CN1730459A - 8-hydroxy-allodihydro-carvacrol formate and its synthesis method and use as repellent - Google Patents
8-hydroxy-allodihydro-carvacrol formate and its synthesis method and use as repellent Download PDFInfo
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- CN1730459A CN1730459A CN 200510019290 CN200510019290A CN1730459A CN 1730459 A CN1730459 A CN 1730459A CN 200510019290 CN200510019290 CN 200510019290 CN 200510019290 A CN200510019290 A CN 200510019290A CN 1730459 A CN1730459 A CN 1730459A
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- hydroxyl
- dihydrocarvone
- repellent
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- epoxypinane
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- 239000005871 repellent Substances 0.000 title claims abstract description 36
- 230000002940 repellent Effects 0.000 title claims abstract description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title abstract 4
- 238000001308 synthesis method Methods 0.000 title abstract 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 8
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- NQFUSWIGRKFAHK-UHFFFAOYSA-N 2,3-epoxypinane Chemical compound CC12OC1CC1C(C)(C)C2C1 NQFUSWIGRKFAHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229930006723 alpha-pinene oxide Natural products 0.000 claims abstract description 7
- 235000019253 formic acid Nutrition 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- AZOCECCLWFDTAP-UHFFFAOYSA-N dihydrocarvone Chemical compound CC1CCC(C(C)=C)CC1=O AZOCECCLWFDTAP-UHFFFAOYSA-N 0.000 claims description 64
- WPGPCDVQHXOMQP-UHFFFAOYSA-N carvotanacetone Natural products CC(C)C1CC=C(C)C(=O)C1 WPGPCDVQHXOMQP-UHFFFAOYSA-N 0.000 claims description 32
- AZOCECCLWFDTAP-RKDXNWHRSA-N dihydrocarvone Natural products C[C@@H]1CC[C@@H](C(C)=C)CC1=O AZOCECCLWFDTAP-RKDXNWHRSA-N 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 238000006735 epoxidation reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 241000256173 Aedes albopictus Species 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 abstract 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 abstract 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 abstract 1
- 150000003505 terpenes Chemical class 0.000 description 11
- 235000007586 terpenes Nutrition 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 241000255925 Diptera Species 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002690 dihydrocarvone group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004920 integrated pest control Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 241000256186 Anopheles <genus> Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 241000931332 Cymbopogon Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 206010060860 Neurological symptom Diseases 0.000 description 1
- 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 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- AOWPVIWVMWUSBD-RNFRBKRXSA-N [(3r)-3-hydroxybutyl] (3r)-3-hydroxybutanoate Chemical class C[C@@H](O)CCOC(=O)C[C@@H](C)O AOWPVIWVMWUSBD-RNFRBKRXSA-N 0.000 description 1
- 231100000460 acute oral toxicity Toxicity 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012395 formulation development Methods 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- -1 hydroxyl ester Chemical class 0.000 description 1
- 230000009357 insect borne transmission Effects 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 235000020245 plant milk Nutrition 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 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 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to 8-hydroxy-allodihydro-carvyl alcohol formate and a synthesis method thereof and application of the formate as a repellent, wherein the synthesis method comprises the steps of epoxidizing alpha-pinene by adopting low-concentration peroxyacetic acid to obtain 2, 3-epoxy pinane, reacting the 2, 3-epoxy pinane with a dilute acid aqueous solution to obtain 8-hydroxy-allodihydro carvyl alcohol, and esterifying the 8-hydroxy-allodihydro carvyl alcohol in an ethyl formate solution of formic acid to obtain 8-hydroxy-allodihydro carvyl alcohol formate. The invention can be used as a repellent, and particularly has good repellent effect on aedes albopictus with strongest blood-sucking attacking force.
Description
Technical field
The present invention relates to repellent, particularly the terpene repellent.
Technical background
Many insect-borne transmission diseases, cause that tetter or harassing and wrecking are serious, using repellent is important preventive means.
Nearly all in recent years insect vector all has the resistance report of pair sterilant, and most sterilant all belongs to nerve toxicant, and quite a few is harmful to human and warm-blooded animal and other nonstandard biology and environment.Therefore (countries in the world are all paid attention to the research and development of this non-killing livestock property protective agent of repellent more for Integratedpest management, common recognition IPM) to have formed the anti-system of harmful organism (Pest control) and integrated pest management.
Present most popular anophelifuge is once to be considered to very ideal Metadelphene (DETA), but find that recently it (Qiu H C such as neurological symptom can occur to important malaria media light color anopheles poor effect, children's allergy, long-term or a large amount of use, et al.Journal of the American mosquito controlassociation, 1998,14 (1): 12.), so better repellent is all being sought by each state.Owing to do not have more suitably kind at present, so can only continue to use DETA.
Many plants can secrete the terpenoid with repellent activity, and (2001,410 (6828): 577), yet and these materials are accepted by consumers in general easily because of deriving from certainly for Moraes C M, et al.Nature.In the repellent of plant-sourced, terpene has occupied major part, and plant-sourced terpene repellent generally all is alcohols, ester class, hydroxyl ester class and the ketone ester class and the derivative thereof of monoterpenes, wherein much be repellent be again spices.
Terpenoid not only has aromaticity, wherein much also has repellent effect preferably, and is therefore pleasant in sense of smell, makes us taking like a shot on consumer psychology.The more important thing is that low toxicity, pungency are little, to human body and environmentally friendly, safe in utilization.These advantages are that other kind repellents are difficult to have both simultaneously, therefore can seek the substitute of DETA in the terpene repellent.
The terpene repellent mainly is directly to utilize plant milk extract and formulation development thereof at present, as (Phytomed such as Tyaig B K, 1998,5 (4): 324) studied the repellent effect of 4 kinds of Cymbopogon plant volatile oils to mosquito, a kind of mosquito-repellent that contains peppermint wet goods plants essential oil of yellow sensible (CN 1046441,1990) exploitation.The report of extraction separation, evaluation and chemosynthesis is still few from plant.
And directly the repellent that obtains of extraction separation often active not enough, cost is too high or raw material easily collecting not, has limited its application.Some synthetic repellents have been developed later on again, the terpene repellent compound (Zhu Chengpu that comprises some alcohols, hygienic biocide medical instruments application guide, 1988), terpene repellent compound (Chen Suwen, the rosin turpentine deep processing technology and the utilization of ester class, 1997), terpene repellent compound (Dong Sun Han of ketone, CN 1105658,1995) and the terpene repellent compound of amides (Li Jie, Chinese media biology and control magazine, 1997,8 (1): 76) etc.But the shortcoming of these repellents is that the repellent effect that has is not enough, the cost height that has.Therefore, be necessary to develop safe, efficient, lower-cost repellent.
Summary of the invention
The object of the present invention is to provide a kind of other dihydrocarvone manthanoate of compound 8-hydroxyl that can be used as anophelifuge.
The present invention also aims to provide a kind of is raw material with terebinthine main ingredient α-Pai Xi, through the synthetic method of epoxidation, hydration, the synthetic other dihydrocarvone manthanoate of 8-hydroxyl of esterification three-step reaction.
The present invention also aims to provide simple and the synthesis technique environmental protection of production process own.In the other dihydrocarvone manthanoate of 8-hydroxyl synthesis technique, adopted the Peracetic Acid of lower concentration (17-22wt%) to carry out the preparation of epoxypinane, when esterification, under normal temperature, carry out.
To achieve these goals, technical scheme provided by the invention is as follows:
Synthesizing of the other dihydrocarvone manthanoate of compound 8-hydroxyl.
Reaction equation is as follows:
1) α-Pai Xi is obtained 2 by the Peracetic Acid epoxidation, the 3-epoxypinane, and the Peracetic Acid of employing lower concentration, especially can adopt commercially available concentration is the Peracetic Acid of 17-22wt%.
The mole proportioning of α-Pai Xi, carbonate, Peracetic Acid, sodium-acetate is 100: 200-300: 100-200: 2-10, and temperature of reaction is 0-5 ℃, the reaction times is 6-10 hour.
2) 2,3-epoxypinane and dilute acid solution effect obtain the other dihydrocarvone of 8-hydroxyl, and diluted acid can use 0.01wt% aqueous sulfuric acid or 0.02wt% oxalic acid aqueous solution.
When using dilute sulfuric acid aqueous solution 2, the mass ratio of 3-epoxypinane, 0.01wt% dilute sulfuric acid aqueous solution is 100: 200-300, and when using rare oxalic acid aqueous solution, 2, the quality proportioning of 3-epoxypinane, the rare oxalic acid aqueous solution of 0.02wt% is 100: 200-350.
Temperature of reaction is 20-30 ℃, and the reaction times is 4-8 hour.
3) can obtain the other dihydrocarvone manthanoate of 8-hydroxyl after the other dihydrocarvone esterification of 8-hydroxyl, be reflected in the ethyl formate solution and under normal temperature, carry out.
The mole proportioning of the other dihydrocarvone of 8-hydroxyl, formic acid is 100: 800-1000.Temperature of reaction is 25-35 ℃, and the reaction times is 8-10 hour.
The other dihydrocarvone manthanoate of compound 8-hydroxyl can be used as repellent.Particularly the strongest Aedes albopictus of aggressivity of sucking blood had good repellent effect.
Specific embodiment
Embodiment 1
Synthesizing of the other dihydrocarvone manthanoate of 8-hydroxyl
In three-necked bottle, add 100 parts of α-Pai Xis, 240 parts of solid sodium carbonates and an amount of toluene successively by the mole proportioning, in 3 hours, in three-necked bottle, slowly drip 150 parts of the Peracetic Acid of the 17-22wt% be dissolved with 6 parts of sodium-acetates, control stirring velocity well, make temperature of reaction remain on 0-5 ℃ with ice-water bath.Drip the back and continue to stir stopped reaction after 5 hours, obtain 2 after the processing, the 3-epoxypinane, GC analyzes: contain raw material 6.7%, contain 2,3-epoxypinane 68.5%.
Add 100 part 2 by the quality proportioning in round-bottomed flask, the aqueous sulfuric acid of 3-epoxypinane, 260 parts of 0.01wt% stirs under water-bath, makes temperature of reaction be no more than 30 ℃.Stopped reaction after 6 hours is used saturated aqueous common salt earlier in B, use the benzene filtering and washing again, obtains the white crystals of the other dihydrocarvone of 8-hydroxyl, and GC content is 93%, and yield is 74%.
In Erlenmeyer flask, add 100 parts of other dihydrocarvones of 8-hydroxyl, 950 parts of formic acid by the mole proportioning, add an amount of ethyl formate,, make temperature be no more than 32 ℃ in stirred in water bath, stopped reaction after 9 hours, repeatedly extract with ethyl formate, with the saturated sodium carbonate solution washing, being washed to the pH value with saturated common salt again is 7 after the merging organic phase, dry, after reclaiming solvent, get little yellow liquid, GC analyzes: contain the other dihydrocarvone manthanoate 89% of 8-hydroxyl.
Embodiment 2
In three-necked bottle, add 100 parts of α-Pai Xis, 280 parts of solid carbonic acid potassium and an amount of toluene successively by the mole proportioning, in 3 hours, in three-necked bottle, slowly drip 160 parts of the Peracetic Acid of the 17-22wt% be dissolved with 7 parts of sodium-acetates, control stirring velocity well, make temperature of reaction remain on 0-5 ℃ with ice-water bath.Drip the back and continue to stir stopped reaction after 4.5 hours, obtain 2 after the processing, the 3-epoxypinane, GC analyzes: contain raw material 6.0%, contain 2,3-epoxypinane 69.1%.
Add 100 part 2 by the quality proportioning in round-bottomed flask, the oxalic acid aqueous solution of 3-epoxypinane, 260 parts of 0.01wt% stirs under water-bath, makes temperature of reaction be no more than 30 ℃.Stopped reaction after 7 hours is used saturated aqueous common salt earlier in B, use the benzene filtering and washing again, obtains the white crystals of the other dihydrocarvone of 8-hydroxyl, and GC content is 92%, and yield is 75%.
In Erlenmeyer flask, add 100 parts of other dihydrocarvones of 8-hydroxyl, 1000 parts of formic acid by the mole proportioning, add an amount of ethyl formate,, make temperature be no more than 34 ℃ in stirred in water bath, stopped reaction after 8 hours, repeatedly extract with ethyl formate, with the saturated sodium carbonate solution washing, being washed to the pH value with saturated common salt again is 7 after the merging organic phase, dry, after reclaiming solvent, get little yellow liquid, GC analyzes: contain the other dihydrocarvone manthanoate 90.4% of 8-hydroxyl.
The structured data of the other dihydrocarvone manthanoate of 8-hydroxyl (anophelifuge R1) is as follows:
1H NMR，δ：8.13(s，1H，CHO)，5.76(m，1H，＝C-H)，5.41(s，1H，6-CH)，2.21(m，1H，3-CH)，2.08(d，1H，6-CH)，2.04(s，1H，5-CH)，1.84-1.71(m，3H，4-CH，3-CH，OH)，1.70(s，3H，7-CH
3)，1.51(m，1H，5-CH)，1.20，1.18(2s，6H，9-CH
3，10-CH
3)。
13C NMR，δ：161.02(C＝O)，130.32(1-C)，128.63(2-C)，71.92(8-C)，70.71(6-C)，39.32(4-C)，29.95(5-C)，27.55(11-C)，26.77(3-C)，26.51(9-C)，20.52(7-C)。
MS m/e(％)：29(7)，31(7)，39(9)，41(6)，43(38)，55(10)，59(73)，67(8)，69(8)，77(23)，79(85)，91(28)，93(43)，94(48)，95(19)，108(19)，109(57)，119(100)，120(11)，134(19)，135(10)，136(16)，137(52)，152(8)，167(1)，180(22)，181(3)。
IR (liquid film, cm
-1): 3438,2972,2922,1720,1445,1374,1166.7,1030.1,915.1,810 (28).
The laboratory method of use standard shows that the other dihydrocarvone manthanoate of 8-hydroxyl belongs to the repellent of little poison.
Select 20 cleaning level big white mouse for use, male and female half and half are divided into 2 groups according to sex before the experiment, press the dosage of 5000mg/, take by weighing and tried thing and be made into required concentration, once irritate stomach by the 1mL/100g body weight after the animal fasting overnight, observe animal poisoning manifestations, death toll in the 14d with edible oil.No animal dead in the 14d, experimental result such as table 1.
The acute oral toxicity test result of the other dihydrocarvone manthanoate of table 18-hydroxyl
| Compound sex dosage (mg/) LD50 and 95% can convince (mg/) |
| Other dihydrocarvone hero 5000＞5000 manthanoate female 5000＞5000 of 8-hydroxyl |
Experimental result shows that the per os toxicity of the other dihydrocarvone manthanoate of 8-hydroxyl belongs to little poison.
The other dihydrocarvone manthanoate of 8-hydroxyl is to the repellency test of Aedes albopictus, and on people's both hands back side 5cm * 5cm area, a hand is by 1.5 μ l/cm
2Smear medicament, the another hand is a blank.In different time stretches into hand in 40 * 30 * 30cm mosquito cage that is no less than 300 female mosquitos, expose the area of coating skin 4cm * 4cm, tightly cover rest part, observe 2min.As long as there is one to sting thorn and promptly declare repellent and lost efficacy at every turn.The record effective protecting time, result such as table 2.
The other dihydrocarvone manthanoate of table 28-hydroxyl is to the repellent effect of Aedes albopictus
| Compound | Working concentration (%) | Effective protecting time (h) |
| 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 · · · · · · · · · · · · · · · 5 0 5 0 5 0 5 0 5 0 5 0 5 0 5 | ||
| The other dihydrocarvone manthanoate of 8-hydroxyl | 10 20 | - - - - - + - - - - - - - - - + |
| Metadelphene (DETA) | 10 20 | - - - - - - - - - - - - - + + - - - - - - - - - - - - - - + |
Annotate: "-" expression does not have mosquito to sting thorn, and "+" is as long as expression has one to sting thorn and promptly declare repellent and lost efficacy.
The other dihydrocarvone manthanoate of 8-hydroxyl is 20% o'clock at working concentration; to the human body effective protecting time is 〉=4.5 hours; reach the B grade standard (〉=4 hours) of GB/T 17322.10-1998 judgement criteria, illustrate that this compound has good repellent effect to the strongest Aedes albopictus of aggressivity of sucking blood.
Claims (6)
1, the other dihydrocarvone manthanoate of compound 8-hydroxyl, structural formula is:
2, the synthetic method of compound as claimed in claim 1 is as follows:
Adopt the Peracetic Acid of lower concentration that the α-Pai Xi epoxidation is obtained 2, the 3-epoxypinane, 2,3-epoxypinane and dilute acid solution effect obtain the other dihydrocarvone of 8-hydroxyl, and the esterification in the ethyl formate solution of formic acid of the other dihydrocarvone of 8-hydroxyl obtains the other dihydrocarvone manthanoate of 8-hydroxyl.
3, the synthetic method of compound as claimed in claim 2 is as follows, wherein epoxidation reaction employing concentration is the Peracetic Acid of 17-22wt%, the mole proportioning of α-Pai Xi, carbonate, Peracetic Acid, sodium-acetate is 100: 200-300: 100-200: 2-10, temperature of reaction is 0-5 ℃, and the reaction times is 6-10h.
4, method as claimed in claim 2, wherein the synthetic of the other dihydrocarvone of 8-hydroxyl is by 2,3-epoxypinane and dilute acid solution effect obtain, when using dilute sulfuric acid aqueous solution, and 2, the mass ratio of 3-epoxypinane, 0.01wt% dilute sulfuric acid aqueous solution is 100: 200-300, when using rare oxalic acid aqueous solution, 2, the quality proportioning of 3-epoxypinane, the rare oxalic acid aqueous solution of 0.02wt% is 100: 200-350, temperature of reaction is 20-30 ℃, and the reaction times is 4-8h.
5, method as claimed in claim 2, wherein the other dihydrocarvone manthanoate of 8-hydroxyl is by other dihydrocarvone of 8-hydroxyl and formic acid esterification, be reflected in the ethyl formate solution and carry out under normal temperature, the mole proportioning of the other dihydrocarvone of 8-hydroxyl, formic acid is 100: 800-1000.Temperature of reaction is 25-35 ℃, and the reaction times is 8-10h.
6, compound as claimed in claim 1 is as repellent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105613529A (en) * | 2016-02-16 | 2016-06-01 | 烟台米罗卡化工科技有限公司 | Insecticide for aedes albopictus |
| CN108090316A (en) * | 2016-11-09 | 2018-05-29 | 成都彩虹电器（集团）股份有限公司 | A kind of spatial repellency product simulation field efficacy test method |
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| DE3143227A1 (en) * | 1981-10-31 | 1983-05-11 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of pinocarveol |
| IT1173550B (en) * | 1984-04-02 | 1987-06-24 | Corvi Camillo Spa | ERYTHROMYCIN SALT WITH MUCOSECRETOLYTIC AND FLUIDIFYING ACTIVITY, PROCESS FOR ITS PREPARATION AND PHARMACEUTICAL COMPOSITIONS |
| IT1217698B (en) * | 1988-05-23 | 1990-03-30 | Corvi Camillo Spa | TIOLIC COMPOUNDS WITH MUCOLITIC ACTIVITY AND PROCEDURE FOR THEIR PREPARATION |
| PL163208B1 (en) * | 1990-09-17 | 1994-02-28 | Akad Rolnicza | Method for manufacturing a new 3,6,8-p-methentriol |
| CN1041303C (en) * | 1994-01-22 | 1998-12-23 | 中国科学院昆明植物研究所 | d-8-acyloxy-allodihydro-carvones compounds and synthetic method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105613529A (en) * | 2016-02-16 | 2016-06-01 | 烟台米罗卡化工科技有限公司 | Insecticide for aedes albopictus |
| CN108090316A (en) * | 2016-11-09 | 2018-05-29 | 成都彩虹电器（集团）股份有限公司 | A kind of spatial repellency product simulation field efficacy test method |
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