CN110227512A - A kind of preparation method and its application of the catalyst preparing beta-unsaturated ketone for Saucy-Marbet reaction - Google Patents
A kind of preparation method and its application of the catalyst preparing beta-unsaturated ketone for Saucy-Marbet reaction Download PDFInfo
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- CN110227512A CN110227512A CN201910519957.XA CN201910519957A CN110227512A CN 110227512 A CN110227512 A CN 110227512A CN 201910519957 A CN201910519957 A CN 201910519957A CN 110227512 A CN110227512 A CN 110227512A
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- catalyst
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- unsaturated
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- active component
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 68
- 150000002576 ketones Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 alkoxy alkene Chemical class 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000005864 Sulphur Substances 0.000 claims abstract description 13
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 9
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 9
- 239000011294 coal tar pitch Substances 0.000 claims description 8
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 4
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 claims description 4
- 229930007744 linalool Natural products 0.000 claims description 4
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 108010024636 Glutathione Proteins 0.000 claims description 3
- 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 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229960003180 glutathione Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 2
- 229960003019 loprazolam Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 238000006563 Carroll rearrangement reaction Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013734 beta-carotene Nutrition 0.000 description 1
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 1
- 239000011648 beta-carotene Substances 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides the preparation method and its application that a kind of Saucy-Marbet reaction prepares beta-unsaturated ketone used catalyst, comprising: (1) using carbon presoma as raw material, is acidified with mixed acid；(2) it washed, dried to get the catalyst for loading main active component is arrived after filtering the mixture that step (1) obtains；(3) catalyst, metal salt, surfactant, phosphorus source and/or the sulphur source of main active component will be loaded, water mixes, hydro-thermal reaction occurs, the load for realizing cocatalyst component, filtered, dry after loaded the catalyst prod of main active component and cocatalyst component.Using unsaturated alcohol and alkoxy alkene as raw material, under carbon dioxide atmosphere, Saucy-Marbet occurs under catalyst effect and reacts obtained beta-unsaturated ketone, with highly selective, high conversion, be easily isolated, it is recyclable apply, the advantages such as small to equipment corrosion, be a kind of green catalyst for synthesizing beta-unsaturated ketone.
Description
Technical field
The present invention relates to beta-unsaturated ketone preparations, and in particular to a kind of to prepare beta-unsaturated ketone for Saucy-Marbet reaction
The preparation method and its application of catalyst.
Background technique
The preparation of beta-unsaturated ketone is an important process of field of fine chemical, and beta-unsaturated ketone is closed as important chemistry
At intermediate, it is widely used in the fields such as pesticide, medicine and new material.For example, pseudo ionone also known as 6,10- dimethyl-
3,5,9- tridecylene -2- ketone are the important source materials for synthesizing vitamin A, beta carotene.
The method for preparing beta-unsaturated ketone can be divided into diethenone process, methyl acetoacetate method (Carroll reaction) and alkoxy
Olefin processes (Saucy-Marbet reaction).Wherein, US3029287, US6184420 describe Saucy-Marbet reaction first,
More favors are received due to the advantages such as it is high with reaction yield, reaction condition is mild.But Saucy-Marbet reacts
Used catalyst is acidic catalyst, such as sulfuric acid, phosphoric acid, Loprazolam, trichloroacetic acid, toluenesulfonic acid, therefore this is anti-
The disadvantages of catalyst can not be recycled, is strong, exothermic heat of reaction is violent to equipment corrosion should be also faced with.
Therefore, environmentally protective, high conversion how is prepared, highly selective, catalyst with long service life becomes restriction
Saucy-Marbet reaction prepares the key factor of beta-unsaturated ketone technological development.
Summary of the invention
One of the objects of the present invention is to provide a kind of catalyst that beta-unsaturated ketone is prepared for Saucy-Marbet reaction
And its preparation method.This method is environmentally protective, it is small to corrode to equipment, and catalyst obtained has selectivity and high conversion rate, is easy to point
From, it is recyclable the advantages such as apply, Saucy-Marbet reaction can be promoted to prepare the sound development of beta-unsaturated ketone technique.
Saucy-Marbet reaction system is carried out using catalyst above-mentioned it is another object of the present invention to provide a kind of
The method of standby beta-unsaturated ketone.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method for the catalyst preparing beta-unsaturated ketone for Saucy-Marbet reaction, includes the following steps:
(1) using carbon presoma as raw material, acidification is carried out using mixed acid；
(2) it after the mixture filtering obtained step (1), washed, dried to get urging to the main active component of load
Agent；
(3) catalyst, metal salt, surfactant, phosphorus source and/or the sulphur of main active component will be loaded obtained by step (2)
Source, water mixing, occur hydro-thermal reaction, and the load of phosphide and/or sulfide is carried out to the catalyst for loading main active component, from
And realize the load of cocatalyst component, filtered, dry after loaded urging for main active component and cocatalyst component
Agent product.
Preferably, in the step (1), carbon presoma is selected from selected from coal tar pitch and petroleum asphalt, coal liquefaction residue, plant straw
One of stalk is a variety of, but not limited to this.
Preferably, in the step (1), mixed acid H2SO4、H3PO4、HNO3、CH3COOH、HClO4, it is any in HCl
Two kinds, preferably H2SO4、H3PO4、HNO3, any two kinds in HCl；In mixed acid, two kinds of sour mass ratioes are 1:1-1:10, excellent
Select 1:2-1:6.Unless otherwise specified, the acid refers to solute component (similarly hereinafter)；The acid can be used with 50wt% aqueous solution.
Mixed acid processing can make the main active component part of catalyst introduce SO4 2-、H2PO4 -、NO3 -Etc. different acidic-groups,
Play the role of major catalyst active component to catalyst Saucy-Marbet reaction, in addition, the introducing of multiple types acidic-group
Play the role of collaboration promotion for promoting reaction selectivity.
Preferably, in the step (1), the mass ratio of carbon presoma and mixed acid is 1:10-1:50, preferably 1:20-
1:40。
Preferably, in the step (1), the time of acidification is 1h-24h, preferably 2h-8h；The temperature of acidification
It is 50-150 DEG C, preferably 80-120 DEG C.
Preferably, in the step (2), drying time 4h-24h, preferably 6h-10h；Drying temperature is 100-150 DEG C,
It is preferred that 120-130 DEG C.
Preferably, in the step (3), metallic element in the metal salt be selected from one of copper, iron, zinc and sodium or
It is a variety of, but not limited to this.
Preferably, in the step (3), the metal salt is selected from sulfate, phosphate, nitrate, sulphite, carbonic acid
One of salt is a variety of, but not limited to this.
Preferably, in the step (3), surfactant is selected from citric acid, ethylenediamine tetra-acetic acid and dodecyl sulphate
One of sodium is a variety of.
Preferably, the sulphur source in the step (3) is selected from one of thiocarbamide, thioacetamide, glutathione or a variety of；
Phosphorus source is selected from red phosphorus and/or white phosphorus；
Phosphorus source and/or sulphur source, wherein the mass percent of phosphorus source is 0-100%, preferably 20-80%, more preferable 40-
60%.
Sulfide (and/or phosphide) introduces catalyst system as cocatalyst component, can effectively promote reaction
Selectivity；And sulfide and phosphide are introduced simultaneously, the two can be by " confinement effect ", can be fast after reacting raw material to product
Speed is detached from catalyst, is avoided reacting with raw material excessive contact, to be further reduced the generation of heavy component, is improved reaction
Selectivity.
Preferably, metal salt, phosphorus source and/or sulphur source in the step (3), surfactant, load main active component
The mass ratio of catalyst is 1:(1-10): (0.1-1.0): (50-100), preferably 1:(2-5): (0.2-0.5): (60-80), water
Dosage guarantee excessive, raw material can be completely covered.
Preferably, the reaction temperature of hydro-thermal reaction is 100-300 DEG C in the step (3), reaction time 5-48h；Into
One step preferable reaction temperature is 150-200 DEG C, reaction time 8-24h.
In the step (3), the selection of drying condition ensures that moisture is evaporated completely, and drying may be selected in this operating procedure
Temperature is 100 DEG C, drying time 12h.
Preferably, in catalyst prepared by the present invention, it is based on catalyst quality, the content of main active component is 7%-
15%, the content of cocatalyst component is 0.5%-1.5%.
The present invention handles carbon presoma using acidification mode, and gained catalyst contains a large amount of SO4 2-、H2PO4 -、NO3 -Deng
Acidic-group plays main facilitation for the raising of Saucy-Marbet reaction conversion ratio and selectivity；Phosphide (sulphur
Compound) it is introduced as cocatalyst component or reaction suppressor component, the generation of reaction heavy component can be effectively reduced, into
One step promotes the selectivity of reaction；Compared to other homogeneous catalysts (such as phosphoric acid, Loprazolam), which is heterogeneous urge
The separation with reaction solution can be realized by filters in agent, to carry out recycled；Compared to other strong acid based catalysts
Agent, the catalyst are also relatively small to the corrosivity of equipment.
The side that Saucy-Marbet reaction prepares beta-unsaturated ketone is carried out using catalyst above-mentioned the present invention also provides a kind of
Method, comprising:
Saucy-Marbet reaction is carried out using tank reactor and prepares beta-unsaturated ketone, with unsaturated alcohol and alkoxy alkene
For raw material, is reacted under the effect of above-mentioned catalyst and beta-unsaturated ketone is made, specific steps include:
A certain amount of unsaturated alcohol and above-mentioned catalyst are added in a kettle, after being warming up to certain temperature, it is preferred to use
Alkoxy alkene is added in the mode of dropwise addition in certain time for adding, and certain time is reacted after being added dropwise to complete, after reaction, will
Reaction solution filtering, preferably by flash distillation removing light component to get beta-unsaturated ketone product, catalyst can stay in a kettle directly into
Row recycled.
Wherein, the structural formula of beta-unsaturated ketone is as follows:
The structure of unsaturated alcohol and alkoxy alkene is as follows,
Wherein R1、R2、R3、R5Independently indicate hydrogen, saturation or unsaturated alkyl, R4、R6Independently indicate saturation or not
Saturated alkyl；Preferably:
R1、R2Independently indicate hydrogen, saturation or unsaturated alkyl containing 1-25 carbon atom,
R3、R5Independently indicate hydrogen, saturation or unsaturated alkyl containing 1-5 carbon atom,
R4、R6Independently indicate saturation or unsaturated alkyl containing 1-5 carbon atom；
It is highly preferred that alkoxy alkene is selected from 2- methoxyl group propylene, 2- ethoxy propylene, 2- methoxyl group -1- butylene, but not
It is confined to this；Unsaturated alcohol is selected from tetrahydro dehydrogenation nerolidol, dehydrogenation different vegetable alcohol, dihydro dehydrogenation linalool, dehydrogenation flores aurantii uncle
Alcohol, dihydro dehydrogenation nerolidol, dehydrogenation linalool, but not limited to this.
Preferably, the molar ratio of unsaturated alcohol and alkoxy alkene is 1:2-1:10, preferably 1:3-1:6.
Preferably, the mass ratio of unsaturated alcohol and catalyst is 1:0.001-1:1, preferably 1:0.01-1:0.1.
Preferably, reaction temperature is 80-160 DEG C, preferably 100-140 DEG C；Reaction gauge pressure is 0.3-2MPa, preferably 0.5-
1MPa。
Preferably, time for adding 0.1-10h, preferably 0.5-2h；Reaction time after being added dropwise to complete is 0.5-20h, excellent
Select 1-6h.
Preferably, the atmosphere of reaction is carbon dioxide.Carbon dioxide is not only acted as the atmosphere of reaction
Completely cut off air, avoids alkoxy alkene from reacting the effect for generating peroxide with oxygen, and carbon dioxide shows faintly acid, it can
Promote the promotion of reaction conversion ratio and selectivity.
Compared with prior art, the invention has the following advantages:
(1) under atmosphere of the invention, Saucy-Marbet reaction is catalyzed using catalyst of the invention
When, reaction conversion ratio reaches 99.0% or more, and reaction selectivity reaches 97.5% or more；Reaction conversion ratio is high, selectivity is high, weight
Matter component yield is few；
(2) catalyst of the invention is heterogeneous catalysis, is easy to separate with reaction solution, to carry out recycled, is dropped
Low production cost；
(3) catalyst of the invention is small to equipment corrosion.
Specific embodiment
Technical solution of the present invention and its effect are described further below by way of specific embodiment.Following embodiment is only
For illustrating that the contents of the present invention, the present invention are not limited to these embodiments.The present invention is carried out using design of the invention
It is simple change all within the scope of the claimed invention.
In following embodiment, all raw materials are commercially available by commercial sources, and all reagents are if not otherwise specified
It analyzes pure；And
Analytical conditions for gas chromatography is as follows:
(1) chromatographic column: non-polar column, HB-5；
(2) injector temperature: 40 DEG C；
(3) split ratio: 1:10；
(4) temperature program: then 40 DEG C of holding 0.5min are warming up to 200 DEG C with the heating rate of 15 DEG C/min, keep
2min；280 DEG C are warming up to the heating rate of 10 DEG C/min again, keeps 2min；Vapor detection device temperature: 220 DEG C.
Using elements such as metallic element, nitrogen, sulphur, phosphorus, chlorine in X-ray photoelectron spectroscopic analysis (XPS) instrument measurement catalyst
Content.
Embodiment (abbreviation S) 1-5 and comparative example (abbreviation D) 1-4
Catalyst using preparation method preparation of the invention for Saucy-Marbet reaction, preparation process include following step
It is rapid:
(1) using carbon presoma as raw material, acidification is carried out using mixed acid；
(2) it after the mixture filtering obtained the step (1), is washed, drying process is to get to loading main activity
The catalyst of component；
(3) catalyst, metal salt, surfactant, phosphorus source and/or the sulphur of main active component will be loaded obtained by step (2)
Source, water mixing, occur hydro-thermal reaction, and the load of phosphide and/or sulfide is carried out to the catalyst for loading main active component, from
And realize the load of cocatalyst component, the catalysis of main active component and cocatalyst component has been loaded after filtering, drying
Agent product.
D1 makes water consumption substitution mixed acid；D2 and D3 carries out acidification using the acid of single kind；D4 does not carry out co-catalysis
The load of agent component.
Catalyst prod made from S1-5 and D1-4 is followed successively by A, B, C, D, E, F, G, H, I.
Prepare the process conditions of catalyst prod as shown in table 1-3.The structure and property for each catalyst prod being prepared
Matter is as shown in table 4.
Process conditions (1) in table 1 S1-5 and D1-4
| Raw material | Sour 1/ acid 2 | Raw material/nitration mixture mass ratio | Sour 2 mass ratioes of acid 1/ | |
| S1 | Coal tar pitch | H2SO4/HNO3 | 1:20 | 1:6 |
| S2 | Asphalt | H2SO4/H3PO4 | 1:40 | 1:2 |
| S3 | Coal liquefaction residue | HCl/H3PO4 | 1:10 | 1:10 |
| S4 | Straw | H3PO4/HClO4 | 1:50 | 1:1 |
| S5 | Coal tar pitch | H3PO4/HNO3 | 1:25 | 1:6 |
| D1 | Coal tar pitch | H2O | 1:20 | / |
| D2 | Coal tar pitch | H2SO4 | 1:20 | / |
| D3 | Coal tar pitch | HCl | 1:20 | / |
| D4 | Coal tar pitch | H2SO4/HNO3 | 1:20 | 1:6 |
Process conditions (2) in table 2 S1-5 and D1-4
| Souring temperature (DEG C) | Acidificatoin time (h) | Step (2) drying temperature (DEG C) | Step (2) drying time (h) | |
| S1 | 120 | 2 | 120 | 6 |
| S2 | 80 | 8 | 130 | 10 |
| S3 | 50 | 24 | 100 | 24 |
| S4 | 150 | 1 | 150 | 4 |
| S5 | 120 | 2 | 120 | 6 |
| D1 | 120 | 2 | 120 | 6 |
| D2 | 120 | 2 | 120 | 6 |
| D3 | 120 | 2 | 120 | 6 |
| D4 | 120 | 2 | 120 | 6 |
Process conditions (3) in table 3 S1-5 and D1-4
Note: (1) m1、m2、m3、m4Respectively represent metal salt, phosphorus source and/or sulphur source, surfactant, the main active group of load
The quality of the catalyst divided；(2) mass ratio of red phosphorus and glutathione is 1:1 in embodiment S5；(3) drying in step (3)
Temperature is 100 DEG C, and drying time is 12h, it is ensured that moisture is evaporated.
The property of gained catalyst prod in table 4 S1-5 and D1-4
According to table 1-4 it is found that S1-S5 can be prepared containing SO4 2-And/or H2PO4 -And/or NO3 -And/or Cl-And/or
ClO4 -The catalyst of equal acidic-groups, and the catalyst is also successfully realized the load of phosphide and/or sulfide, it can be by it
For being catalyzed Saucy-Marbet reaction.
Embodiment (abbreviation S) 6-10 and comparative example (abbreviation D) 5-9
Under certain temperature and pressure and carbon dioxide atmosphere, be added in a kettle a certain amount of unsaturated alcohol and
Solid catalyst after being warming up to certain temperature, is added alkoxy alkene in certain time for adding by the way of dropwise addition, is added dropwise
Saucy-Marbet is carried out after the completion and reacts certain time, then insatiable hunger will can be obtained after reaction solution filtering, removing light component
With ketone product.
Catalyst used by embodiment 6-10, comparative example 5-9 is respectively to urge made from embodiment 1-5 and comparative example 1-4
Agent product A, B, C, D, E, F, G, H, I, A, respectively obtain reactor product.Wherein, the reaction of comparative example D9 (using catalyst A)
Atmosphere is nitrogen, and the reaction atmosphere of remaining all embodiment and comparative example is carbon dioxide.The process conditions respectively reacted are detailed in
Table 5 and table 6, reaction result is as shown in table 6.
The process conditions (1) respectively reacted in table 5 S6-10 and D5-9
The process conditions (2) and result respectively reacted in table 6 S6-10 and D5-9
| Time for adding (h) | Reaction time (h) | Reaction temperature (DEG C) | Reaction pressure (MPa) | Conversion ratio | Selectivity | |
| S6 | 2 | 6 | 100 | 1 | 99.4% | 97.9% |
| S7 | 0.5 | 1 | 140 | 0.5 | 99.3% | 97.8% |
| S8 | 0.1 | 0.5 | 160 | 2 | 99.0% | 97.6% |
| S9 | 10 | 20 | 80 | 0.3 | 99.5% | 97.5% |
| S10 | 6 | 15 | 120 | 0.8 | 99.4% | 98.6% |
| D5 | 2 | 6 | 100 | 1 | 10.2% | 90.2% |
| D6 | 2 | 6 | 100 | 1 | 97.2% | 92.3% |
| D7 | 2 | 6 | 100 | 1 | 96.1% | 89.6% |
| D8 | 2 | 6 | 100 | 1 | 99.3% | 85.3% |
| D9 | 2 | 6 | 100 | 1 | 98.6% | 93.5% |
According to table 5 and table 6, compared as the data of embodiment S6-10 it is found that being carried out using catalyst prepared by the present invention
Saucy-Marbet reaction, reaction conversion ratio and selectivity are high, show excellent catalytic performance.
From the comparison of S6-10 and D5: using the D5 of catalyst F relative to the S6-10 for using catalyst A-E, D5's
Conversion ratio is very low, and it is conclusive that this illustrates that the use of mixed acid plays the role of the conversion ratio of promotion reaction.If using water
Come substitute mixed acid preparation catalyst, without obvious catalytic action.
By the comparison of S6-10 and D6, D7 it is found that using catalyst G D6 and catalyst H D7 relative to using catalyst
The selectivity of the S6-10 of A-E, Saucy-Marbet reaction, conversion ratio have decline, this illustrates the catalyst of mixed acid processing
Obtained a variety of acidic functionalities；For the processing of single acid, the presence of a variety of functional groups is for promoting Saucy-
The selectivity of Marbet reaction, conversion ratio play facilitation.In addition, by the comparison of D6, D7 it is found that-SO4Than-Cl function
The promotion of selectivity and conversion ratio that group can more promote Saucy-Marbet to react.
By the comparison of S6-10 and D8 it is found that using the D8 of catalyst I relative to the S6-10 for using catalyst A-E,
The selectivity of Saucy-Marbet reaction is substantially reduced, this illustrates the introducing of phosphide (or sulfide), for reducing heavy group
The generation divided plays facilitation, is conducive to the selectivity for promoting reaction, but reaction conversion ratio is not decreased obviously.
By the comparison of S6-10 and D9 it is found that using the D9 of nitrogen atmosphere relative to the S6-10 for using carbon dioxide atmosphere,
The selectivity of its Saucy-Marbet reaction is substantially reduced, and also slightly reduce this explanation shows weakly acidic carbon dioxide gas to conversion ratio
Body atmosphere may advantageously facilitate the promotion of reaction rate and reaction selectivity.
Claims (11)
1. a kind of preparation method of catalyst, includes the following steps:
(1) using carbon presoma as raw material, acidification is carried out using mixed acid；
(2) it after the mixture filtering obtained the step (1), washed, dried to get urging to the main active component of load
Agent；
(3) catalyst, metal salt, surfactant, phosphorus source and/or sulphur source, the water of main active component will be loaded obtained by step (2)
Hydro-thermal reaction occurs for mixing, and the load of phosphide and/or sulfide is carried out to the catalyst for loading main active component, thus real
The load of existing cocatalyst component, filtered, dry after loaded the catalyst of main active component and cocatalyst component
Product.
2. preparation method according to claim 1, which is characterized in that in the step (1), carbon presoma be selected from coal tar pitch,
One of asphalt, coal liquefaction residue, straw are a variety of；
Mixed acid is H2SO4、H3PO4、HNO3、CH3COOH、HClO4, any two kinds in HCl, preferably H2SO4、H3PO4、HNO3、
Two kinds in HCl, in mixed acid, two kinds of sour mass ratioes are 1:1-1:10, preferably 1:2-1:6；And/or:
The mass ratio of carbon presoma and mixed acid is 1:10-1:50, preferably 1:20-1:40.
3. preparation method according to claim 1 or 2, which is characterized in that in the step (1), the acidification time is 1h-
For 24 hours, preferably 2h-8h；Acidification temperature is 50-150 DEG C, preferably 80-120 DEG C；And/or:
In the step (2), drying time 4h-24h, preferably 6h-10h；Drying temperature is 100-150 DEG C, preferably 120-130
℃。
4. preparation method according to claim 1, which is characterized in that in the step (3), the metallic element in the metal salt
Selected from one of copper, iron, zinc and sodium or a variety of；
The metal salt is selected from one of sulfate, phosphate, nitrate, sulphite, carbonate or a variety of；
The surfactant is selected from one of citric acid, ethylenediamine tetra-acetic acid and lauryl sodium sulfate or a variety of；
Phosphorus source and/or sulphur source, wherein the mass percent of phosphorus source is 0-100%, preferably 20-80%, more preferable 40-
60%；The sulphur source be selected from one of thiocarbamide, thioacetamide, glutathione or a variety of, phosphorus source be selected from red phosphorus and/or
White phosphorus.
5. preparation method according to claim 1 or 4, which is characterized in that in the step (3), metal salt, phosphorus source and/or sulphur
Source, surfactant, the main active component of load the mass ratio of catalyst be 1:(1-10): (0.1-1.0): (50-100), it is excellent
Select 1:(2-5): (0.2-0.5): (60-80)；
The reaction temperature of hydro-thermal reaction is 100-300 DEG C, preferably 150-200 DEG C；Reaction time is 5-48h, preferably 8-24h.
6. catalyst made from any one of -5 preparation methods according to claim 1；It is preferably based on catalyst quality, it is prepared
Catalyst in, the content of main active component is 7%-15%, and the content of cocatalyst component is 0.5%-1.5%.
7. a kind of method that Saucy-Marbet reaction prepares beta-unsaturated ketone, which is characterized in that be added in a kettle a certain amount of
Unsaturated alcohol and catalyst, after being warming up to certain temperature, alkoxy alkene is slowly added within a certain period of time, after the completion of addition
Certain time is reacted, beta-unsaturated ketone product will can be obtained after reaction solution filtering, removing light component, wherein the catalyst is
Catalyst described in catalyst made from any one of -5 preparation methods or claim 6 according to claim 1.
8. the method according to the description of claim 7 is characterized in that the structure of the unsaturated alcohol and alkoxy alkene is respectively such as
Shown in lower,
Wherein R1、R2、R3、R5Independently indicate hydrogen, saturation or unsaturated alkyl, R4、R6Independently indicate saturation or unsaturated
Alkyl, preferably:
R1、R2Independently indicate hydrogen, saturation or unsaturated alkyl containing 1-25 carbon atom,
R3、R5Independently indicate hydrogen, saturation or unsaturated alkyl containing 1-5 carbon atom,
R4、R6Independently indicate saturation or unsaturated alkyl containing 1-5 carbon atom；
It is highly preferred that alkoxy alkene is selected from 2- methoxyl group propylene, 2- ethoxy propylene, 2- methoxyl group -1- butylene, unsaturated alcohol
Selected from tetrahydro dehydrogenation nerolidol, dehydrogenation different vegetable alcohol, dihydro dehydrogenation linalool, dehydrogenation nerolidol, dihydro dehydrogenation flores aurantii uncle
Alcohol, dehydrogenation linalool.
9. method according to claim 7 or 8, which is characterized in that the molar ratio of unsaturated alcohol and alkoxy alkene is 1:
2-1:10, preferably 1:3-1:6；The mass ratio of unsaturated alcohol and catalyst is 1:0.001-1:1, preferably 1:0.01-1:0.1.
10. according to the described in any item methods of claim 7-9, which is characterized in that reaction temperature is 80-160 DEG C, preferably 100-
140℃；Reaction meter pressure is 0.3-2MPa, preferably 0.5-1MPa；Alkoxy alkene, time for adding are added by the way of dropwise addition
For 0.1-10h, preferably 0.5-2h, being added dropwise to complete the rear reaction time is 0.5-20h, preferably 1-6h.
11. according to the described in any item methods of claim 7-10, which is characterized in that the atmosphere of reaction is carbon dioxide.
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