CN113651696A - Synthesis method of cis (trans) -8-dodecenol acetate - Google Patents
Synthesis method of cis (trans) -8-dodecenol acetate Download PDFInfo
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- acetoxyl
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- petroleum ether
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- SUCYDSJQVVGOIW-AATRIKPKSA-N 8E-Dodecenyl acetate Chemical compound CCC\C=C\CCCCCCCOC(C)=O SUCYDSJQVVGOIW-AATRIKPKSA-N 0.000 title claims abstract description 42
- 238000001308 synthesis method Methods 0.000 title description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 99
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 60
- YXXBWDUFNZATIK-UHFFFAOYSA-N 8-hydroxyoctyl acetate Chemical compound CC(=O)OCCCCCCCCO YXXBWDUFNZATIK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003208 petroleum Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 41
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 38
- KYCLIHYYHGOPPW-UHFFFAOYSA-N 8-oxooctyl acetate Chemical compound CC(=O)OCCCCCCCC=O KYCLIHYYHGOPPW-UHFFFAOYSA-N 0.000 claims abstract description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000007530 organic bases Chemical class 0.000 claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 25
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 22
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 claims abstract description 20
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 18
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims abstract description 18
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007239 Wittig reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000002779 inactivation Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- -1 (trans) -8-dodecenyl Chemical group 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 5
- UPQNPBHYPACBSK-UHFFFAOYSA-N methylsulfinylmethane;sodium Chemical compound [Na].CS(C)=O UPQNPBHYPACBSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 14
- 241000659001 Grapholitha molesta Species 0.000 description 10
- 239000000877 Sex Attractant Substances 0.000 description 10
- 235000013399 edible fruits Nutrition 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 241000607479 Yersinia pestis Species 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 241001441330 Grapholita molesta Species 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 241000220324 Pyrus Species 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000014443 Pyrus communis Nutrition 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002420 orchard Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000447 pesticide residue Substances 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- 235000014493 Crataegus Nutrition 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5352—Phosphoranes containing the structure P=C-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Abstract
The invention discloses a method for synthesizing cis (trans) -8-dodecenol acetate, which comprises the following steps: at normal temperature, 1, 8-octanediol is placed in an acetic acid aqueous solution, sulfuric acid is used as a catalyst, and the mixture is continuously stirred to react; continuously extracting the reaction system with petroleum ether in a centrifugal extractor, and distilling and recovering the petroleum ether to obtain 8-acetoxyl-1-octanol; adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring, adding tetramethylpiperidine oxide, then dropwise adding sodium hypochlorite while stirring, and reacting to generate 8-acetoxyl-1-octanal; adding butyl triphenyl phosphonium bromide into tetrahydrofuran, dropwise adding organic base while stirring to react, and continuously dropwise adding 8-acetoxyl-1-octanal to perform wittig reaction to generate cis (trans) -8-dodecenol acetate. The method has the advantages of short period, few steps, high yield, simple post-treatment and the like, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of artificial synthesis of insect sex pheromones. In particular to a method for synthesizing cis (trans) -8-dodecenol acetate.
Background
Grapholithamolesta (Grapholithamolesta) is a worldwide pest, also known as fruit moth of the small fruit moth of the pear and moth of the oriental fruit moth, abbreviated as small pear, and belongs to the family of Tolypocladidae of Lepidoptera. The oriental fruit moths are widely distributed in China, are common in North China, south China and northeast China except Tibet and are harmful to fruit trees such as pears, apples, peaches, hawthorns, apricots, cherries and the like. The larvae of the oriental fruit moths eat fruits and young shoots, and the larvae of the oriental fruit moths are large in occurrence in recent years and become increasingly harmful. The general annual pear damage rate reaches about 10 percent, the individual orchard reaches 20 to 30 percent, and the insect fruit rate of the orchard without pesticide spraying can reach more than 80 percent.
For many years, the prevention and treatment of the oriental fruit moth is mainly based on chemical agents. The use of a large amount of chemical pesticides not only does not control pests, but also causes the pests to generate drug resistance due to the destruction of the virtuous cycle of the biological chain, so that the situation of 'killing the pesticide every year and increasing the number of the pests every year' is formed, and meanwhile, the use of a large amount of chemical pesticides also brings about a plurality of problems of ecological environment imbalance, pesticide residues and the like.
Along with the development of economy, the national importance on the ecological environment is increased day by day, the public requirements on pollution-free fruits and pesticide residues are strong day by day, and the traditional prevention and control concept and prevention and control means can not meet the requirements of current ecological construction and sustainable development of the forest and fruit industry.
Therefore, the grapholitha molesta pheromone is introduced into China from a new technical product, and the grapholitha molesta is prevented and controlled by using a high-tech biological control means, so that the safety and the pollution-free of fruits can be ensured, the use of chemical pesticides is greatly reduced, the traditional chemical control means is gradually replaced, the increasingly worsened ecological environment can be protected, and the ecological balance is gradually restored. The method conforms to national policies and industrial development plans, can comprehensively carry out the prevention of implementation, scientific prevention and control, legal treatment and promotion of health, further promotes the pollution-free prevention and control level of agricultural and forestry pests, protects the ecological environment and the diversity of organisms and promotes the sustainable and healthy development of the forest and fruit industry; meanwhile, conditions are created for large-area application and popularization of the products in domestic pest control, and the products have wide development prospect and epoch-making significance.
The current synthesis of the grapholitha molesta sex pheromone analogue mainly comprises the following two routes:
1. synthetic route from alkynes. The synthetic route is characterized in that: the grapholitha molesta sex pheromone analogue is synthesized by using a raw material containing an acetylene bond, and then cis-form and trans-form grapholitha molesta sex pheromones are obtained by partial reduction, wherein the terminal group is directly brought by the raw material or is converted by a functional group. In 1973 Holan G proposed a synthetic route by partial reduction of borane and conversion of the terminal group for the synthetic acetylenic intermediate. In 1977, the Peking animal research institute pesticide group of Chinese academy of sciences refers to the synthesis method of the compound for improvement, and provides two routes for synthesizing cis-Grapholitha molesta sex pheromone analogues; the first route is characterized by the use of Pd-CaCO for the reduction of the intermediate acetylenic bond3And (4) catalytic hydrogenation reduction. Wherein the second route is similar to the first route except that Pd-CaCO is used for reduction of the acetylenic bond3And (4) catalytic hydrogenation reduction. The synthetic route has the defect that long-chain terminal alkyne is not easy to obtain. In 1982 paragonism et al proposed a synthetic route to multi-positional isomerisation of acetylenic hydrocarbons, in 1986, Mithran S et al and 1995 Yuan, Gu proposed a synthetic method similar to the above but with a slight change in the choice of starting materials, but using acetylenic-containing starting materials.
2. Synthetic routes starting from aldehydes. The synthesis of the route is characterized in that: the preparation method is characterized in that appropriate aldehyde is used as a raw material, and carbonyl alkene is generated through a Wittig reaction to directly establish a double bond required in the grapholitha molesta sex pheromone. The terminal groups are generally introduced directly from the starting materials. The cis-and trans-synthetic routes proposed by Schaub B et al in 1985 are typical methods for the synthesis of sex pheromones of this type, and they start with omega-hydroxyalkylphosphorium salt and a suitable aldehyde to synthesize cis-and trans-Grapholitha molesta sex pheromones, and are related to this type of methodThere are many reports of synthesis methods, and the synthesis methods are similar, but there are differences in the choice of raw materials. Such as: leseng and the like take cyclooctanone as a raw material to synthesize (Z/E) -8-dodecene-1-alcohol acetate through 8 steps; vinczer, Peter et al with 1, 8-octanediol and pH3Synthesizing (Z/E) -8-dodecen-1-ol mixture by taking p ═ CHPr as a raw material; and Yuan, Gu as HO (CH) in 19952)nOH and CH3(CH2) mCHO is used as raw material to synthesize (Z/E) -8-dodecene-1-alcohol acetate (n is 8, m is 2).
In nearly thirty years, organic chemistry experts do a great deal of work on the synthesis of grapholitha molesta sex pheromone, and target products are synthesized from various raw materials; however, the operation is complicated, or the raw materials are not easily available. Therefore, how to provide a synthetic method with simple and safe operation and low cost is a problem that needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for synthesizing cis (trans) -8-dodecenol acetate, so as to solve the problems of difficult obtainment of raw materials, complicated operation process, high synthesis cost and the like in the current synthesis of grapholitha molesta sex pheromone.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for synthesizing cis (trans) -8-dodecenol acetate comprises the following steps:
(1) at normal temperature, 1, 8-octanediol is placed in an acetic acid aqueous solution, sulfuric acid is used as a catalyst, and the mixture is continuously stirred to react the 1, 8-octanediol with acetic acid to generate 8-acetoxyl-1-octanol; continuously extracting the generated 8-acetoxyl-1-octanol with petroleum ether in a centrifugal extractor, extracting to obtain a petroleum ether phase, and distilling to recover the petroleum ether in the petroleum ether phase to obtain the 8-acetoxyl-1-octanol;
(2) adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring to dissolve the sodium bromide and the sodium acetate trihydrate, then adding tetramethyl piperidine oxide, continuously dropwise adding a sodium hypochlorite solution, and reacting to generate 8-acetoxyl-1-octanal;
(3) adding butyl triphenyl phosphonium bromide into tetrahydrofuran, dropwise adding organic base while stirring, and reacting to generate phosphorus ylide; 8-acetoxyl-1-octanal is dripped into the phosphorus ylide to lead the phosphorus ylide and the 8-acetoxyl-1-octanal to carry out wittig reaction to generate cis (trans) -8-dodecenyl alcohol acetate.
In the method for synthesizing cis (trans) -8-dodecenol acetate, in the step (1), the molar ratio of 1, 8-octanediol, sulfuric acid and acetic acid is 1: (0.5-5): (5-15); in the acetic acid aqueous solution, the mass concentration of acetic acid is 10-25 wt%; the concentration of the sulfuric acid is 1.5 wt% -14 wt%.
In the step (1), continuously extracting 8-acetoxyl-1-octanol generated by the reaction by using petroleum ether by using a continuous centrifugal extractor, continuously extracting for 10-24 hours to obtain a petroleum ether phase, distilling the petroleum ether in the petroleum ether phase, and obtaining 8-acetoxyl-1-octanol after evaporating the petroleum ether to dryness; the rotating speed of the continuous centrifugal extractor is 1450r/min, the distilled petroleum ether continuously enters the continuous centrifugal extractor, and the petroleum ether is recycled. Under the catalysis of strong acid at room temperature, acetic acid in 10-25 wt% acetic acid water solution performs selective unilateral esterification reaction on 1, 8-octanediol; the 8-acetoxyl-1-octanol generated by the reaction is continuously extracted by petroleum ether, 1, 8-octanediol is hardly dissolved in the petroleum ether, and the 8-acetoxyl-1-octanol is easily extracted by the petroleum ether due to the existence of a large amount of water in a reaction system, and simultaneously, the generation of suberoyl diacetate is greatly hindered, so that the 8-acetoxyl-1-octanol has higher yield.
In the method for synthesizing cis (trans) -8-dodecenol acetate, in the step (2), the molar ratio of 8-acetoxyl-1-octanol to water to ethyl acetate to sodium bromide to sodium acetate trihydrate to tetramethylpiperidine oxide to sodium hypochlorite is 1: (15-30): (10-25): (0.5-1.5): (0.5-3): (0.005-0.01): (1-2), wherein the available chlorine of the sodium hypochlorite solution is 7-11 wt%; the reaction temperature in the step (2) is controlled to be 0-10 ℃. In the step (2), water and ethyl acetate are used as reaction solvents, sodium bromide and sodium hypochlorite are converted to generate sodium hypobromite which is used as an oxidant, and sodium acetate trihydrate is used as a two-phase catalyst.
The method for synthesizing cis (trans) -8-dodecenol acetate comprises the following specific operation method in the step (2):
step (2-1): adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring to dissolve the sodium bromide and the sodium acetate trihydrate, and then adding tetramethylpiperidine oxide to obtain a reaction system A;
step (2-2): reducing the temperature of the reaction system A to 0 ℃, dropwise adding a sodium hypochlorite solution, controlling the temperature of the reaction system A to be 0-10 ℃, and after dropwise adding of the sodium hypochlorite solution is completed, carrying out heat preservation reaction at the temperature of 0-10 ℃ for 1h to obtain a reaction system B;
step (2-3): sampling and detecting the content of 8-acetoxyl-1-octanol in a reaction system B, if the content of 8-acetoxyl-1-octanol is less than 3% of the initial content, adding sodium sulfite into the reaction system B for inactivation, standing and layering, and layering the reaction system B to obtain an aqueous phase layer and an organic phase layer; the adding amount of the sodium sulfite is 1 percent of the molar mass of the 8-acetoxyl group-1-octanol; the reason why the present invention does not use pyridinium chlorochromate for oxidation is that: hexavalent chromium has high toxicity; firstly, the post-treatment is difficult, and thirdly, the cost is high; the invention selects cheap and easily available sodium hypochlorite and sodium bromide as raw materials to be converted into sodium hypobromite, uses tetramethyl piperidine oxide TEMPO as a catalyst, and can oxidize 8-acetoxyl group-1-octanol into 8-acetoxyl group-1-octanol under mild reaction conditions; the method has the advantages of simple operation, safety, simple and convenient post-treatment and high yield.
Step (2-4): extracting the aqueous layer with ethyl acetate for 3 times, wherein the volume ratio of ethyl acetate to 8-acetoxy-1-octanol for each extraction is 2: 1, combining ethyl acetate phases after 3 times of extraction to obtain an organic phase A; combining the organic phase layers, washing for 3 times by using an ammonium chloride solution with the mass fraction of 20-25 wt%, wherein the volume ratio of the ammonium chloride solution to 8-acetoxyl-1-octanol in each washing is 1:1, marking the washed organic phase layer as an organic phase B; extracting the washed ammonium chloride solution phase with ethyl acetate for 2 times, wherein the volume ratio of the ethyl acetate to the 8-acetoxyl-1-octanol in each extraction is 2: 1, combining ethyl acetate phases after 2 times of extraction to obtain an organic phase C;
step (2-5): and combining and drying the organic phase A, the organic phase B and the organic phase C, performing suction filtration after drying, and distilling and recovering ethyl acetate from filtrate obtained by suction filtration to obtain the 8-acetoxyl-1-octanal.
In the above method for synthesizing cis (trans) -8-dodecenol acetate, in the step (3), the preparation method of the organic base comprises the following steps: under the protection of inert gas, stirring and mixing tetrahydrofuran, sodium hydride and dimethyl sulfoxide, then heating to 50-70 ℃, carrying out heat preservation reaction for 2 hours, and obtaining the organic base dimethyl sulfoxide sodium after the reaction liquid is clarified. In the invention, n-butyllithium and sodium hexamethyldisilazide which are high in price and dangerous to operate are not used as organic base raw materials, but sodium dimethyl sulfoxide is obtained by self-preparation by adopting the method and is used as the organic base, so that the cost is low, and the safety is good. In the invention, the organic base is prepared firstly, and then the prepared liquid organic base is used for the phosphorus ylide reaction, which is mainly because butyl triphenyl phosphonium bromide is not dissolved in tetrahydrofuran, and the dimethyl sulfoxide sodium prepared in the step forms the liquid organic base in the tetrahydrofuran, so that the organic base is easier to react with the butyl triphenyl phosphonium bromide.
In the method for synthesizing the cis (trans) -8-dodecenol acetate, the molar ratio of sodium hydride to tetrahydrofuran to dimethyl sulfoxide is 1: (1-5): (2-10).
In the method for synthesizing cis (trans) -8-dodecenol acetate, in the step (3), the molar ratio of the organic base, the butyl triphenyl phosphonium bromide and the 8-acetoxyl-1-octanal is (1-2.5): 1: (0.5 to 1); the reaction temperature in the step (3) is controlled to be between minus 10 ℃ and minus 50 ℃.
The method for synthesizing cis (trans) -8-dodecenol acetate comprises the following specific operation method in the step (3):
step (3-1): putting tetrahydrofuran and butyl triphenyl phosphonium bromide into a reaction kettle in sequence, reducing the temperature of a mixed system of the tetrahydrofuran and the butyl triphenyl phosphonium bromide to (-10) (-50) ° C, then slowly dropwise adding organic base into the reaction kettle, and reacting for 1h to obtain a reaction system C;
step (3-2): controlling the temperature of the reaction system C to be (-10) (-50) ° C, diluting 8-acetoxyl-1-octanal with tetrahydrofuran, then dropwise adding into a reaction kettle, wherein the volume ratio of the 8-acetoxyl-1-octanal to the tetrahydrofuran is 1:1, and reacting for 1h after dropwise adding is finished to obtain a reaction system D;
step (3-3): sampling and detecting the content of 8-acetoxyl-1-octanal in the reaction system D, and if the content is less than 1% of the initial content, adding a saturated ammonium chloride aqueous solution into the reaction system D for inactivation; after inactivation, distilling and recovering tetrahydrofuran to obtain concentrated feed liquid A;
step (3-4): extracting the concentrated feed liquid A for 3 times by using petroleum ether, wherein the volume ratio of the petroleum ether to the 8-acetoxyl-1-octanal is 2: 1, combining the petroleum ether phases after the 3 times of extraction to obtain an organic phase D;
step (3-5): drying the organic phase D by using anhydrous sodium sulfate, performing suction filtration after drying, and distilling and recovering petroleum ether from filtrate obtained by suction filtration to obtain concentrated feed liquid B; and rectifying the concentrated feed liquid B to obtain cis (trans) -8-dodecenol acetate.
In the method for synthesizing cis (trans) -8-dodecenol acetate, in the step (3), the molar ratio of tetrahydrofuran to butyl triphenyl phosphonium bromide is 1: 18.
The technical scheme of the invention achieves the following beneficial technical effects:
(1) the synthetic raw materials used in the invention are cheap, have wide sources and are easy to obtain; the synthesis method provided by the invention has the advantages of short period, few steps, high yield, simple post-treatment and the like, and is suitable for large-scale industrial production.
(2) The invention takes 1, 8-octanediol and acetic acid water solution as raw materials, firstly single side acetylation is carried out to obtain 8-acetoxyl group-1-octanol; then oxidizing the 8-acetoxyl-1-octanol by using sodium hypochlorite aqueous solution to obtain 8-acetoxyl-1-octanal; and then reacting butyl triphenyl phosphonium bromide serving as a raw material with organic alkali to generate phosphorus ylide, and then carrying out wittig reaction on the generated phosphorus ylide and 8-acetoxyl-1-octanal to generate cis (trans) -8-dodecenol acetate. The synthesis method can synthesize the cis (trans) -8-dodecenol acetate by only three steps.
(3) By adopting the synthesis method, the yield of the 8-acetoxyl-1-octanol can reach more than 75 percent; the yield of the 8-acetoxyl-1-octanal can reach more than 94 percent; the yield of the cis (trans) -8-dodecenol acetate can reach more than 75 percent. The invention has the advantages of easily obtained raw materials, simple production flow, strong operability of industrial production and low production cost, and is suitable for industrial application.
Drawings
FIG. 1 is a flow chart of the process for the synthesis of cis (trans) -8-dodecenol acetate according to the invention;
FIG. 2 is a nuclear magnetic spectrum (carbon spectrum) of a cis (trans) -8-dodecenyl enol acetate standard according to the present invention;
FIG. 3 is a nuclear magnetic spectrum (hydrogen spectrum) of a cis (trans) -8-dodecenyl enol acetate standard according to the present invention;
FIG. 4 nuclear magnetic spectrum (carbon spectrum) of the synthesized product of cis (trans) -8-dodecenol acetate in example 1 of the present invention;
FIG. 5 nuclear magnetic spectrum (hydrogen spectrum) of the synthesized product of cis (trans) -8-dodecenol acetate in example 1 of the present invention.
The reference numbers in the figures denote: 1-1, 8-octanediol; 2-acetic acid; 3-8-acetoxy-1-octanol; 4-sodium hypochlorite; 5-8-acetoxy-1-octanal; 6-butyltriphenylphosphonium bromide; sodium 7-dimethyl sulfoxide; 8-phosphorus ylide.
Detailed Description
The scheme of the method for synthesizing cis (trans) -8-dodecenol acetate is shown in figure 1, and the method for synthesizing the same is further illustrated by the following examples in conjunction with figure 1.
Example 1
A method for synthesizing cis (trans) -8-dodecenol acetate comprises the following steps:
(1) at normal temperature, 1, 8-octanediol is placed in an acetic acid aqueous solution, sulfuric acid is used as a catalyst, and the mixture is continuously stirred to react the 1, 8-octanediol with acetic acid to generate 8-acetoxyl-1-octanol; continuously extracting 8-acetoxyl-1-octanol generated by the reaction by using petroleum ether by using a continuous centrifugal extractor, continuously extracting for 20 hours to obtain a petroleum ether phase, distilling the petroleum ether in the petroleum ether phase, and evaporating the petroleum ether to dryness to obtain 8-acetoxyl-1-octanol; the rotating speed of the continuous centrifugal extractor is 1450r/min, the evaporated petroleum ether continuously enters the continuous centrifugal extractor, and the petroleum ether is recycled;
(2) adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring to dissolve the sodium bromide and the sodium acetate trihydrate, then adding tetramethyl piperidine oxide, continuously dropwise adding a sodium hypochlorite solution, and reacting to generate 8-acetoxyl-1-octanal;
(3) adding butyl triphenyl phosphonium bromide into tetrahydrofuran, dropwise adding organic base while stirring, and reacting to generate phosphorus ylide; 8-acetoxyl-1-octanal is dripped into the phosphorus ylide to lead the phosphorus ylide and the 8-acetoxyl-1-octanal to carry out wittig reaction to generate cis (trans) -8-dodecenyl alcohol acetate.
In step (1), the molar ratio of 1, 8-octanediol, sulfuric acid and acetic acid is 1: 5: 15; in the acetic acid aqueous solution, the mass concentration of acetic acid is 10 wt%; the concentration of sulfuric acid was 14 wt%.
In the step (2), the molar ratio of 8-acetoxyl-1-octanol to water to ethyl acetate to sodium bromide to sodium acetate trihydrate to tetramethylpiperidine oxide to sodium hypochlorite is 1: 30: 25: 1.5: 3: 0.01: 2, wherein the available chlorine in the sodium hypochlorite solution is 11 wt%;
the specific operation method of the step (2) is as follows:
step (2-1): adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring to dissolve the sodium bromide and the sodium acetate trihydrate, and then adding tetramethylpiperidine oxide to obtain a reaction system A;
step (2-2): reducing the temperature of the reaction system A to 0 ℃, dropwise adding a sodium hypochlorite solution, controlling the temperature of the reaction system A to be 0 ℃, and after dropwise adding of the sodium hypochlorite solution is completed, carrying out heat preservation reaction at the temperature of 0 ℃ for 1h to obtain a reaction system B;
step (2-3): sampling and detecting the content of 8-acetoxyl-1-octanol in a reaction system B, wherein the content of 8-acetoxyl-1-octanol is 1.88 percent of the initial content and is less than 3 percent of the initial content, adding sodium sulfite into the reaction system B for inactivation, standing and layering, and obtaining an aqueous phase layer and an organic phase layer after the reaction system B is layered; the addition of sodium sulfite is 1 percent of the molar mass of 8-acetoxyl-1-octanol.
Step (2-4): extracting the aqueous layer with ethyl acetate for 3 times, wherein the volume ratio of ethyl acetate to 8-acetoxy-1-octanol for each extraction is 2: 1, combining ethyl acetate phases after 3 times of extraction to obtain an organic phase A; combining the organic phase layers, washing the organic phase layers for 3 times by using an ammonium chloride solution with the mass fraction of 25 wt%, wherein the volume ratio of the ammonium chloride solution to the 8-acetoxy-1-octanol in each washing is 1:1, marking the washed organic phase layer as an organic phase B; extracting the washed ammonium chloride solution phase with ethyl acetate for 2 times, wherein the volume ratio of the ethyl acetate to the 8-acetoxyl-1-octanol in each extraction is 2: 1, combining ethyl acetate phases after 2 times of extraction to obtain an organic phase C;
step (2-5): and combining and drying the organic phase A, the organic phase B and the organic phase C, performing suction filtration after drying, and distilling and recovering ethyl acetate from filtrate obtained by suction filtration to obtain the 8-acetoxyl-1-octanal.
In the step (3), the preparation method of the organic base comprises the following steps: under the protection of inert gas, stirring and mixing tetrahydrofuran, sodium hydride and dimethyl sulfoxide, then heating to 70 ℃, preserving heat and reacting for 2 hours, and obtaining the organic base dimethyl sulfoxide sodium after the reaction solution is clarified; the molar ratio of sodium hydride, tetrahydrofuran and dimethyl sulfoxide is 1: 5: 10.
in the step (3), the molar ratio of the organic base, the butyl triphenyl phosphonium bromide and the 8-acetoxy-1-octanal is 1: 1: 0.5;
the specific operation method of the step (3) is as follows:
step (3-1): adding butyl triphenyl phosphonium bromide and tetrahydrofuran into a reaction kettle, wherein the molar ratio of the tetrahydrofuran to the butyl triphenyl phosphonium bromide is 1:18, reducing the temperature of a mixed system of the butyl triphenyl phosphonium bromide and the tetrahydrofuran to-10 ℃, then slowly dropwise adding an organic base into the reaction kettle, controlling the reaction temperature to-10 ℃, and reacting for 1h to obtain a reaction system C;
step (3-2): controlling the temperature of the reaction system C to be-10 ℃, diluting 8-acetoxyl-1-octanal with tetrahydrofuran, and then dropwise adding into a reaction kettle, wherein the volume ratio of 8-acetoxyl-1-octanal to tetrahydrofuran is 1: 1; reacting for 1h after the dropwise adding is finished to obtain a reaction system D;
step (3-3): sampling and detecting the content of 8-acetoxyl-1-octanal in the reaction system D, wherein the content of the 8-acetoxyl-1-octanal is 0.27 percent of the initial content and is less than 1 percent of the initial content, adding a saturated ammonium chloride aqueous solution into the reaction system D for inactivation, and the adding volume of the saturated ammonium chloride aqueous solution is equal to the volume of dimethyl sulfoxide used in the step (3) for preparing the organic base; after inactivation, distilling and recovering tetrahydrofuran to obtain concentrated feed liquid A;
step (3-4): extracting the concentrated feed liquid A for 3 times by using petroleum ether, wherein the volume ratio of the petroleum ether to the 8-acetoxyl-1-octanal is 2: 1, combining the petroleum ether phases after the 3 times of extraction to obtain an organic phase D;
step (3-5): drying the organic phase D by using anhydrous sodium sulfate, performing suction filtration after drying, and distilling and recovering petroleum ether from filtrate obtained by suction filtration to obtain concentrated feed liquid B; and rectifying the concentrated feed liquid B to obtain cis (trans) -8-dodecenol acetate.
In this example, the yield of 8-acetoxy-1-octanol prepared in step (1) was 76%, and the yield of 8-acetoxy-1-octanal prepared in step (2) was 98%; the yield of cis (trans) -8-dodecenol acetate prepared in the step (3) was 79%.
FIGS. 2 and 3 are a carbon spectrum and a hydrogen spectrum of a cis (trans) -8-dodecenyl enol acetate standard, respectively; FIGS. 4 and 5 are a carbon spectrum and a hydrogen spectrum, respectively, of cis (trans) -8-dodecenol acetate prepared in this example; as can be seen from the comparison of FIGS. 2 and 4 and FIGS. 3 and 5, the carbon spectrum and the hydrogen spectrum of the product prepared in this example are consistent with those of the cis (trans) -8-dodecenol acetate standard, which indicates that the target product, cis (trans) -8-dodecenol acetate, is prepared in this example.
Example 2
This example is similar to the method of example 1, with the following differences:
in step (1), the molar ratio of 1, 8-octanediol, sulfuric acid and acetic acid is 1: 0.5: 5; in the acetic acid aqueous solution, the mass concentration of acetic acid is 25 wt%;
in the step (2), the molar ratio of 8-acetoxyl-1-octanol to water to ethyl acetate to sodium bromide to sodium acetate trihydrate to tetramethylpiperidine oxide to sodium hypochlorite is 1: 15: 10: 0.5: 0.5: 0.005: 1;
in the step (3), the organic base is prepared by a method comprising: the molar ratio of sodium hydride, tetrahydrofuran and dimethyl sulfoxide is 1: 1: 2; in step (3), the molar ratio of the organic base, butyltriphenylphosphonium bromide and 8-acetoxy-1-octanal is 2.5: 1: 1.
in this example, the yield of 8-acetoxy-1-octanol prepared in step (1) was 80%, and the yield of 8-acetoxy-1-octanal prepared in step (2) was 98%; the yield of cis (trans) -8-dodecenol acetate prepared in step (3) was 78%.
Example 3
This example is similar to the method of example 1, with the following differences:
in the step (1), the extraction time is 10 hours;
in the step (2-2), reducing the temperature of the reaction system A to 0 ℃, dropwise adding a sodium hypochlorite solution, controlling the temperature of the reaction system A to be 10 ℃, and after dropwise adding of the sodium hypochlorite solution is completed, carrying out heat preservation reaction at the temperature of 10 ℃ for 1h to obtain a reaction system B;
in the step (3-1) and the step (3-2), the reaction temperature was controlled at-50 ℃.
In this example, the yield of 8-acetoxy-1-octanol prepared in step (1) was 75% and the yield of 8-acetoxy-1-octanal prepared in step (2) was 94%; the yield of cis (trans) -8-dodecenol acetate prepared in the step (3) was 75%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (10)
1. A method for synthesizing cis (trans) -8-dodecenol acetate is characterized by comprising the following steps:
(1) at normal temperature, 1, 8-octanediol is placed in an acetic acid aqueous solution, sulfuric acid is used as a catalyst, and the mixture is continuously stirred to react the 1, 8-octanediol with acetic acid to generate 8-acetoxyl-1-octanol; continuously extracting the generated 8-acetoxyl-1-octanol with petroleum ether in a centrifugal extractor, extracting to obtain a petroleum ether phase, and distilling to recover the petroleum ether in the petroleum ether phase to obtain the 8-acetoxyl-1-octanol;
(2) adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring to dissolve the sodium bromide and the sodium acetate trihydrate, then adding tetramethyl piperidine oxide, dropwise adding a sodium hypochlorite solution, and reacting to generate 8-acetoxyl-1-octanal;
(3) adding butyl triphenyl phosphonium bromide into tetrahydrofuran, dropwise adding organic base while stirring, and reacting to generate phosphorus ylide; 8-acetoxyl-1-octanal is dripped into the phosphorus ylide to lead the phosphorus ylide and the 8-acetoxyl-1-octanal to carry out wittig reaction to generate cis (trans) -8-dodecenyl alcohol acetate.
2. The process for the synthesis of cis (trans) -8-dodecenol acetate as claimed in claim 1, wherein in step (1), the molar ratio of 1, 8-octanediol, sulfuric acid and acetic acid is 1: (0.5-5): (5-15); in the acetic acid aqueous solution, the mass concentration of acetic acid is 10-25 wt%; the concentration of the sulfuric acid is 1.5 wt% -14 wt%.
3. The method for synthesizing cis (trans) -8-dodecenol acetate according to claim 1, wherein in the step (1), a continuous centrifugal extractor is used, 8-acetoxyl-1-octanol generated by the reaction is continuously extracted by petroleum ether, a petroleum ether phase is obtained after continuous extraction is carried out for 10-24 hours, the petroleum ether in the petroleum ether phase is distilled, and the 8-acetoxyl-1-octanol is obtained after the petroleum ether is dried by distillation; the rotating speed of the continuous centrifugal extractor is 1450r/min, the distilled petroleum ether continuously enters the continuous centrifugal extractor, and the petroleum ether is recycled.
4. The method for synthesizing cis (trans) -8-dodecenol acetate as claimed in claim 1, wherein in step (2), the molar ratio of 8-acetoxy-1-octanol, water, ethyl acetate, sodium bromide, sodium acetate trihydrate, tetramethylpiperidine oxide and sodium hypochlorite is 1: (15-30): (10-25): (0.5-1.5): (0.5-3): (0.005-0.01): (1-2), wherein the available chlorine of the sodium hypochlorite solution is 7-11 wt%.
5. The method for synthesizing cis (trans) -8-dodecenol acetate as claimed in claim 1, wherein the specific operation method of step (2) is:
step (2-1): adding water, ethyl acetate, sodium bromide and sodium acetate trihydrate into 8-acetoxyl-1-octanol, stirring to dissolve the sodium bromide and the sodium acetate trihydrate, and then adding tetramethylpiperidine oxide to obtain a reaction system A;
step (2-2): reducing the temperature of the reaction system A to 0 ℃, dropwise adding a sodium hypochlorite solution, controlling the temperature of the reaction system A to be 0-10 ℃, and after dropwise adding of the sodium hypochlorite solution is completed, carrying out heat preservation reaction at the temperature of 0-10 ℃ for 1h to obtain a reaction system B;
step (2-3): adding sodium sulfite into the reaction system B for inactivation, standing and layering, and obtaining an aqueous phase layer and an organic phase layer after layering the reaction system B; the adding amount of the sodium sulfite is 1 percent of the molar mass of the 8-acetoxyl group-1-octanol;
step (2-4): extracting the aqueous layer with ethyl acetate for 3 times, wherein the volume ratio of ethyl acetate to 8-acetoxy-1-octanol for each extraction is 2: 1, combining ethyl acetate phases after 3 times of extraction to obtain an organic phase A; washing the organic phase layer for 3 times by using an ammonium chloride solution with the mass fraction of 20-25 wt%, wherein the volume ratio of the ammonium chloride solution to 8-acetoxyl-1-octanol in each washing is 1:1, marking the washed organic phase layer as an organic phase B; extracting the washed ammonium chloride solution phase with ethyl acetate for 2 times, wherein the volume ratio of the ethyl acetate to the 8-acetoxyl-1-octanol in each extraction is 2: 1, combining ethyl acetate phases after 2 times of extraction to obtain an organic phase C;
step (2-5): and combining and drying the organic phase A, the organic phase B and the organic phase C, performing suction filtration after drying, and distilling and recovering ethyl acetate from filtrate obtained by suction filtration to obtain the 8-acetoxyl-1-octanal.
6. The method for synthesizing cis (trans) -8-dodecenol acetate as claimed in claim 1, wherein in step (3), the preparation method of the organic base is: under the protection of inert gas, tetrahydrofuran, sodium hydride and dimethyl sulfoxide are stirred and mixed, then heated to 50-70 ℃, the temperature is kept for reaction for 2 hours, and the organic base dimethyl sulfoxide sodium is prepared after reaction liquid is clarified.
7. The method for synthesizing cis (trans) -8-dodecenol acetate as claimed in claim 6, wherein the molar ratio of sodium hydride, tetrahydrofuran and dimethyl sulfoxide is 1: (1-5): (2-10).
8. The method for synthesizing cis (trans) -8-dodecenol acetate according to claim 1, wherein in step (3), the molar ratio of the organic base, butyltriphenylphosphonium bromide and 8-acetoxy-1-octanal is (1-2.5): 1: (0.5 to 1).
9. The method for synthesizing cis (trans) -8-dodecenol acetate as claimed in claim 1, wherein the specific operation method of step (3) is:
step (3-1): putting tetrahydrofuran and butyl triphenyl phosphonium bromide into a reaction kettle in sequence, reducing the temperature of a mixed system of the tetrahydrofuran and the butyl triphenyl phosphonium bromide to (-10) (-50) ° C, then slowly dropwise adding organic base into the reaction kettle, and reacting for 1h to obtain a reaction system C;
step (3-2): controlling the temperature of the reaction system C to be (-10) (-50) ° C, diluting 8-acetoxyl-1-octanal with tetrahydrofuran, then dropwise adding into a reaction kettle, wherein the volume ratio of the 8-acetoxyl-1-octanal to the tetrahydrofuran is 1:1, and reacting for 1h after dropwise adding is finished to obtain a reaction system D;
step (3-3): adding saturated ammonium chloride aqueous solution into the reaction system D for inactivation; after inactivation, distilling and recovering tetrahydrofuran to obtain concentrated feed liquid A;
step (3-4): extracting the concentrated feed liquid A for 3 times by using petroleum ether, wherein the volume ratio of the petroleum ether to the 8-acetoxyl-1-octanal is 2: 1, combining the petroleum ether phases after the 3 times of extraction to obtain an organic phase D;
step (3-5): drying the organic phase D by using anhydrous sodium sulfate, performing suction filtration after drying, and distilling and recovering petroleum ether from filtrate obtained by suction filtration to obtain concentrated feed liquid B; and rectifying the concentrated feed liquid B to obtain cis (trans) -8-dodecenol acetate.
10. The method for synthesizing cis (trans) -8-dodecenol acetate as claimed in claim 1, wherein in step (3), the molar ratio of tetrahydrofuran and butyltriphenylphosphonium bromide is 1: 18.
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| CN102795998A (en) * | 2012-08-23 | 2012-11-28 | 昆明博鸿生物科技有限公司 | Method for synthesis of sex pheromone compound of grapholitha molesta |
| CN105218361A (en) * | 2015-10-19 | 2016-01-06 | 石家庄中硕药业有限公司 | A kind of synthetic method of dodecylene alcohol acetic ester |
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| CN102206151A (en) * | 2010-03-30 | 2011-10-05 | 上海灏翔生物科技有限公司 | Synthetic method of royaljelly acid |
| CN102795998A (en) * | 2012-08-23 | 2012-11-28 | 昆明博鸿生物科技有限公司 | Method for synthesis of sex pheromone compound of grapholitha molesta |
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