 90%, m.p.74.8-75.2 DEG C, Yield:65.8%.IR (cm
-1): 2925,2864 (-CH
3,-CH
2); 1749 (C=O); 1605 (C=N); 831 (Ar-H).
1hNMR (CDCl
3. δ/ppm.300MHz), 7.71 (t, J=8.7Hz, 4H, Ar-H); 6.88 (t, J=9.0Hz, 4H, Ar-H); 5.42 (S, H, C=CH-); 3.82 (m, 6H, CH
3-O-); 2.62 (S, H ,=CH-(CH
3)
2); 2.42-2.50 (m, H ,-CH-C=O-); 2.33 (d, J=13Hz, 3H ,-CH-); 2.30 (S, 6H, N=C-CH
3); 1.05-1.54 (m, 14H ,-CH
2-); 0.67-1.28 (S, 12H ,-CCH
3) .MS (ESI (+)) m/s 691 (M+Na
+) .C
41h
52n
2o
4ultimate analysis (calculated value)/%:C, 73.62 (74.05); H, 7.84 (7.98); N, 4.19 (4.03).
Embodiment 13
Adopt filter paper enzyme, precision takes sample respectively, is placed in sterile test tube, adds ethanol in proper amount and dissolves, add sterilized water and obtain 256 μ g/mL solution.Be tested bacterial classification with intestinal bacteria, beef extract-peptone is adopted to cultivate tested bacteria, to take a morsel (scraping 1 ~ 2 ring) Fresh bacterial from above-mentioned substratum with transfering loop, add in nutrient solution, and take turns doing 10 times and increase progressively diluent, select bacterial concentration to be (5.0 ~ 10.0) × 10
6the diluent of cfu/ml uses bacterium liquid as test.Get 1ml bacteria suspension to be uniformly coated on the beef extract-peptone plate culture medium of 90mm.Cut-off footpath is that 6mm aseptic filter paper is drawn liquid to be measured and is placed on and is coated with on the flat board of bacteria suspension, the repetition of 3, each sample.Cultivate after 24 hours and observe, measure inhibition zone diameter around filter paper.
Claims (6)
1. the two oxime ester derivative of propylene Korean pine, it is characterized in that, general structure is as follows:
Wherein R
1for any one in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, rubigan; R
2for any one in-H, methyl, phenmethyl, benzyl, or R
1and R
2cheng Huanwei cyclobutyl.
2. prepare a method for the two oxime ester derivative of propylene Korean pine according to claim 1, it is characterized in that: by following formula reaction,
Wherein R
1for any one in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, rubigan; R
2for any one in-H, methyl, phenmethyl, phenyl, or R
1and R
2cheng Huanwei cyclobutyl; Described rosin acrylic acid with any one in methylene dichloride, trichloromethane or tetrahydrofuran (THF) for solvent; During described aldehydes or ketones reaction with dehydrated alcohol or acetone for solvent; Be solvent with methylene dichloride in oxime compounds reaction.
3. prepare the method for the two oxime ester derivative of propylene Korean pine as claimed in claim 2, it is characterized in that: described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, triphosgene; The temperature of reaction of chloride is the reflux temperature of chloride reagent; Ratio 1:2.0 ~ 4.0 that propylene Korean pine acyl chlorides and oxime compounds press amount of substance are reacted.
4. prepare the method for the two oxime ester derivative of propylene Korean pine as claimed in claim 2, it is characterized in that: described aldehydes or ketones is any one in acetaldehyde, acetone, phenyl aldehyde, methyl phenyl ketone, 1,3-dibenzyl ketone, parachloroacetophenone, 4-methoxyacetophenone, benzophenone, p-methyl aceto phenone, p-tolyl aldehyde, pimelinketone, benzyl acetone.
5. prepare the method for the two oxime ester derivative of propylene Korean pine as claimed in claim 2, it is characterized in that: described acid binding agent is any one in sodium carbonate, sodium bicarbonate, triethylamine, pyridine.
6. the two oxime ester derivative of propylene Korean pine according to claim 1 is being prepared for the application in colibacillary sterilant.
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