CN102219707A - 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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- CN102219707A CN102219707A CN2011101033206A CN201110103320A CN102219707A CN 102219707 A CN102219707 A CN 102219707A CN 2011101033206 A CN2011101033206 A CN 2011101033206A CN 201110103320 A CN201110103320 A CN 201110103320A CN 102219707 A CN102219707 A CN 102219707A
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- Prior art keywords
- korean pine
- add
- methyl
- oxime
- propylene korean
- Prior art date
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- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 oxime compound Chemical class 0.000 claims abstract description 34
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 42
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 41
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 41
- 238000010992 reflux Methods 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- 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
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 24
- 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 abstract description 24
- 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 abstract description 24
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 2
- 239000002994 raw material Substances 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000007787 solid Substances 0.000 description 36
- 229910052717 sulfur Inorganic materials 0.000 description 27
- 238000001035 drying Methods 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 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
- 238000012544 monitoring process Methods 0.000 description 12
- 238000001953 recrystallisation Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 9
- 150000003462 sulfoxides Chemical class 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- 239000003905 agrochemical Substances 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
- 230000001580 bacterial effect Effects 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000004141 diterpene derivatives Chemical group 0.000 description 2
- 239000002917 insecticide Substances 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
- 239000000575 pesticide Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 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 1
- 239000002028 Biomass Substances 0.000 description 1
- 0 CC(CCC1)(C(CC2)C3(CC4)C=C(*)C2C3C(ON=C(C)C)=O)C4C1(C)C(ON=C)=O Chemical compound CC(CCC1)(C(CC2)C3(CC4)C=C(*)C2C3C(ON=C(C)C)=O)C4C1(C)C(ON=C)=O 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
- 238000007259 addition reaction Methods 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
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 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
- 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
- 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
- 230000003248 secreting effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- 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 the natural product chemistry field, relating to the rosin acrylic acid is the method for the two oxime ester derivatives of feedstock production propylene Korean pine, also relates to the antibacterial application of this analog derivative.
Background technology
The oxime Ester is owing to have extensive biological activity, has been used to sterilant, Insecticides (tech) ﹠ Herbicides (tech), antitumor and antiviral etc. at present, and many kinds also have advantages such as low toxicity, low residue.Since developing first oxime ester pesticides tranid (Tranid) in 1963, aldicarb (Aldicard), methomyl (Methomy1), thiofanox (Tbiofanox) and alanycarb (Alanyacarb) the oxime carbamate insecticides of etc.ing have been developed in succession, oxime phosphoric acid ester sterilant Volaton (Phoxime), phoxiom_methyl (Phoxime-methy1) and chlorphoxim (Chlorpoxime) and have organophosphorus and the sterilant phosphorus of oxime carbamate dual structure Asia prestige.Wherein methomyl, aldicarb and Volaton etc. have been used the many decades time, are still large pesticide species in the world at present.After a while eighties in 20th century except that a few oxime ester insecticides, the great majority of exploitation all are weedicides.The nineties in 20th century, the development of oximes agricultural chemicals has been developed large quantities of sterilant and weedicide rapidly.At present the molecular designing of oxime compounds, synthetic and bioactivity research remain one of focus that agricultural chemicals formulates.
Rosin is the thick liquid of secreting out from pine tree and is distilled and a kind of natural resin of obtaining that main component is the resinous acid of tricyclic diterpene structure.China is rosin big producing country, and annual production ranks first in the world.The diprotic acid of the rosin acrylic acid luxuriant and rich with fragrance skeleton of tricyclic diterpene that to be rosin and vinylformic acid obtain by the addition reaction of Diels-Alder diene has two active carboxyl structure.At present, the existing research that applies it to coating, tackiness agent, tensio-active agent etc., but yet there are no report in the biological activity field.
Summary of the invention
The purpose of this invention is to provide two oxime ester derivatives of a kind of propylene Korean pine and preparation method thereof and antibacterial application, products therefrom is active high, and cost is low, and the preparation method is simple.
The present invention adopts following technical scheme: the two oxime ester derivatives of a kind of propylene Korean pine, and general structure is as follows:
R wherein
1Be in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, the rubigan any one; R
2Be in-H, methyl, phenmethyl, the benzyl any one, or R
1And R
2The Cheng Huanwei cyclobutyl.
A kind of method for preparing the two oxime ester derivatives of described propylene Korean pine is pressed the following formula reaction,
R wherein
1Be in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, the rubigan any one; R
2Be in-H, methyl, phenmethyl, the phenyl any one, or R
1And R
2The Cheng Huanwei cyclobutyl.
Described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, the triphosgene; The temperature of reaction of chloride is the reflux temperature of chloride reagent; Propylene Korean pine acyl chlorides reacts with the ratio 1: 2.0～4.0 that oxime compounds is pressed amount of substance.
Described aldehydes or ketones is acetaldehyde, acetone, phenyl aldehyde, methyl phenyl ketone, 1, any one in 3-dibenzyl ketone, parachloroacetophenone, 4-methoxyacetophenone, benzophenone, p-methyl aceto phenone, p-tolyl aldehyde, pimelinketone, the benzyl acetone.
Described acid binding agent is any one in yellow soda ash, sodium bicarbonate, triethylamine, the pyridine.
The application of the two oxime ester derivatives of described propylene Korean pine in the preparation sterilant.
Beneficial effect:
1. the present invention is with the biomass resource rosin derivative--and rosin acrylic acid is a raw material, rosiny is condensed the greasiness ring structure be incorporated in the oxime compounds, two oxime ester derivatives of preparation rosin acrylic acid.Not only increase the fat-soluble of this compounds, and improved the rosiny added value.
2. the filter paper method is adopted in bacteriostatic activity test of the present invention.Experimental result shows that synthetic compound a of the present invention, b, c, d and e are higher than commercially available sterilant bromogeramine to colibacillary fungistatic effect; 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 used rosin acrylic acid of the present invention is to disclose patent of invention " preparation method of rosin acrylic acid " (publication number: the method preparation CN101591238A) according to the contriver.Below described embodiment be to of the present invention for example, rather than limitation of the invention.
Embodiment 1
The two oxime ester derivatives of a kind of propylene Korean pine, general structure is as follows:
R wherein
1Be in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, the rubigan any one; R
2Be in-H, methyl, phenmethyl, the benzyl any one, or R
1And R
2The Cheng Huanwei cyclobutyl.
A kind of method for preparing the two oxime ester derivatives of described propylene Korean pine is pressed the following formula reaction,
R wherein
1Be in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, the rubigan any one; R
2Be in-H, methyl, phenmethyl, the benzyl any one, or R
1And R
2The Cheng Huanwei cyclobutyl.During preparation propylene Korean pine acyl chlorides, operable solvent is methylene dichloride, trichloromethane, tetrahydrofuran (THF); Operable solvent is dehydrated alcohol, anhydrous methanol, acetone during the preparation oxime compounds; Operable solvent is the mixed solvent of methylene dichloride and triethylamine or pyridine during the two oxime ester derivative of preparation propylene Korean pine.
Described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, the triphosgene; The temperature of reaction of chloride is the reflux temperature of chloride reagent; Propylene Korean pine acyl chlorides that makes and ratio 1: 2.0～4.0 reactions of oxime compounds by amount of substance.
Described aldehydes or ketones is acetaldehyde, acetone, phenyl aldehyde, methyl phenyl ketone, 1, any one in 3-dibenzyl ketone, parachloroacetophenone, 4-methoxyacetophenone, benzophenone, p-methyl aceto phenone, p-tolyl aldehyde, pimelinketone, the benzyl acetone.
Described acid binding agent is any one in yellow soda ash, sodium bicarbonate, triethylamine, the pyridine.
With the two oxime ester derivatives of described propylene Korean pine is the application of activeconstituents in the preparation sterilant.
Embodiment 2
Compound a
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol sulfur oxychloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol p-tolyl aldehyde, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add the 1.0mol sodium bicarbonate in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make the p-tolyl aldehyde oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol p-tolyl aldehyde oxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides, dropwises under the room temperature of back and reacts 12h.Reaction finishes, separate purify compound a.Yield 78.0%, m.p.:108.9-110.3 ℃ 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 the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol phosphorus trichloride, behind the reflux 4h, leave standstill filtration.Decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol acetone, 0.15mol oxammonium hydrochloride and 150mL anhydrous methanol, be stirred to the solid dissolving.Under the room temperature, add 1.0mol yellow soda ash in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make acetoxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol acetoxime, 40mL methylene dichloride and 10mL pyridine.-5～0 ℃ drips aforesaid propylene Korean pine acyl chlorides, dropwises under the room temperature of back and reacts 24h.Reaction finishes, separate purify compound b.Yield 79.4%, m.p.:87.1-87.5 ℃ 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 the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL trichloromethane, be stirred to the solid dissolving, add the 0.05mol phosphorus pentachloride, behind the reflux 4h, leave standstill filtration.Decompression steams solvent, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol benzyl acetone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, drip the 15mL triethylamine.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make the benzyl acetone oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol benzyl acetone oxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down, dropwises under the room temperature of back and reacts 12h.Reaction finishes, separate purify compound c.Yield 85%, m.p.56.0-56.6 ℃ 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL tetrahydrofuran (THF), be stirred to the solid dissolving, add the 0.05mol triphosgene, decompression steams solvent and excessive triphosgene behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol p-methyl aceto phenone, 0.15mol oxammonium hydrochloride and 150mL acetone, be stirred to the solid dissolving.Under the room temperature, drip the 15mL pyridine.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make the p-methyl aceto phenone oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol p-methyl aceto phenone oxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down, dropwises under the room temperature of back and reacts 24h.Reaction finishes, separate purify compound d.Yield 85%, m.p.78.9-80.1 ℃, 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 the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol oxalyl chloride, behind the reflux 4h, leave standstill filtration.Decompression steams solvent, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol pimelinketone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add 0.5mol yellow soda ash in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make cyclohexanone-oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.08mol cyclohexanone-oxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down, dropwises under the room temperature of back and reacts 12h.Reaction finishes, separate purify Verbindung.Yield 85%, m.p.:61.9-62.1 ℃; 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol sulfur oxychloride, behind the reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol acetaldehyde, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add 0.5mol yellow soda ash in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make ethylidenehydroxylamine with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol ethylidenehydroxylamine, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down.After dropwising, react 12h under the room temperature.Reaction finishes, separate purify compound a.Yield 70.4%, m.p.175.0-176.2 ℃ 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol sulfur oxychloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol phenyl aldehyde, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add the 1.0mol sodium bicarbonate in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make benzaldoxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.08mol benzaldoxime, 40mL methylene dichloride and 10mL triethylamine.0 ℃ drips aforesaid propylene Korean pine acyl chlorides, dropwises under the room temperature of back and reacts 24h.Reaction finishes, separate purify compound b.Yield 65.8%, m.p.:172.9-173.6 ℃ 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol phosphorus pentachloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol methyl phenyl ketone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add the 0.5mol pyridine in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make acetophenone oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.08mol acetophenone oxime, 40mL methylene dichloride and 10mL triethylamine.-5～0 ℃ drips aforesaid propylene Korean pine acyl chlorides, dropwises under the room temperature of back and reacts 24h.Reaction finishes, separate purify Verbindung.Yield 84%, m.p.167.3-168.9 ℃ 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol phosphorus trichloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
Add 0.1mol1 in the 500mL there-necked flask, 3-dibenzyl acetone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol are stirred to the solid dissolving.Under the room temperature, drip the 20mL pyridine.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make 1 with ethanol-hexanaphthene recrystallization, 3-dibenzyl acetoxime.
In the 250mL there-necked flask, add 0.06mol1,3-dibenzyl acetoxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down, dropwises under the room temperature of back and reacts 24h.Reaction finishes, separate purify 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol sulfur oxychloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol parachloroacetophenone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add the 0.5mol triethylamine in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make the parachloroacetophenone oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.08mol parachloroacetophenone oxime, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides under 5 ℃ of conditions, dropwise under the room temperature of back and react 24h.Reaction finishes, separate purify compound j.Yield 65.8%, m.p.85.7-86.6 ℃, 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol sulfur oxychloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol benzophenone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add 0.5mol yellow soda ash in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make diphenylketoxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol diphenylketoxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down, dropwises under the room temperature of back and reacts 12h.Reaction finishes, separate purify compound 1.Yield 85%, m.p.71.8-72.1 ℃, 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
In the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, add 0.02mol rosin acrylic acid and 80mL methylene dichloride, be stirred to the solid dissolving, add the 0.05mol sulfur oxychloride, decompression steams solvent and excess chlorination sulfoxide behind the reflux 4h, makes propylene Korean pine acyl chlorides.
In the 500mL there-necked flask, add 0.1mol p-methoxy-acetophenone, 0.15mol oxammonium hydrochloride and 150mL dehydrated alcohol, be stirred to the solid dissolving.Under the room temperature, add 0.5mol yellow soda ash in batches, add in 30 minutes and finish.TLC monitoring reaction process.Reaction finishes, and filters, and filtrate is dropped in the frozen water, separates out solid.Filtration, drying make the p-methoxy-acetophenone oxime with ethanol-hexanaphthene recrystallization.
In the 250mL there-necked flask, add 0.06mol p-methoxy-acetophenone oxime, 40mL methylene dichloride and 10mL triethylamine.0～5 ℃ drips aforesaid propylene Korean pine acyl chlorides down, dropwises under the room temperature of back and reacts 24h.Reaction finishes, separate purify compound i.Yield 90%, m.p.74.8-75.2 ℃, 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 the filter paper method, precision takes by weighing sample respectively, places sterile test tube, adds an amount of dissolve with ethanol, adds sterilized water and gets 256 μ g/mL solution.With intestinal bacteria for being tried bacterial classification, adopt beef extract-peptone to cultivate tested bacteria, from above-mentioned substratum (scraping 1～2 ring) the fresh bacterium that takes a morsel, add in the nutrient solution with transfering loop, and take turns doing 10 times and increase progressively diluent, selecting bacterial concentration is (5.0～10.0) * 10
6The diluent of cfu/ml is as test bacterium liquid.Get on the beef extract-peptone plate culture medium that the 1ml bacteria suspension is uniformly coated on 90mm.Cut-off is directly drawn liquid to be measured for the 6mm aseptic filter paper and is placed on the flat board that is coated with bacteria suspension, 3 repetitions of each sample.Cultivate after 24 hours and observe, measure filter paper inhibition zone diameter on every side.
Claims (6)
1. two oxime ester derivatives of a propylene Korean pine is characterized in that general structure is as follows:
R wherein
1Be in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, the rubigan any one; R
2Be in-H, methyl, phenmethyl, the benzyl any one, or R
1And R
2The Cheng Huanwei cyclobutyl.
2. method for preparing the two oxime ester derivatives of the described propylene Korean pine of claim 1 is characterized in that: press following formula and reacts,
R wherein
1Be in methyl, phenyl, phenmethyl, styroyl, p-methylphenyl, p-methoxyphenyl, the rubigan any one; R
2Be in-H, methyl, phenmethyl, the phenyl any one, or R
1And R
2The Cheng Huanwei cyclobutyl.
3. the method for preparing the two oxime ester derivatives 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, the triphosgene; The temperature of reaction of chloride is the reflux temperature of chloride reagent; Propylene Korean pine acyl chlorides reacts with the ratio 1: 2.0～4.0 that oxime compounds is pressed amount of substance.
4. the method for preparing the two oxime ester derivatives of propylene Korean pine as claimed in claim 2, it is characterized in that: described aldehydes or ketones is acetaldehyde, acetone, phenyl aldehyde, methyl phenyl ketone, 1, any one in 3-dibenzyl ketone, parachloroacetophenone, 4-methoxyacetophenone, benzophenone, p-methyl aceto phenone, p-tolyl aldehyde, pimelinketone, the benzyl acetone.
5. the method for preparing the two oxime ester derivatives of propylene Korean pine as claimed in claim 2, it is characterized in that: described acid binding agent is any one in yellow soda ash, sodium bicarbonate, triethylamine, the pyridine.
6. the application of the two oxime ester derivatives of the described propylene Korean pine of claim 1 in the preparation sterilant.
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| CN109957349A (en) * | 2017-12-14 | 2019-07-02 | 常州强力电子新材料股份有限公司 | Anisotropic conductive film, the composition for being used to form it and its application |
| CN116730932A (en) * | 2023-06-12 | 2023-09-12 | 西北农林科技大学 | Preparation and application of propylene pimara (1, 5-o-nitrobenzyl) -1,2, 4-triazole |
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| US20080096115A1 (en) * | 2004-08-18 | 2008-04-24 | Junichi Tanabe | Oxime Ester Photoinitiators |
| CN101870663A (en) * | 2010-07-15 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric amide derivative as well as preparation method and application thereof |
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| US20080096115A1 (en) * | 2004-08-18 | 2008-04-24 | Junichi Tanabe | Oxime Ester Photoinitiators |
| CN101870663A (en) * | 2010-07-15 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric amide derivative as well as preparation method and application thereof |
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| CN109957349A (en) * | 2017-12-14 | 2019-07-02 | 常州强力电子新材料股份有限公司 | Anisotropic conductive film, the composition for being used to form it and its application |
| CN116730932A (en) * | 2023-06-12 | 2023-09-12 | 西北农林科技大学 | Preparation and application of propylene pimara (1, 5-o-nitrobenzyl) -1,2, 4-triazole |
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