CN1041303C - d-8-acyloxy-allodihydro-carvones compounds and synthetic method thereof - Google Patents
d-8-acyloxy-allodihydro-carvones compounds and synthetic method thereof Download PDFInfo
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- CN1041303C CN1041303C CN94100746A CN94100746A CN1041303C CN 1041303 C CN1041303 C CN 1041303C CN 94100746 A CN94100746 A CN 94100746A CN 94100746 A CN94100746 A CN 94100746A CN 1041303 C CN1041303 C CN 1041303C
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Abstract
The present invention provides d-8-acyloxy-allodihydro-carvone type compounds formulated by the general formula (I), a synthetic method thereof and an application thereof to repellents for harmful insects, wherein the synthetic method is characterized in that d-a-pinene is used as a raw material, and the compounds formulated by the general formula (I) is obtained through an epoxidation reaction, a hydration reaction, an oxidation reaction and an acylation reaction; a-carvone is used as a raw material, and the compounds formulated by the general formula (I) can be obtained through an addition reaction, a decomposition reaction and an acylation reaction; a-terpineol is used as a raw material, and the compounds formulated by the general formula (I) can be obtained through an acylation reaction and an oxidation reaction. The compounds are formulated by the general formula (I) disclosed in the specifications, wherein R is CH3, C2H5 and C3H7.
Description
The present invention relates to the to have general formula other dihydro Eucarvone of the d-8-acyloxy compounds of (I), their preparation method, and be used as repellent, in particular as the repellent that is harmful insect.
General formula (I) is: R=CH in the formula
3, C
2H
5, C
3H
7 
Can take several different routes from the synthetic other dihydro Eucarvone of d-8-acyloxy of terebinthine principal constituent α-Pai Xi, the report that synthetic Eucarvone (Carone) only arranged in the prior art, and the resulting product component complexity of using of synthetic method, yield is lower, and cost is also high.As Japanese T.Suga at Bull.Chem.Soc.Japan, 31, disclose in 569-77 (1958) document and a kind ofly set out by the dl-alpha-terpineol, prepare the method for Eucarvone with the oxidation of tertiary butyl chromate, only just reach the purpose of chemosynthesis, there is no the industrial application attempt.And for example, Chinese dragon Hou Kang discloses a kind of with α-Pai Xi and the inferior nitrogen compound of nitrous anhydride reaction generation at " Zhongshan University's journal " 2 phase 197-205 (1965), be decomposed into the synthetic method of Eucarvone then in methylene dichloride.
Do not see the report of making the harmful insect repellent with the other dihydro Eucarvone of d-8-acyloxy compounds in the prior art.
In order to make synthesis technique simple, reduce cost, the present invention has taked three kinds of synthetic methods to prepare the other dihydro Eucarvone of d-8-acyloxy compounds, it is the compound shown in the general formula (I), the insect that these compounds are detrimental to health to mosquito, midge, buffalo gnat, ant, leech etc. all with stronger repellent action is arranged, and toxicity is little, has no side effect.
The object of the present invention is to provide the three kinds of other dihydro Eucarvone of d-8-acyloxy compounds shown in the general formula (I) that can be used as repellent.
The present invention also aims to provide a kind of employing d-α-Pai Xi is raw material, through the method for epoxidation, hydration, oxidation, the synthetic other dihydro Eucarvone of the d-8-acyloxy compounds of acidylate four-step reaction.
The present invention also aims to provide a kind of Eucarvone that adopts is the method for the synthetic other dihydro Eucarvone of the d-8-acyloxy compounds of raw material.
The present invention also aims to provide a kind of employing d-Terpineol 350 is raw material, through the method for acidylate, the synthetic other dihydro Eucarvone of the d-8-acyloxy compounds of oxidizing reaction.
To achieve these goals, the invention provides following three kinds of technical schemes:
Obtain d-α-Pai Xi epoxide by the d-α-Pai Xi through the peracid epoxidation reaction; make d-α-sobrerol with the diluted acid hydration; make the other dihydro Eucarvone of d-8-hydroxyl with the oxygenant oxidation then, after acylation reaction obtains the other dihydro Eucarvone of the d-8-acyloxy compounds shown in the general formula (I).
General formula (I) is: R=CH in the formula
3, C
2H
5, C
3H
7 
In order to reach better effect, the epoxidation reaction employing in the above-mentioned chemical reaction contains the 14-51% peracetic acid soln to be carried out with the d-α-Pai Xi in the alkaline matter existence, obtains d-α-Pai Xi epoxide.
Diluted acid hydration reaction in the above-mentioned chemical reaction is preferably carried out with d-α-Pai Xi epoxide with 0.01% aqueous citric acid solution, obtains d-α-sobrerol.
Oxidizing reaction in the above-mentioned chemical reaction is preferably carried out the other dihydro Eucarvone of prepared in reaction d-8-hydroxyl with d-α-sobrerol with the Beckman oxygenant under room temperature in acetone solvent.
The excellent Manganse Dioxide of also selecting for use of oxidizing reaction in the above-mentioned chemical reaction carries out with d-α-sobrerol in benzene solvent, obtains the other dihydro Eucarvone of d-8-hydroxyl.
Whole building-up reactions equation is:
The present invention also provides the method for the other dihydro Eucarvone of the d-8-acyloxy compounds shown in the another kind of synthetic general formula (I).It is raw material that this method adopts the d-Eucarvone, adds 30-40%NaHSO
3Solution; reflux Eucarvone Sodium Metabisulphate 65 affixture; get d-8-hydroxyl Eucarvone Sodium Metabisulphate 65 affixture through the sour water addition, add NaOH solution branch then and solve the other dihydro Eucarvone of d-8-hydroxyl, after acylation reaction obtains the other dihydro Eucarvone of d-8-acyloxy compounds.Available equation is expressed as:
The present invention also provides the method for the other dihydro Eucarvone of the d-8-acyloxy compounds shown in the another kind of synthetic general formula (I) simultaneously.It is raw material that this method adopts alpha-terpineol, gets the acyloxy Terpineol 350 through acylation reaction, and then through SeO
2Oxidation gets the other dihydro Eucarvone of d-8-acyloxy compounds.Available equation is expressed as:
The other dihydro Eucarvone of d-8-acyl hydrogen base compounds shown in the general formula of the present invention (I) is used as repellent, in particular as the repellent that is harmful insect.
From the above, the method for three kinds of compounds shown in the preparation general formula provided by the invention (I) is finished the industrial preparation of the other dihydro Eucarvone of d-8-acyloxy compounds, and serves as the repellent of harmful insect.This method raw materials used general, be easy to get, synthetic route is short, operation steps is simple, the yield of final product reaches more than 30%.
Below given preferred embodiment, be intended to further illustrate the preparation method of The compounds of this invention, and and the scope of non-limiting compound of giving an example, the technical scheme that proposes in the also also non-limiting claim of the present invention that is to say by the described method of these embodiment to make general formula (I) compound at an easy rate.To the exchange or the change of the inventive method, and using the necessary intermediate and the solvent of same type, is not need the property created to make work for the those of ordinary skill of this professional domain.
Embodiment 1 usefulness d-α-Pai Xi is made the other dihydro Eucarvone of feedstock production d-8-propionyloxy.
(1) α-Pai Xi synthesizing epoxy pinane:
Add 30kg α-Pai Xi 40kg anhydrous sodium carbonate, 60kg solvent in reactor, under fully stirring, slowly drip the peracetic acid of 45kg 30%, control reaction temperature is lower than 40 ℃, and the reaction times is no less than 5 hours.Work as CO
2Emit not for a long time, solvent is reclaimed in the chuck heating.Cooling allows its layering, and oil reservoir is epoxypinane.
(2) the epoxypinane hydration becomes pinol:
Add the epoxypinane of 20kg, water and the 0.2kg citric acid of 200kg in being with the uncovered device of interlayer that stirs, the control reacting liquid temperature is no more than 40 ℃, stirs four hours, and inclining solids, excess oil and water, centrifuge dehydration, and washing gets the solid pinol.
(3) pinol is oxidized to the other dihydro Eucarvone of d-8-hydroxyl:
The pinol that the last step was obtained is got 20kg and is placed reactor, add 200kg solvent (acetone), drip the Beckman oxygenant that 65kg prepares, control reaction temperature is lower than 35 ℃, reacts 2 hours, after question response finishes, emit the bottom of a pan dope, reclaim solvent, remaining water, oil mixt ethyl acetate extraction, the saturated NaHCO of extraction liquid
3Solution and water clean, the reclaim under reduced pressure ethyl acetate, and excess oil is the other dihydro Eucarvone of d-8-hydroxyl.
(4) the propionyl reaction of the other dihydro Eucarvone of d-8-hydroxyl:
Press the other dihydro Eucarvone of 20kg d-8-hydroxyl, 16kg propionic anhydride, the anhydrous Sodium Propionate of 0.1kg, reflux is 4 hours in reactor, adds the acid anhydrides of water decomposition remainder, adds the 80kg sherwood oil and divides oil-yielding stratum, oil reservoir NaHCO
3The aqueous solution cleans, and washes with water to neutrality again, and drying reclaims sherwood oil, and residuum is the other dihydro Eucarvone of final product d-8-propionyloxy.
Embodiment 2: make the other dihydro Eucarvone of feedstock production d-8-butyryl acyloxy with Eucarvone
Get Eucarvone 10kg and 30-40%NaHCO
4Aqueous solution 30kg, reflux 4-5 hour together, disappear substantially to oil reservoir, add 1: 1 (w/w) aqueous sulfuric acid 20kg after being chilled to room temperature, placed 5-10 days.Then, stirring adds 30%NaOH solution 30kg down to strong basicity, divides oil-yielding stratum, uses the saturated common salt water washing, gets light yellow oil, and vacuum fractionation is got the 105-135 ℃/1-2 millimeter section of heating up in a steamer, and gets the other dihydro Eucarvone of d-8-hydroxyl.Get the other dihydro Eucarvone of the d-8-hydroxyl 10kg that the step makes then, add the anhydrous Sodium propanecarboxylate of 10kg butyryl oxide and 0.1kg, reflux added water 10kg in 4 hours subsequently and decomposes, and added the jolting of 10kg sherwood oil then, and room temperature was placed 24 hours.Oil reservoir washes with water 3-4 time, uses 5% Na again
2CO
3The solution choosing is washed once, with washing once to slight alkalinity on a small quantity, promptly gets the other dihydro Eucarvone of d-8-butyryl acyloxy behind the recovery solvent again.
Embodiment 3: with alpha-terpineol is raw material, preparation d-8-acetoxycarvotanacetone
(1) preparation of alpha-terpineol acetic ester:
In flask at the bottom of the garden, add 100 gram alpha-terpineols and 80 gram aceticanhydrides and 1 gram sodium acetate, anhydrous, reflux 4 hours adds the remaining aceticanhydride of water decomposition, and with saturated sodium bicarbonate solution and washing, dry back vacuum fractionation is reserved liquid and is the alpha-terpineol acetic ester.
(2) d-8-acetoxycarvotanacetone preparation:
Alpha-terpineol acetic ester 100g that last step reaction is obtained and solvent 500ml place flask at the bottom of the 1000ml garden, add tin anhydride 25g, reflux 4 hours, the filtering post precipitation, steaming desolventizes, through vacuum fractionation, collect 110-130 ℃/1-2mmHg cut, be product d-8-acetoxycarvotanacetone.
With above-mentioned similar method, acylation reaction diacetyl oxide, propionic anhydride, butyryl oxide ... replace, be easy to make the compound shown in the general formula (I).
The physical-chemical data of compound shown in the general formula (I): ethyl ester:
1H NMR:1.98 (2H, 3-H), 2.32 (1H, 4-H), 2.30,2.01 (2H, 5-H), 6.60 (1H, 6-H), 1.68 (3H, 7-H), 1.38 (6H, 9,10-H), 2.18 (3H ,-COCH
3)
13C NMR:134.7 (C-1), 198.5 (C-2), 38.6 (C-3), 43.9 (C-4), 26.3 (C-5), 143.8 (C-6), 14.8 (C-7), 81.1 (C-8), 22.6 (C-9), 22.8 (C-10), 172.6,20.2 (COCH
3) IRV:2979,1740,1662,1378,1258,1213,1110,925UV λ
Max MeOHnm: 235MS m/z:221,195,169,150,135,122,108,95,81,69,59[α]-[D]+27.4 (C=10, CHCl
3) n
D 201.4848d
4 17: 114 ℃ of (4mmHg) propyl ester of 1.0570bp:
1H NMR:2.16 (2H, 3-H), 2.51 (1H, 4-H), 2.39,1.98 (2H, 5-H), 6.70 (1H, 6-H), 1.72 (3H, 7-H), 1.06 (6H, 9,10-H), 2.22,1.05 (5H ,-COCH
2CH
3)
13C NMR:134.4 (C-1), 198.1 (C-2), 38.4 (C-3), 43,5 (C-4), 26.2 (C-3), 143.6 (C-6), 14.6 (C-7), 81.5 (C-8), 22.3 (C-9), 22.5 (C-10), 172.42,27.8,8.4 (COCH
2CH
3) IR V
Max KBrCm
-1: 2968,1722,1668,1445,1361,1195,1160,896UV λ
Max MeOHNm:235MS m/z:209,197,168,150,135,122,108,95,82,67,57[α
D 20+ 4.5 (C=1, CHCl
3) n
D 201.4850d
4 17: 1.0418bp.135 ℃ of butyl ester:
1H NMR:2.10 (2H, 3-H), 2.38 (1H, 4-H), 2.30,2.19 (2H, 5-H), 6.58 (1H, 6-H), 2.03,1.42,0.35 (COCH
2CH
2CH
3)
13C NMR:134.9 (C-1), 198.9 (C-2), 38.8 (C-3) 44.1 (C-4), 26.6 (C-5), 144.1 (C-6), 15.1 (C-7), 82.0 (C-8), 22.8 (C-9), 22.9 (C-10), 172.2,37,0,18.2,13,1 (COCH
2CH
2CH
3) IR V
Max KBrCm
-1: 2965,1728,1674,1480,1338,1095,904UV λ
Max MeOHNm:235MS m/z:256,236,220,199,180,168,150,135,122,108,95,82,71,53,43[α
D 20+ 14 (C=1, CHCl
3) n
D 201.4851d
4 17: 1.0314bp.148 ℃ (4mmHg)
The laboratory method of use standard can detect the character and the relevant usefulness of the present invention's compound at an easy rate.
As, mouse is carried out acute oral toxicity and skin absorption test, rabbit is carried out can proving easily that the present invention's compound belongs to low toxicity, bland repellent after skin is smeared subacute toxicity test.In mouse test, press different weight and dosed administration respectively, the crystallization of d-8-acetoxycarvotanacetone or other dihydro Eucarvone of d-8-propionyloxy or the other dihydro Eucarvone of d-8-butyryl acyloxy is mixed with 100mg/ml emulsion, write down symptom and the death toll in 10 days that occurs after irritating stomach, and calculate LD with simplifying the probability graph solution
50, the results are shown in Table one.
Table one compound L D
50(mg/kg) 95% fiducial limit (mg/kg) d-8-acetoxycarvotanacetone or the other dihydro Eucarvone of d-8-propionyloxy 1400-1450 1800-1100 or the other dihydro Eucarvone of d-8-butyryl acyloxy DETA 1390-1410 1575-1244
And for example, the other dihydro Eucarvone of d-8-acyloxy compounds is mixed with 30% emulsion, smears test at the indoor skin that carries out then, can observe the insect that mosquito, midge, buffalo gnat, ant, leech etc. are detrimental to health has significant repellent action; The result that outdoor skin is smeared test shows, to mosquito, midge, buffalo gnat, 1-3 hour repellent action is arranged, wherein to the guard time of midge between 2-3 hour, at southern area mosquito is had 6-8 hour repellent action (see Table two, table three).The on-the-spot repelling effect of table two
Midge, buffalo gnat, horsefly effect are driven in table three scene
| On-the-spot area on probation | The repellent title | On probation person-time | In 2 hours | In 3 hours | In 4 hours | In 5 hours | In 6 hours | |||||
| Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | |||
| Heilungkiang, Kunming Areas Hekou, Yunnan Province Heilungkiang | The same DETA emulsion of general formula (I) compound emulsion (30%) (3%) | 238 33 819 52 | 238 33 770 30 | 100 100 94 57.7 | 238 33 524 21 | 100 100 64 40.4 | 238 33 246 7 | 100 100 30 13.5 | 238 31 42 0 | 100 93.9 5.1 0 | 228 25 | 95.8 75.7 |
| The test address | Medicine name and formulation | On probation person-time | In 1 hour | In 2 hours | In 3 hours | In 4 hours | More than 4 hours | |||||
| Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | Effective person-time | Protection ratio % | |||
| The Heilungkiang Fuyuan County | General formula (I) compound emulsion (30%) DETA emulsion (30%) | 297 35 | 292 25 | 98.3 71.4 | 277 15 | 93.3 42.8 | 217 8 | 73.1 22.8 | 118 4 | 39.7 11.4 | 97 0 | 32.6 0 |
The observation on probation that the present invention's compound is on-the-spot more than 5000 person-time through north and south all has repellent effect preferably to multiple harmful insect (mosquito, midge, buffalo gnat, horsefly etc.), and is non-stimulated to skin, no anaphylaxis.Compare with DETA, repellent effect is better, and toxicity is lower.
Claims (9)
1. by the other dihydro Eucarvone of the d-8-acyloxy compounds shown in the general formula (I), R=CH in the formula
3, C
2H
5, C
3H
7 
2. the method for the compound shown in synthetic claim 1 general formula (I); it is characterized in that getting the rare epoxide of d-australene through the peracid epoxidation reaction by the d-α-Pai Xi; make d-α-sobrerol with the diluted acid hydration; make the other dihydro Eucarvone of d-8-hydroxyl with the oxygenant oxidation then, after acylation reaction obtains the other dihydro Eucarvone of d-8-acyloxy.
3. method according to claim 2 is characterized in that described epoxidation reaction adopts peracetic acid soln to carry out in the presence of alkaline matter, the concentration of Peracetic Acid is 14%-51%.
4. method according to claim 2 is characterized in that diluted acid hydration reaction wherein adopts 0.01% aqueous citric acid solution to handle.
5. method according to claim 2 is characterized in that oxidizing reaction wherein adopts the oxidation under room temperature in acetone soln of Beckman oxygenant.
6. method according to claim 2 is characterized in that described oxidizing reaction adopts activated manganese dioxide to carry out in benzene solvent, oxidizing temperature is 50-55 ℃.
7. the method for the compound shown in synthetic claim 1 general formula (I), it is characterized in that adopting α-Eucarvone is raw material, adds 30-40% NaHSO
3Solution, reflux Eucarvone Sodium Metabisulphate 65 affixture, add NaOH solution branch then and solve the other dihydro Eucarvone of d-8-hydroxyl, after acidylate obtains the other dihydro Eucarvone of d-8-acyloxy.
8. the method for the compound shown in synthetic claim 1 general formula (I) is characterized in that with the alpha-terpineol being raw material, gets the acyloxy Terpineol 350 through acidylate, then through SeO
2Oxidation gets the other dihydro Eucarvone of d-8-acyloxy.
9. application rights requires the other dihydro Eucarvone of 1 described d-8-acyloxy compounds as repellent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000013658A1 (en) * | 1998-09-02 | 2000-03-16 | The Procter & Gamble Company | A composition containing insect repellent |
| WO2001033963A1 (en) * | 1999-11-09 | 2001-05-17 | The Procter & Gamble Company | A composition comprising solubilized repellent active component |
| AU1911400A (en) * | 1999-11-09 | 2001-06-06 | Procter & Gamble Company, The | Cyclodextrin compositions for odor, insect and dust mite contol |
| SE0002385L (en) * | 2000-06-26 | 2001-12-27 | Forskarpatent I Syd Ab | Composition |
| CN100338014C (en) * | 2005-08-12 | 2007-09-19 | 江西农业大学 | 8-hydroxy-allodihydro-carvacrol formate and its synthesis method and use as repellent |
| CN108821942A (en) * | 2018-08-02 | 2018-11-16 | 湖南师范大学 | A method of sobrerol is directly catalyzed and synthesized by australene |
| CN110269071B (en) * | 2019-07-31 | 2021-04-13 | 王鹏 | Mosquito-repellent composition and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0380047A2 (en) * | 1989-01-23 | 1990-08-01 | Freund Industrial Co., Ltd. | A percutaneous or trans-mucosal absorption enhancer and a percutaneous or trans-mucosal medicine |
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1994
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0380047A2 (en) * | 1989-01-23 | 1990-08-01 | Freund Industrial Co., Ltd. | A percutaneous or trans-mucosal absorption enhancer and a percutaneous or trans-mucosal medicine |
Non-Patent Citations (3)
| Title |
|---|
| 《中山大学学报》1965.1.1 龙侯康 * |
| 《中山大学学报》1965.1.1 龙侯康;BULL.CHEM.900.JAPAN,31 1958.1.1 T.Suga * |
| BULL.CHEM.900.JAPAN,31 1958.1.1 T.Suga * |
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