CN115093341B - 2-cyclopentene-1-alcohol derivative and synthetic method and application thereof - Google Patents
2-cyclopentene-1-alcohol derivative and synthetic method and application thereof Download PDFInfo
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- CN115093341B CN115093341B CN202210924582.7A CN202210924582A CN115093341B CN 115093341 B CN115093341 B CN 115093341B CN 202210924582 A CN202210924582 A CN 202210924582A CN 115093341 B CN115093341 B CN 115093341B
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- 238000010189 synthetic method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000006196 deacetylation Effects 0.000 claims abstract description 4
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- PSBABBDEUFNFKJ-UHFFFAOYSA-N cyclopent-2-en-1-ol Chemical class OC1CCC=C1 PSBABBDEUFNFKJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 238000004809 thin layer chromatography Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002274 desiccant Substances 0.000 claims description 4
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- 230000001427 coherent effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 230000000749 insecticidal effect Effects 0.000 abstract description 11
- 239000000575 pesticide Substances 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 8
- 241000500437 Plutella xylostella Species 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 6
- 229920000053 polysorbate 80 Polymers 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 241001124076 Aphididae Species 0.000 description 5
- NWZXFAYYQNFDCA-UHFFFAOYSA-N cyclopenten-1-ol Chemical compound OC1=CCCC1 NWZXFAYYQNFDCA-UHFFFAOYSA-N 0.000 description 5
- 241001600408 Aphis gossypii Species 0.000 description 4
- 241000255967 Helicoverpa zea Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- CFAKWWQIUFSQFU-UHFFFAOYSA-N 2-hydroxy-3-methylcyclopent-2-en-1-one Chemical compound CC1=C(O)C(=O)CC1 CFAKWWQIUFSQFU-UHFFFAOYSA-N 0.000 description 2
- RGPBQGGBWIMGMA-BJMVGYQFSA-N 5-[(e)-[5-(4-bromophenyl)-6-hydroxy-3,6-dihydro-1,3,4-oxadiazin-2-ylidene]methyl]-1h-pyrimidine-2,4-dione Chemical compound OC1O\C(=C\C=2C(NC(=O)NC=2)=O)NN=C1C1=CC=C(Br)C=C1 RGPBQGGBWIMGMA-BJMVGYQFSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000985245 Spodoptera litura Species 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229930184190 jasminoid Natural products 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- LKVXQCKDIYHFGZ-UHFFFAOYSA-N n-naphthalen-1-yl-3-oxobutanamide Chemical compound C1=CC=C2C(NC(=O)CC(=O)C)=CC=CC2=C1 LKVXQCKDIYHFGZ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FXUAIOOAOAVCGD-WCTZXXKLSA-N swainsonine Chemical compound C1CC[C@@H](O)[C@@H]2[C@H](O)[C@H](O)CN21 FXUAIOOAOAVCGD-WCTZXXKLSA-N 0.000 description 1
- FXUAIOOAOAVCGD-UHFFFAOYSA-N swainsonine Natural products C1CCC(O)C2C(O)C(O)CN21 FXUAIOOAOAVCGD-UHFFFAOYSA-N 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/82—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Insects & Arthropods (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and discloses a 2-cyclopentene-1-alcohol derivative and a synthesis method thereof, which take an alpha-carbonyl cyclopropylamide compound and a 1, 3-dicarbonyl compound as raw materials, take organic base as a catalyst, dissolve in an organic solvent, and carry out [3+2] cyclization/deacetylation/oxygen oxidation reaction at 80-100 ℃ to quickly construct a series of polyfunctional 2-cyclopentene-1-alcohol compounds; the method has the advantages of mild reaction conditions, diversified structures, easy operation, step economy and high yield. The 2-cyclopentene-1-alcohol derivative has excellent insecticidal activity and good application prospect in the field of pesticides.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a 2-cyclopentene-1-alcohol derivative, and a synthesis method and application thereof.
Background
Cyclopenten-2-ol and its derivatives are important components of various natural products and pharmaceutical intermediates, and researchers have obtained compounds containing core skeletons of cyclopenten-2-ol with various functions through separation, structural modification and chemical synthesis means from natural products, which have excellent biological activities in terms of pharmacological activities such as antibiosis, antitumor, antiviral, anti-HIV, disinsection, mite removal, weeding and the like, for example, cabavir (anti-HIV)/cyclofenthrin (weeding) and the like; it can also be used for preparing daily chemical products and edible essence such as maple lactone. In addition, they are also considered key synthetic intermediates for the natural products neplanocineAfredericamycinA analogue, jasminoids and (-) -swainsonine. In recent years the construction of the cyclopenten-2-ol backbone has attracted extensive attention by pharmaceutical chemists and researchers of synthetic chemistry and has achieved significant success. At present, common synthetic methods for cyclopenten-2-ol and analogues thereof mainly comprise: 1. cyclopentene-2-ol compounds are further synthesized by ring opening rearrangement reactions, metathesis reactions, and the like of cyclopentene-2-one or 1, 2-epoxypentane, for example, cyclopentene-cyclopentalactone intermediates formed by intermolecular cyclization of cyclopentadiene and aldehyde acid or intramolecular cyclization of cyclopentene carboxylic acid (Tetrahedron: asymmetry1997,22,3785; J.org.chem.1993,58, 5298); 2. ring opening of 1, 2-epoxycyclopentane catalyzed by vitamin B12 (Helv. Chim. Acta.,1991,74,1425) and oxidation of cyclopentene (Angew.Chem., int.Ed.,2007,46,5951). However, the conventional synthesis method has the disadvantages of complex starting materials, low universality, harsh reaction conditions, complicated synthesis steps, low final yield and the like.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a 2-cyclopenten-1-ol derivative, and a synthesis method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a 2-cyclopenten-1-ol derivative having the structural formula:
wherein R is 2 Selected from Me, et, ph, 4-MePh, 4-MeOPh, 4-ClPh, 2-MePh, 2,4-Me 2 C 6 H 3 One of 2-ClPh, bn, naphth;
R 3 selected from Me, et, ph, 4-MePh, 2-BrPh, 2-MePh, 4-NO 2 One of Ph and 2-furyl;
R 4 selected from Me, et, cyclohexyl, CF 3 、CONHPh、CONH(4-MePh)、CONH(4-MeOPh)、CONH(4-ClPh)、CONH(2-MePh)、CONHCH 2 Ph、CN、Ph、4-MePh、2-BrPh、2-MePh、4-NO 2 One of Ph, 4-MeOPh, 4-COOMePh, naphth.
A synthetic method of 2-cyclopentene-1-alcohol derivative takes alpha-carbonyl cyclopropylamide compound A and 1, 3-dicarbonyl compound B as raw materials, takes organic base as catalyst, and is dissolved in organic solvent to carry out [3+2] cyclization/deacetylation/oxygen oxidation reaction at 80-100 ℃ to prepare 2-cyclopentene-1-alcohol compound C;
the reaction route is as follows:
wherein R is 1 One selected from Me, et and Ph;
R 2 selected from Me, et, ph, 4-MePh, 4-MeOPh, 4-ClPh, 2-MePh, 2,4-Me 2 C 6 H 3 One of 2-ClPh, bn, naphth;
R 3 selected from Me, et, ph, 4-MePh, 2-BrPh, 2-MePh, 4-NO 2 One of Ph and 2-furyl;
R 4 selected from Me, et, cyclohexyl, CF 3 、CONHPh、CONH(4-MePh)、CONH(4-MeOPh)、CONH(4-ClPh)、CONH(2-MePh)、CONHCH 2 Ph、CN、Ph、4-MePh、2-BrPh、2-MePh、4-NO 2 One of Ph, 4-MeOPh, 4-COOMePh, naphth.
Further, the above-mentioned α -carbonyl cyclopropylamide compound a and 1, 3-dicarbonyl compound B have a molar ratio of 1:1 to 1.2mmol, the ratio of the dosage of the alpha-carbonyl cyclopropylamide compound A, the organic solvent and the organic base is 1mmol: 8-10 mL:1 to 1.5mmol.
Further, the organic base is one of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), N-Dimethylethanolamine (DABCO), 4-Dimethylaminopyridine (DMAP), 1, 5-diazabicyclo [4.3.0] -5-nonene (DBN) and pyridine.
Further, the organic solvent is one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetonitrile and ethanol.
Further, the reaction time is 8 to 10 hours.
Further, the synthesis method of the 2-cyclopentene-1-alcohol derivative comprises the steps of monitoring the reaction progress by using thin layer chromatography TLC, adding water into a reaction system to stop the reaction after the reactant A completely disappears, extracting by using an extracting agent, and combining organic phases; the organic phase is dried by a desiccant, filtered, concentrated and subjected to column chromatography to obtain the 2-cyclopentene-1-alcohol compound C.
Further, the extractant is dichloromethane, ethyl acetate, diethyl ether or chloroform.
Further, the organic coherent desiccant is anhydrous sodium sulfate, anhydrous calcium chloride or anhydrous magnesium sulfate.
Another object of the invention is to provide the use of a 2-cyclopenten-1-ol derivative for the preparation of a pesticide.
Further, the pesticide is a pesticide for preventing and controlling pests such as aphids, plutella xylostella, cotton bollworms and prodenia litura.
Insecticidal activity test: the agricultural insect is used for an indoor common screening activity experiment, an impregnation method is adopted for testing the insecticidal activity of the 2-cyclopentene-1-alcohol compound C, the 2-cyclopentene-1-alcohol compound C has good insecticidal activity under the common screening concentration (500 mug/mL), and the mortality of different insect pests (aphids, plutella xylostella, cotton bollworms and prodenia litura) is between 55% and 80%.
By adopting the technical scheme, the invention has the following advantages:
the synthetic method of the 2-cyclopentene-1-alcohol derivative has a concise and efficient synthetic route, uses an alpha-carbonyl cyclopropylamide compound and a 1, 3-dicarbonyl compound as starting materials, and rapidly constructs a series of polyfunctional 2-cyclopentene-1-alcohol compounds through a serial reaction process of intermolecular [3+2] cyclization reaction/deacetylation/oxygen oxidation reaction under a mild reaction condition; the method has the advantages of low cost and easy obtainment of raw materials, higher oxidation-reduction economy and route economy, mild reaction conditions, diversified structures, easy operation, step economy and high yield.
The 2-cyclopentene-1-alcohol derivative has excellent insecticidal activity, has good control effect on various agricultural pests such as aphids, plutella xylostella and the like, and has good application prospect in the field of pesticides.
Drawings
FIG. 1 is the target product C of example 1 1 Is a hydrogen spectrogram of (2);
FIG. 2 is the target product C of example 3 3 Hydrogen profile of (c).
Detailed Description
The invention will be described in further detail with reference to the following examples; however, the following examples are merely illustrative, and the present invention is not limited to these examples.
Example 1
Into a 50mL pressure-resistant bottle was charged α -carbonyl cyclopropylamide A 1 (0.203 g,1 mmol), acetylacetone B 1 (0.1 mL,1 mmol), DMF (6 mL), then DBU (0.15 mL,1 mmol) was added slowly and stirred at 80deg.C for 10h; TLC monitoring reaction, A 1 After complete disappearance, the reaction solution was poured into ice water, stirred vigorously, extracted three times with dichloromethane (3X 10 mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and purified by column chromatography to give the white product C 1 0.23g, yield 88%.
The specific reaction formula is:
compound C 1 A kind of electronic device 1 HNMR(CDCl 3 ,400MHz)：δ：1.99-2.04(m,4H),2.34(s,3H),2.62-2.68(m,1H),2.82-2.85(m,2H),3.20(s,1H),7.15(t,J＝8.0Hz,1H),7.33-7.37(q,J＝4.0Hz,2H),7.57(d,J＝8.0Hz,2H),8.29(s,1H)。
Compound C 1 Is used for testing the insecticidal activity: taking cotton aphids as a test object, and adopting an impregnation method; 10mg of Compound C was weighed out 1 The sample is dissolved by using a 5mL liquid-transfering gun to obtain 2mL of acetone/methanol mixed solvent, 18mL of aqueous solution containing 0.1% Tween-80 is added, and the mixture is fully and uniformly mixed to obtain 500 mug/mL measuring solution. The result shows that the death rate of cotton aphids after 24 hours reaches 70 percent.
Example 2
Into a 50mL pressure-resistant bottle was charged α -carbonyl cyclopropylamide A 2 (0.217 g,1 mmol), benzoylacetone B 2 (0.16 mL,1 mmol), DMSO (6 mL), then DBU (0.15 mL,1 mmol) was added slowly and stirred at 90deg.C for 10h; TLC monitoring reaction, A 2 After complete disappearance, the reaction solution was poured into ice water, stirred vigorously, extracted three times with dichloromethane (3X 10 mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and purified by column chromatography to give the white product C 2 0.28g, yield 85%.
The specific reaction formula is:
compound C 2 A kind of electronic device 1 HNMR(CDCl 3 ,400MHz)：δ：1.96-2.01(m,4H),2.37(s,3H),2.65-2.68(m,1H),2.81-2.86(m,2H),3.24(s,1H),7.05(d,J＝8.0Hz,2H),7.49(d,J＝8.0Hz,2H),7.52(t,J＝4.0Hz,1H)7.55-7.58(m,2H),7.71-7.73(m,2H),8.74(s,1H)。
Compound C 2 Is used for testing the insecticidal activity: using plutella xylostella as a test object, and adopting an immersion method; 10mg of Compound C was weighed out 2 The sample is dissolved by using a 5mL liquid-transfering gun to obtain 2mL of acetone/methanol mixed solvent, 18mL of aqueous solution containing 0.1% Tween-80 is added, and the mixture is fully and uniformly mixed to obtain 500 mug/mL measuring solution. The result shows that the death rate of the plutella xylostella after 48 hours reaches 55 percent.
Example 3
Into a 50mL pressure-resistant bottle was charged α -carbonyl cyclopropylamide A 1 (0.203 g,1 mmol), ethyl acetoacetate B 3 (0.14 mL,1.1 mmol), NMP (8 mL), and then DMAP (0.15 g,1.2 mmol) was slowly added and stirred at 100deg.C for 8h; TLC monitoring reaction, A 1 After complete disappearance, the reaction solution was poured into ice water, stirred vigorously, extracted three times with ethyl acetate (3X 10 mL), the organic phases combined, dried over anhydrous sodium sulfate, the solvent removed by rotary evaporation, and purified by column chromatography to give the white product C 3 0.23g, yield 81%.
The specific reaction formula is:
compound C 3 A kind of electronic device 1 HNMR(CDCl 3 ,400MHz)：δ：1.30-1.33(t,J＝6.0Hz,3H),2.17(s,3H),2.27(m,1H),2.83-2.85(m,2H),3.50-3.54(t,J＝8.0Hz,1H),4.20-4.25(q,J＝8.0Hz,2H),7.11-7.18(m,2H)，7.32-7.36(m,2H),7.52-7.54(d,J＝8.0Hz,2H)。
Compound C 3 Is used for testing the insecticidal activity: taking cotton aphids as a test object, and adopting an impregnation method; 10mg of Compound C was weighed out 3 The sample is dissolved by using a 5mL liquid-transfering gun to obtain 2mL of acetone/methanol mixed solvent, 18mL of aqueous solution containing 0.1% Tween-80 is added, and the mixture is fully and uniformly mixed to obtain 500 mug/mL measuring solution. The result shows that the death rate of cotton aphids after 24 hours reaches 73 percent.
Example 4
Into a 50mL pressure-resistant bottle was charged α -carbonyl cyclopropylamide A 4 (0.217 g,1 mmol), 1, 3-diphenyl-1, 3-propanedione B 5 (0.224 g,1.0 mmol) ethanol (10 mL) was added DABCO (0.1 g,1.2 mmol) and stirred at 95℃for 10h; TLC monitoring reaction, A 4 After complete disappearance, the reaction solution was poured into ice water, stirred vigorously, extracted three times with diethyl ether (3X 10 mL), the organic phases combined, dried over anhydrous calcium chloride, the solvent removed by rotary evaporation, and purified by column chromatography to give the white product C 5 0.27g, 71% yield.
The specific reaction formula is:
compound C 5 A kind of electronic device 1 HNMR(CDCl 3 ,400MHz)：δ：2.11-2.15(m,1H),2.27-2.29(m,1H),2.36-2.38(m,2H),4.33(s,1H),7.05-7.12(m,2H),7.27-7.35(m,4H),7.78-7.86(m,5H),8.01-8.04(m,4H),8.95(s,1H)。
Compound C 5 Is used for testing the insecticidal activity: the cotton bollworms are used as test objects, and an impregnation method is adopted. 10mg of Compound C was weighed out 5 The sample is dissolved by using a 5mL liquid-transfering gun to obtain 2mL of acetone/methanol mixed solvent, 18mL of aqueous solution containing 0.1% Tween-80 is added, and the mixture is fully and uniformly mixed to obtain 500 mug/mL measuring solution. The result shows that the death rate of the cotton bollworms after 24 hours reaches 66 percent.
Example 5
Into a 50mL pressure-resistant bottle was charged α -carbonyl cyclopropylamide A 5 (0.217 g,1 mmol), acetoacetanilide B 6 (0.177 g,1.0 mmol), DMF (10 mL) and then DBU (0.2 mL,1.3 mmol) were added and stirred at 100deg.C for 8h; TLC monitoring reaction, A 5 After complete disappearance, the reaction solution was poured into ice water, stirred vigorously, extracted three times with diethyl ether (3X 10 mL), the organic phases combined, dried over anhydrous sodium sulfate, the solvent removed by rotary evaporation, and purified by column chromatography to give the white product C 6 0.26g, yield 74%.
The specific reaction formula is:
compound C 6 A kind of electronic device 1 HNMR(CDCl 3 ,400MHz)：δ：1.73(s,3H),2.21-2.24(m,1H),2.29-2.32(m,1H),2.41-2.44(m,2H),4.47(s,2H),6.93-6.96(m,1H),7.18-7.27(m,3H),7.32-7.44(m,2H),7.55-7.61(m,2H),7.73-7.78(s,2H),8.92(s,1H),8.99(s,1H)。
Compound C 6 Is used for testing the insecticidal activity: using plutella xylostella as a test object, and adopting an immersion method; weighing scale10mg of Compound C was taken 6 The sample is dissolved by using a 5mL liquid-transfering gun to obtain 2mL of acetone/methanol mixed solvent, 18mL of aqueous solution containing 0.1% Tween-80 is added, and the mixture is fully and uniformly mixed to obtain 500 mug/mL measuring solution. The result shows that the death rate of the plutella xylostella after 48 hours reaches 57 percent.
Example 6
Into a 50mL pressure-resistant bottle was charged α -carbonyl cyclopropylamide A 6 (0.257 g,1 mmol) acetoacetyl naphthylamine B 7 (0.227 g,1.0 mmol) and DMSO (9 mL), then pyridine (0.1 mL,1.2 mmol) was added and stirred at 80℃for 9.5h; TLC monitoring reaction, A 6 After complete disappearance, the reaction solution was poured into ice water, stirred vigorously, extracted three times with chloroform (3X 10 mL), the organic phases combined, dried over anhydrous calcium chloride, the solvent removed by rotary evaporation, and purified by column chromatography to give the white product C 7 0.26g, yield 68%.
The specific reaction formula is:
compound C 7 A kind of electronic device 1 HNMR(CDCl 3 ,400MHz)：δ：1.71(s,3H),2.21-2.25(m,1H),2.30-2.32(m,1H),2.42-2.46(m,2H),7.11-7.16(m,1H),7.22-7.27(m,4H),7.35-7.41(m,2H),7.66-7.73(m,3H),7.84-7.91(m,2H),8.88(s,1H),8.94(s,1H)。
Compound C 7 Is used for testing the insecticidal activity: taking aphids as test objects, and adopting an immersion method; 10mg of Compound C was weighed out 7 The sample is dissolved by using a 5mL liquid-transfering gun to obtain 2mL of acetone/methanol mixed solvent, 18mL of aqueous solution containing 0.1% Tween-80 is added, and the mixture is fully and uniformly mixed to obtain 500 mug/mL measuring solution. The result shows that the death rate of aphids after 24 hours reaches 61 percent.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A 2-cyclopenten-1-ol derivative characterized by: which is any one of the following structural formulas:
2. a method for synthesizing a 2-cyclopenten-1-ol derivative according to claim 1, wherein: the method comprises the steps of taking an alpha-carbonyl cyclopropylamide compound A and a 1, 3-dicarbonyl compound B as raw materials, taking organic base as a catalyst, dissolving in an organic solvent, and carrying out [3+2] cyclization/deacetylation/oxygen oxidation reaction at 80-100 ℃ to prepare a 2-cyclopentene-1-alcohol compound C; the molar ratio of the alpha-carbonyl cyclopropylamide compound A to the 1, 3-dicarbonyl compound B is 1:1 to 1.2mmol, the ratio of the dosage of the alpha-carbonyl cyclopropylamide compound A, the organic solvent and the organic base is 1mmol: 8-10 mL:1 to 1.5mmol;
the reaction route is as follows:
the 2-cyclopentene-1-alcohol compound C is any one of the following structural formulas:
3. the method for synthesizing 2-cyclopenten-1-ol derivatives according to claim 2, wherein: the organic base is one of 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-dimethylethanolamine, 4-dimethylaminopyridine and 1, 5-diazabicyclo [4.3.0] -5-nonene.
4. The method for synthesizing 2-cyclopenten-1-ol derivatives according to claim 2, wherein: the organic solvent is one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile and ethanol.
5. The method for synthesizing 2-cyclopenten-1-ol derivatives according to claim 2, wherein: the reaction time is 8-10 h.
6. The method for synthesizing 2-cyclopenten-1-ol derivatives according to claim 2, wherein: monitoring the reaction progress by using thin layer chromatography TLC, adding water into a reaction system to stop the reaction after the reactant A completely disappears, extracting by using an extractant, and merging organic phases; the organic phase is dried by a desiccant, filtered, concentrated and subjected to column chromatography to obtain the 2-cyclopentene-1-alcohol compound C.
7. The method for synthesizing 2-cyclopenten-1-ol derivatives according to claim 2, wherein: the extractant is dichloromethane, ethyl acetate, diethyl ether or chloroform; the organic coherent desiccant is anhydrous sodium sulfate, anhydrous calcium chloride or anhydrous magnesium sulfate.
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| CN1100406A (en) * | 1993-06-03 | 1995-03-22 | 住友化学工业株式会社 | A process for the production of a cyclopentenol derivative |
| CN110734394A (en) * | 2018-12-21 | 2020-01-31 | 江西省科学院应用化学研究所 | Synthesis method of 3, 6-dihydropyridone compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1100406A (en) * | 1993-06-03 | 1995-03-22 | 住友化学工业株式会社 | A process for the production of a cyclopentenol derivative |
| CN110734394A (en) * | 2018-12-21 | 2020-01-31 | 江西省科学院应用化学研究所 | Synthesis method of 3, 6-dihydropyridone compounds |
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