CN1218030A - Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine - Google Patents
Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine Download PDFInfo
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- CN1218030A CN1218030A CN 98113306 CN98113306A CN1218030A CN 1218030 A CN1218030 A CN 1218030A CN 98113306 CN98113306 CN 98113306 CN 98113306 A CN98113306 A CN 98113306A CN 1218030 A CN1218030 A CN 1218030A
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- Prior art keywords
- acyl chlorides
- pyrethrin
- dimethylamino pyridine
- catalytic esterification
- alcohol
- Prior art date
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- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000032050 esterification Effects 0.000 title claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 20
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 title claims abstract description 19
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims description 14
- 238000003786 synthesis reaction Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000575 pesticide Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- BTSIZIIPFNVMHF-UHFFFAOYSA-N 2-penten-1-ol Chemical compound CCC=CCO BTSIZIIPFNVMHF-UHFFFAOYSA-N 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 claims description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 3
- -1 acyl ammonia Chemical compound 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- AGWVQASYTKCTCC-UHFFFAOYSA-N (2,3,5,6-tetrafluorophenyl)methanol Chemical compound OCC1=C(F)C(F)=CC(F)=C1F AGWVQASYTKCTCC-UHFFFAOYSA-N 0.000 claims description 2
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- QQHOVRKETYPQHY-UHFFFAOYSA-N 2-(hydroxymethyl)-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound O=C1N(CO)C(=O)C2=C1CCCC2 QQHOVRKETYPQHY-UHFFFAOYSA-N 0.000 claims 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 241000723353 Chrysanthemum Species 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 3
- 229960000490 permethrin Drugs 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- CXBMCYHAMVGWJQ-CABCVRRESA-N (1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)methyl (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-CABCVRRESA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229960005199 tetramethrin Drugs 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- FJDPATXIBIBRIM-QFMSAKRMSA-N (1R)-trans-cyphenothrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 FJDPATXIBIBRIM-QFMSAKRMSA-N 0.000 description 1
- FEOMFFKZOZMBKD-UHFFFAOYSA-N (4-phenoxyphenyl)methanol Chemical compound C1=CC(CO)=CC=C1OC1=CC=CC=C1 FEOMFFKZOZMBKD-UHFFFAOYSA-N 0.000 description 1
- XLOPRKKSAJMMEW-SFYZADRCSA-M (R,R)-chrysanthemate Chemical compound CC(C)=C[C@@H]1[C@@H](C([O-])=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960003536 phenothrin Drugs 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
A catalytic esterification process for synthesizing pyrethrin pesticides features that 4-dimethylamino pyridine (DMAP) is used as ultrahigh-effect catalyst for the esterification of acylchlorine and alcohol in mole ratio of (0.95-1.20) : 1, the organoamine or inorganic alkali or their mixture is used as acid capturer, and reaction takes place at -15-100 deg.C for 10 min -24 hr. Its advantages are high output rate, high quality of product, low cost and less generation of waste.
Description
The present invention relates to a kind of manufacture method of agrochemicals, particularly relate to a kind of manufacture method of pyrethrin.
Pyrethroid is the big insecticides of one in the pesticide industry, especially in hygienic insecticide, because it occupies epochmaking position to pest efficient to people and animals' low toxicity in pesticide industry.The esterification synthetic method of this class agricultural chemicals mainly contains following several:
The 1st kind of method is classic methods, also be the method for present domestic and international industrial widespread usage, but this method exists weak point, mainly is must use anhydrous pyridine in the reaction as acid binding agent and catalyzer.Anhydrous pyridine not only costs an arm and a leg but also very easily suction, and is obvious to the influence of producing yield under the bigger environment of humidity; Next is that the pyridine smell is very unpleasant, influences surrounding environment; It is also very complicated to reclaim anhydrous pyridine in addition.As without pyridine, use cheap triethylamine instead, N, organic amines such as accelerine are as acid binding agent, and then esterification yield and quality product are lower 10～20 percentage points than pyridine method, all can not accept economically with on producing.
The 2nd kind of method is the industrialized preparing process of early stage Tetramethrin, permethrin and valerate, though do not use pyridine in this method as acid binding agent, but because corresponding alcohol moiety intermediate difficult quality guarantee, be reflected at long-time heating under the alkaline condition, to optical activity chrysanthemum ester also is disadvantageous, now progressively is eliminated.
The 3rd kind of method, i.e. ester exchange method.At some chrysanthemum ester then is important in permethrin synthetic for example, but the shortcoming of this method also is tangible.Because the catalyzer that present method adopts is a titanic acid ester, it is hydrolysis very easily, and hydrolysate can not be removed and can not be water-washed away with general filter method, is restricted when practical application.
The objective of the invention is to solve the deficiency of above-mentioned existing method and provide a kind of can make to produce be easy to control, the reaction conditions gentleness can make the product yield height again, the method for the measured esterification synthesis of pyrethrin of matter ester pesticides.
For reaching above-mentioned purpose, technical scheme of the present invention is: use the ultra-high efficiency catalyzer of 4-Dimethylamino pyridine (DMAP) as acyl chlorides and pure esterification, add acid binding agent, wherein the molar feed ratio of acyl chlorides and alcohol is an acyl chlorides: alcohol is 0.95～1.20: 1.00, the mole dosage of DMAP is 0.05～2% of an acyl chlorides, the mole dosage of acid binding agent is 0.5～3 times of acyl chlorides, and reaction promptly made pyrethrin in 10 minutes to 24 hours under-15 ℃～100 ℃ temperature, and its reaction equation is:
In the formula, X representative-CH
3,-Cl; R ' representative
Acid binding agent of the present invention is an organic amine, mineral alkali or both miscellanys.Organic amine comprises Trimethylamine 99, triethylamine, tri-isopropyl amine, N, accelerine, N, N-Diethyl Aniline.Mineral alkali comprises sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and calcium hydroxide.
Acyl chlorides of the present invention comprises cis-trans chrysanthemum acyl chlorides, is 1～25/99～75 and corresponding optical isomer along anti-body ratio; Cis-trans DV-chrysanthemum acyl chlorides is 0～45/100～55 and the trans DV-chrysanthemum of d-acyl chlorides along anti-body ratio; The acyl chlorides that the present invention uses also can replace with corresponding acid anhydrides.
Alcohol of the present invention comprises the 3-phenoxy benzenemethanol, alpha-cyano-3-phenoxy benzenemethanol, N-methylol-3,4,5, the 6-tetrahydric phthalimide, 2,3,5,6-tetrafluorobenzyl alcohol, 2-methyl-3-(2-allyl group)-4-oxo-ring penta-2-enol and 2-methyl-3-(2-propargyl)-4-oxo-ring penta-2-enol.
Acyl chlorides of the present invention is preferably 1.00～1.05 with both molar feed ratios of alcohol: 1.00; The mole dosage of DMAP is preferably 0.1～0.5% of acyl chlorides; The mole dosage of acid binding agent is preferably 1～2.5 times of acyl chlorides; Temperature of reaction is preferably-5 ℃～60 ℃; Reaction times is preferably 1～8 hour.
The main raw material of usefulness required for the present invention, chrysanthemum acyl chlorides for example, purity will have certain requirement, should avoid bringing into activity and high-boiling-point impurity, as containing chrysanthemumic acid etc. in the chrysanthemum acyl chlorides.In the corresponding alcohol, its purity also has higher requirement, should not bring activity or high-boiling-point impurity into, for example should not bring 4-phenoxy benzenemethanol etc. in the 3-phenoxy benzenemethanol.
The present invention requires very not strict to reaction solvent, can be aromatic hydrocarbons, for example toluene, dimethylbenzene etc.; Also can be alkane, for example normal hexane, normal heptane, sherwood oil, hexanaphthene etc.; Even can be water or organic solvent/water two-phase system.
The present invention compares with the traditional method of producing pyrethrin in the past, have very big advantage: at first be fully need not expensive pyridine in producing as acid binding agent and catalyzer, reduce environmental pollution, also do not had the problem that reclaims pyridine, reduced production cost; Also without titanic acid ester as catalyzer, save the trouble of removing hydrolysate; Next is that catalyzer DMAP low price of the present invention, source are abundant, and the product yield height of producing, and quality is good; Be that the inventive method can be produced under the bigger environment of humidity once more, even can carry out, produce and to be easy to control, and traditional method is very strict to the requirement of moisture content at aqueous phase.
The present invention is described in further detail below in conjunction with embodiment.Example 1
Agitator is being housed, thermometer, in the there-necked flask of dropping funnel and calcium chloride tube, add amine alcohol 18.49 grams (0.10 mole), 50 milliliters of triethylamine 15.18 grams, DMAP18 milligram and toluene, under agitation heating makes all dissolvings of amine alcohol slightly, be cooled to about about 10 ℃ of liquid temperature with ice-water bath again, begin to drip toluene solution 26.67 grams of chrysanthemum acyl chlorides, the control rate of addition makes reaction solution liquid temperature remain on 10～20 ℃, drips off the back and continues to react under room temperature to spend the night.With reacting liquid filtering, filtrate is used 5% hydrochloric acid successively, and 5% sodium bicarbonate and be washed to neutrality is sloughed toluene after drying and got light yellow Tetramethrin crude oil 34.55 grams, content 92.00%, yield 95.91%.Example 2
Agitator is being housed, in the there-necked flask of thermometer and dropping funnel, add phenylate alcohol 20.20 grams (0.10 mole), triethylamine 2.00 grams, liquid caustic soda 24.0 grams, 50 milliliters of DMAP18 milligram and toluene, under agitation bathe the cooling reaction solution to below-5 ℃ with cryosel, slowly drip toluene solution 26.67 grams of dextrorotation chrysanthemum acyl chlorides, stirring reaction 3 hours at room temperature after dripping off, reaction solution is used 5% hydrochloric acid after adding an amount of dilution of water successively, 5% sodium bicarbonate and be washed to neutrality, precipitation gets faint yellow d-phenothrin crude oil 35.00 grams after drying, product is through hydrolysis, and with the optical agents menthol reaction, recording dextrorotation trans-chrysanthemate content is 82.37% after the chloride.Example 3
In the device with example 2, add phenylate aldehyde 20.00 grams (0.10 mole), triethylamine 2.00 grams, sodium cyanide 5.25 grams (0.105 mole), DMAP18 milligram and sherwood oil 50 milliliters, when under agitation being cooled to 5 ℃ of reaction solutions, begin to drip petroleum ether solution 27.47 grams of dextrorotation chrysanthemum acyl chlorides, drip off the back and continue reaction 6 hours in 5～10 ℃ with ice-water bath, reaction solution is through alkali cleaning, pickling, washing gets trans cyphenothrin crude oil 38.33 grams of dextrorotation behind the precipitation.Example 4
In the device with example 2, add phenylate alcohol 20.20 grams (0.10 mole), yellow soda ash 21.2 grams, 50 milliliters of DMAP18 milligram and toluene, under agitation with below the ice-water bath cooling reaction solution to 5 ℃, slowly drip toluene solution 32.50 grams of dichloro chrysanthemum acyl chlorides, drip off the back and under room temperature, continue reaction 4 hours, add 100 milliliters in water to reaction solution, wait solids all to dissolve the back and divide water-yielding stratum, oil reservoir washes with water to neutrality, get light yellow transparent permethrin crude oil 39.06 grams behind the decompression precipitation, content 94.92%, yield 94.75% does not change along anti-body ratio.
Claims (11)
1, a kind of method of 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, raw material comprises acyl chlorides and alcohol, it is characterized in that: use the ultra-high efficiency catalyzer of 4-Dimethylamino pyridine (DMAP) as acyl chlorides and pure esterification, add acid binding agent, wherein the molar feed ratio of acyl chlorides and alcohol is an acyl chlorides: alcohol is 0.95～1.20: 1.00, the mole dosage of DMAP is 0.05～2% of an acyl chlorides, the mole dosage of acid binding agent is 0.5～3 times of acyl chlorides, and reaction promptly made pyrethrin in 10 minutes to 24 hours under-15 ℃～100 ℃ temperature.
2, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 1 is characterized in that: acyl chlorides is an acyl chlorides with both molar feed ratios of alcohol: alcohol is 1.00～1.05: 1.00; The mole dosage of DMAP is 0.1～0.5% of an acyl chlorides; The mole dosage of acid binding agent is 1～2.5 times of acyl ammonia; Temperature of reaction is-5 ℃～60 ℃; Reaction times is 1～8 hour.
3, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 2, it is characterized in that: described acid binding agent is an organic amine.
4, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 2, it is characterized in that: described acid binding agent is a mineral alkali.
5, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 2, it is characterized in that: described acid binding agent is the miscellany of organic amine and mineral alkali.
6, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described acyl chlorides is cis-trans chrysanthemum acyl chlorides and corresponding optical isomer, is 1～25/99～75 along anti-body ratio.
7, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described acyl chlorides is cis-trans DV-chrysanthemum acyl chlorides and corresponding optical isomer, is 0～45/100～55 along anti-body ratio.
8, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described acyl chlorides can replace with corresponding acid anhydrides.
9, as the method for claim 3 or 4 or 5 described 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides, it is characterized in that: described alcohol is the 3-phenoxy benzenemethanol, alpha-cyano-3-phenoxy benzenemethanol, N-methylol-3,4,5,6-tetrahydric phthalimide, 2,3,5,6-tetrafluorobenzyl alcohol, any in 2-methyl-3-(2-allyl group)-4-oxo-ring penta-2-enol and 2-methyl-3-(2-the propargyl)-4-oxo-ring penta-2-enol.
10, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 3, it is characterized in that: described organic amine is Trimethylamine 99, triethylamine, tri-isopropyl amine, N, accelerine, N, any in the N-Diethyl Aniline.
11, the method for 4-Dimethylamino pyridine synthesis of pyrethrin by catalytic esterification ester pesticides as claimed in claim 4, it is characterized in that: described mineral alkali is any in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and the calcium hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98113306A CN1115325C (en) | 1998-08-05 | 1998-08-05 | Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113306A CN1115325C (en) | 1998-08-05 | 1998-08-05 | Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine |
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| CN1218030A true CN1218030A (en) | 1999-06-02 |
| CN1115325C CN1115325C (en) | 2003-07-23 |
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| CN98113306A Expired - Lifetime CN1115325C (en) | 1998-08-05 | 1998-08-05 | Method for synthesis of pyrethrin by catalytic esterification of 4-dimethylaminopyridine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026885A1 (en) * | 2002-09-23 | 2004-04-01 | General Electric Company | Process for the preparation of acid esters |
| CN102351694A (en) * | 2011-10-17 | 2012-02-15 | 三明市海斯福化工有限责任公司 | Preparation method of trifluoroacetic acid ethyl ester |
| CN106810444B (en) * | 2015-12-01 | 2018-09-04 | 中国科学院大连化学物理研究所 | A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester |
| CN106810411B (en) * | 2015-12-01 | 2018-09-04 | 中国科学院大连化学物理研究所 | A kind of method of acyl chlorides and 1,2- dichloroethanes reaction generation ester |
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeled pyrethroid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620546A (en) * | 1979-07-27 | 1981-02-26 | Sumitomo Chem Co Ltd | Carboxylic acid ester |
-
1998
- 1998-08-05 CN CN98113306A patent/CN1115325C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026885A1 (en) * | 2002-09-23 | 2004-04-01 | General Electric Company | Process for the preparation of acid esters |
| CN102351694A (en) * | 2011-10-17 | 2012-02-15 | 三明市海斯福化工有限责任公司 | Preparation method of trifluoroacetic acid ethyl ester |
| CN106810444B (en) * | 2015-12-01 | 2018-09-04 | 中国科学院大连化学物理研究所 | A kind of method of chlorobenzoyl chloride and halogenated alkane reaction generation ester |
| CN106810411B (en) * | 2015-12-01 | 2018-09-04 | 中国科学院大连化学物理研究所 | A kind of method of acyl chlorides and 1,2- dichloroethanes reaction generation ester |
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeled pyrethroid |
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| CN1115325C (en) | 2003-07-23 |
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