CN113666814B - Synthesis method of high-purity raspberry ketone - Google Patents
Synthesis method of high-purity raspberry ketone Download PDFInfo
- Publication number
- CN113666814B CN113666814B CN202111083967.7A CN202111083967A CN113666814B CN 113666814 B CN113666814 B CN 113666814B CN 202111083967 A CN202111083967 A CN 202111083967A CN 113666814 B CN113666814 B CN 113666814B
- Authority
- CN
- China
- Prior art keywords
- acid
- tert
- raspberry ketone
- catalyst
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NJGBTKGETPDVIK-UHFFFAOYSA-N raspberry ketone Chemical compound CC(=O)CCC1=CC=C(O)C=C1 NJGBTKGETPDVIK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- VWMVAQHMFFZQGD-UHFFFAOYSA-N p-Hydroxybenzyl acetone Natural products CC(=O)CC1=CC=C(O)C=C1 VWMVAQHMFFZQGD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003377 acid catalyst Substances 0.000 claims abstract description 23
- OZGYFEDCHSTRRC-UHFFFAOYSA-N 4-(2,6-ditert-butyl-4-hydroxyphenyl)butan-2-one Chemical compound CC(=O)CCC1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C OZGYFEDCHSTRRC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 25
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 25
- 239000000010 aprotic solvent Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920001429 chelating resin Polymers 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical group CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002304 perfume Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 235000011034 Rubus glaucus Nutrition 0.000 description 10
- 244000235659 Rubus idaeus Species 0.000 description 10
- 235000009122 Rubus idaeus Nutrition 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000003205 fragrance Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000012047 saturated solution Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000013995 raspberry juice Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 244000111489 Gardenia augusta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 102100024295 Maltase-glucoamylase Human genes 0.000 description 1
- ALHUZKCOMYUFRB-OAHLLOKOSA-N Muscone Chemical compound C[C@@H]1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-OAHLLOKOSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 102000023984 PPAR alpha Human genes 0.000 description 1
- 244000014047 Polianthes tuberosa Species 0.000 description 1
- 235000016067 Polianthes tuberosa Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- TYGDMAQFSSHPRP-UHFFFAOYSA-N acetaldehyde;acetic acid Chemical compound CC=O.CC(O)=O TYGDMAQFSSHPRP-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 230000001270 agonistic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 108010028144 alpha-Glucosidases Proteins 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002418 insect attractant Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 1
- 108091008725 peroxisome proliferator-activated receptors alpha Proteins 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of perfume and fine chemical industry, and particularly relates to a method for synthesizing high-purity raspberry ketone. The synthesis method of the invention takes 2, 6-di-tert-butylphenol as a raw material, and carries out alkylation reaction with butenone or 4-hydroxy butanone under the catalysis of an acid catalyst a to generate 2, 6-di-tert-butyl-4-hydroxy benzyl acetone, and then the raspberry ketone is obtained by catalyzing and removing tert-butyl by the acid catalyst b. The invention takes 2, 6-di-tert-butylphenol with 2, 6-site occupation protection as a raw material, and can be positioned at the para position by 100% in alkylation reaction with butenone or 4-hydroxy butanone, thus obtaining 2, 6-di-tert-butyl-4-hydroxy benzyl acetone with high yield; then obtaining high-yield and high-purity raspberry ketone through a tert-butyl removing process; the method has the advantages of simple process, short reaction time, high product purity, recycling of reaction byproducts, recycling of the catalyst and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of perfume and fine chemical industry, and particularly relates to a method for synthesizing high-purity raspberry ketone.
Background
Raspberry ketone, the chemical name of which is 4-p-hydroxyphenyl-2-butanone (4-p-hydroxyphenly) -2-butanone), is the main aroma component of raspberry fruit, and has characteristic sweet fruit aroma and fragrance. The raspberry ketone is an internationally recognized synthetic spice which is safe and widely applied, and has elegant fruit aroma and aroma enhancement and sweetness. The latest edition of food additive sanitation standards in China (GB 2760-2014) prescribes raspberry ketone as a permissible edible spice (FEMA code: 2588). The raspberry ketone is used for preparing raspberry, grape, pineapple, peach, plum, strawberry, raspberry, jasmine, gardenia, tuberose and other essence, can keep fragrance for a long time, and is used as a modifier or a fragrance fixative in a large amount of daily fragrances, food fragrances, daily chemical fragrances and tobacco fragrances. The raspberry ketone has certain whitening effect and anti-inflammatory effect, and is widely used for preparing cosmetics. Acetate of raspberry ketone is used in agriculture as a highly effective insect attractant (muscone). Recent researches show that the raspberry ketone has alpha-glucosidase inhibitory activity and PPAR-alpha agonistic activity, and shows the application prospect in the field of metabolic diseases treatment. Therefore, raspberry ketone is a fine chemical with good development value and high added value.
The natural raspberry ketone is found in raspberry juice such as raspberry (raspberry), raspberry, etc., but is very rare, and is found as early as 18 th century in raspberry juice at only about 0.1-0.2ppm, and it was confirmed in 1957 that raspberry is the main flavor substance in raspberry. Because the content is extremely low and is difficult to separate, the large-scale commercial production of raspberry ketone can be developed to the greatest extent at present. The chemical synthesis method of raspberry ketone is more, including condensation and reduction of p-hydroxybenzaldehyde and acetone, friedel-Crafts alkylation reaction synthesis of phenol and 4-hydroxy-2-butanone, friedel-Crafts alkylation reaction synthesis of phenol and methyl vinyl ketone, condensation, reduction and hydrolysis synthesis of p-alkoxybenzaldehyde and acetone, friedel-Crafts alkylation reaction of phenyl acetate and methyl vinyl ketone, hydrolysis synthesis and the like.
The raspberry ketone synthesis methods are discussed in detail in two recent documents (crown, perfume, essence and cosmetics, 2017, NO4, 14-20; zhangheng, acetaldehyde acetic acid chemical industry, 2014, 9 th stage, 12-18), and the methods have thousands of times, but most of the methods have the problems of long working procedures, more synthesis steps, complex processes or long reaction time, more byproducts, low yield and the like.
Disclosure of Invention
The invention aims to provide a synthesis method of high-purity raspberry ketone, which adopts a two-step method, takes 2, 6-site occupied and protected phenol (2, 6-di-tert-butylphenol) as a raw material, and can be positioned at para position by 100% in alkylation reaction with butenone or 4-hydroxy butanone, so that the yield of the obtained 2, 6-di-tert-butyl-4-hydroxy benzyl acetone is high; then the raspberry ketone with high purity and high quality is obtained through the tert-butyl removing process, and the method has the advantages of simple process, short reaction time, high product purity and low cost, and is suitable for industrial production.
The invention provides a method for synthesizing high-purity raspberry ketone, which adopts Friedel-Crafts alkylation reaction method, takes 2, 6-di-tert-butylphenol as raw material, carries out alkylation reaction with butenone or 4-hydroxy butanone under the catalysis of an acid catalyst a to generate 2, 6-di-tert-butyl-4-hydroxy benzyl acetone, and then carries out catalytic de-tert-butyl through an acid catalyst b to obtain the high-purity raspberry ketone.
Friedel-Crafts alkylation refers to the reaction of aromatic hydrocarbons with an alkylating agent under the catalytic action of an acid, where the hydrogen on the aromatic ring is replaced by an alkyl group.
In the technical scheme, 2, 6-tertiary butyl protected phenol (2, 6-di-tertiary butyl phenol) is used as a raw material, friedel-Crafts alkylation reaction is carried out with butenone or 4-hydroxy butanone with electrophilic groups, 100% of the Friedel-Crafts alkylation reaction can be carried out, the obtained raspberry ketone precursor compound (2, 6-di-tertiary butyl-4-hydroxy benzyl acetone) has high yield, then isobutene protective agent is removed in the presence of an acidic catalyst, high-purity raspberry ketone is obtained through distillation, and the byproduct isobutene can be recovered for synthesizing the 2, 6-di-tertiary butyl phenol, so that recycling is realized.
Further, the method specifically comprises the following steps:
(1) Preparation of raspberry ketone precursor compound: dissolving 2, 6-di-tert-butylphenol by using an aprotic solvent A, adding the solution into a reactor, adding an acid catalyst a, stirring and heating to 0-120 ℃, then dropwise adding butenone or 4-hydroxybutanone dissolved in the aprotic solvent A within 1-5 hours, continuing to react for 3-5 hours, cooling to room temperature, filtering, regulating the pH value of filtrate to be neutral, recovering the aprotic solvent A at normal pressure, and distilling under reduced pressure to obtain raspberry ketone precursor 2, 6-di-tert-butyl-4-hydroxybenzyl acetone;
(2) Preparation of raspberry ketone: adding an acid catalyst B and an aprotic solvent B into a reactor, mixing, heating to 90-150 ℃, then dropwise adding 2, 6-di-tert-butyl-4-hydroxybenzyl acetone dissolved in the aprotic solvent B, reacting for 1.5-5h, collecting generated isobutene gas, cooling to room temperature after the reaction is finished, filtering out a solid catalyst, regulating the pH value of filtrate to be neutral, recovering the aprotic solvent B at normal pressure, and distilling under reduced pressure to obtain raspberry ketone.
Specifically, the reactor is provided with a thermometer, a reflux condenser pipe and a constant pressure dropping funnel, so that the temperature, the dropping speed and the pressure can be conveniently controlled; and the upper end of the reflux condensing pipe is connected with an air duct so as to lead out isobutene gas generated in the reaction process, thereby being convenient for recycling isobutene as a reaction byproduct.
Further, the technical scheme further comprises the steps of (3) preparing 2, 6-di-tert-butylphenol: freezing and collecting isobutene which is a reaction product in the step (2), and reacting with phenol under the action of a catalyst to obtain the 2, 6-di-tert-butylphenol. The 2, 6-di-tert-butylphenol obtained in the technical scheme can be used as a raw material for synthesizing the covered plate for recycling.
Further, in the above technical scheme, the acid catalyst a is any one of an inorganic acid, an organic acid, an acid resin and a solid acid.
Further, in the above technical solution, the inorganic acid is any one of sulfuric acid, phosphoric acid or hydrochloric acid; the organic acid is any one of p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid or hexadecylsulfonic acid; the acid resin is Amberlyst series acid resin or perfluorinated sulfonic acid resin; the solid acid is acid diatomite or acid alumina; preferably Amberlyst series acidic resins
Specifically, from the viewpoint of environment and safety, amberlyst series acidic resins are preferable as the catalyst, and the resins can be used more than 10 times, and 10% of new resins are additionally added for each use.
Specifically, when perfluorinated sulfonic acid resin is used, the catalyst activity is high, the reaction is completed after the dripping is finished, and the perfluorinated sulfonic acid resin can be reused or not added with new resin.
Specifically, when trifluoromethanesulfonic acid is used, the reaction is completed after the completion of the dropwise addition, and the activity is high. In particular, when the acid diatomite is used, the acid diatomite can be used only three times because of poor reusability, and the yield of the product is reduced to about 30%.
Further, in the above technical scheme, the aprotic solvent a is an aromatic hydrocarbon or a polar solvent a; the aromatic hydrocarbon comprises toluene, xylene, dioxane or tetraethylene glycol dimethyl ether; the polar solvent a comprises acetonitrile, N-dimethylformamide or N, N-diethylacetamide. Specifically, toluene-series aromatic hydrocarbons are preferable as the reaction solvent for more convenient purification of the product.
Further, in the step (2) of the above technical scheme, the acid catalyst b is any one of Lweis acid, inorganic acid, organic acid and acid resin, and the Lweis acid is any one of aluminum trichloride, zinc chloride, tin tetrachloride and titanium chloride; the inorganic acid is sulfuric acid or phosphoric acid; the organic acid is any one of methylbenzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid; the acid resin is perfluorinated sulfonic acid resin.
Further, in the step (2) of the above technical scheme, the aprotic solvent B is a high boiling aromatic hydrocarbon or polar solvent B; the aromatic hydrocarbon is any one of toluene, xylene, decane or dodecane; the polar solvent b is any one of dimethyl sulfoxide, sulfolane, N-dimethylformamide or N, N-diethylformamide. In the technical scheme, since the removed tertiary butyl has acid during the removal reaction, aromatic hydrocarbon can be subjected to alkylation reaction, and therefore, for recycling isobutene, hydrocarbon inert solvents such as decane, dodecane and the like can be preferred.
Further, in the step (3) of the above technical scheme, the catalyst is an acidic resin.
Compared with the prior art, the beneficial effects are that:
1. The invention adopts 2, 6-di-tert-butylphenol with 2, 6-site occupation protection as a raw material, and can be positioned at the para position by 100% in alkylation reaction with butenone, and the obtained 2, 6-di-tert-butyl-4-hydroxybenzyl acetone has high yield; the raspberry ketone with high yield and high purity can be obtained through the process of tert-butyl removal;
2. The isobutene serving as a reaction byproduct can be recovered and used as a raw material for synthesizing the 2, 6-di-tert-butylphenol, and can be reused, so that the cost can be saved;
3. The invention further saves the production cost by selecting the recyclable catalyst;
4. the two-step reaction of the invention is conventional chemical operation, has simple process, short reaction time, high product purity and low cost, and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of the recovery of the synthetic raspberry ketone and isobutylene of the present invention.
Detailed Description
The above-described features of the invention and those specifically described in the following (example embodiments) may be combined with each other to constitute new or preferred embodiments, but the invention is not limited to these embodiments, nor is they limited to them in any way.
The experimental methods in the following examples are conventional methods unless otherwise specified. The preparations according to the examples below are commercially available and are commercially available unless otherwise specified.
The invention is described in further detail below in connection with the figures and examples:
FIG. 1 is a flow chart of recovery of the synthetic raspberry ketone and isobutylene of the present invention, comprising three steps, the first step being the reaction of 2, 6-di-tert-butylphenol with butenone to produce 2, 6-di-tert-butyl-4-hydroxybenzyl acetone; the second step is that 2, 6-di-tert-butyl-4-hydroxybenzyl acetone is heated and decomposed under the action of an acid catalyst to obtain target products of raspberry ketone and isobutene; the third step is that the isobutene and phenol are catalyzed by acid resin to obtain 2, 6-di-tert-butylphenol, and the 2, 6-di-tert-butylphenol can participate in the reaction to obtain the target product, thus realizing the recycling of byproducts.
Example 1
300ML of toluene, 51.6g of 2, 6-di-tert-butylphenol, 10g of Amberlyst15 resin, and then 17.5g of butenone dissolved in 50mL of toluene are added into a 500mL three-neck flask with a thermometer, a reflux condenser and a constant pressure dropping funnel, electromagnetic stirring is started, the temperature of the reaction flask is slowly raised to 90 ℃, then 17.5g of butenone dissolved in 50mL of toluene is added into the reaction flask dropwise within 2 hours, after the completion of the dropwise addition, the reaction is continued for 3 hours, the reaction solution mixture is cooled to room temperature, amberlyst15 resin is filtered out by a sand core filter funnel, the pH of the filtrate is adjusted to be neutral by one drop of saturated solution of sodium carbonate, the reaction solution is transferred into a 500mL one-neck flask, toluene is recovered at normal pressure, 65.1g of raspberry ketone precursor compound (chemical name: 2, 6-di-tert-butyl-4-hydroxybenzyl acetone) is obtained by distillation under reduced pressure, and the yield is 94.0%, purity is 99%). 170-174 ℃/1-2mmHg, can crystallize after being placed, and has a melting point: 80-90 ℃.
The resin catalyst may be used 10 times or more, and 1g of a new resin may be added to each use.
Example 2
100ML of toluene is added into a 250mL three-neck flask with a thermometer, a reflux condenser and a constant pressure dropping funnel, the toluene is frozen to below 0 ℃ by using a cold bath, 2g of sulfuric acid with the concentration of 98% is slowly dropped into the toluene, the mixture is stirred for 20min, 12.6g of 2, 6-di-tert-butylphenol is then added into a reaction bottle, electromagnetic stirring is started, about 0 ℃ of 4.5g of butenone dissolved in 50mL of toluene is slowly dropped into the reaction bottle (the dropping is completed in 1 h), after the dropping is completed, the reaction is continued for 3h, the reaction solution mixture is cooled to room temperature, the pH value is regulated to be neutral by using a saturated solution of sodium carbonate, a water layer is separated, the organic layer is dried by using magnesium sulfate, toluene is recovered under normal pressure, 13.1g of raspberry ketone precursor compound (2, 6-di-tert-butyl-4-hydroxybenzyl acetone) is obtained by distillation under reduced pressure, and the purity is 98%.
Example 3
120ML of toluene and 5g of p-toluenesulfonic acid are added into a 250mL three-neck flask with a thermometer, a reflux condenser and a constant pressure dropping funnel, the reaction mixture is heated to 80 ℃ and stirred for 10min, 18.2g of 2, 6-di-tert-butylphenol is added into the reaction flask, electromagnetic stirring is started, 8.17g of 4-hydroxy butanone dissolved in 40mL of toluene is slowly dropped into the reaction flask at 80 ℃ (the dropping is completed in 2.5 h), after the dropping is completed, the reaction is continued for 4h, the reaction dissolution mixture is cooled to room temperature, 20mL of water is added into the reaction solution, p-toluenesulfonic acid is dissolved into a water layer, a water layer is separated, the pH of an organic layer is adjusted to be neutral by using a saturated solution of sodium carbonate, the water layer is separated, the organic layer is dried by using magnesium sulfate, toluene is recovered under normal pressure, and distilled under reduced pressure to obtain 22.3g of a raspberry ketone precursor compound (2, 6-di-tert-butyl-4-hydroxybenzyl acetone) with the purity of 91.7 percent and 98 percent.
Example 4
500ML of toluene and 30g of acid diatomite (dried at 300 ℃) are added into a 1000mL three-neck flask with a thermometer, a reflux condenser and a constant pressure dropping funnel, the mixture is heated to 100 ℃, stirred for 30min, 126.2g of 2, 6-di-tert-butylphenol is added into a reaction bottle, electromagnetic stirring is started, 43.4g of butenone dissolved in 100mL of toluene is slowly added into the reaction bottle at 100 ℃ in a dropwise manner (the dropwise manner is completed in 5 h), after the dropwise manner is completed, the reaction is continued for 5h, the reaction dissolution mixture is cooled to room temperature, suction filtration is performed by using a Buchner funnel, the catalyst diatomite is filtered out, a small amount of saturated solution of sodium carbonate is added into the reaction solution to neutralize, a water layer is separated out, an organic layer is dried by using magnesium sulfate, toluene is recovered at normal pressure, and distilled under reduced pressure, so that the product raspberry ketone precursor compound (2, 6-di-tert-butyl-4-hydroxybenzyl acetone) is obtained, and the yield is 79.1%, and the purity is 98%.
Wherein, the acidic diatomite has poor repeated applicability and can be only used repeatedly for three times to lose activity.
Example 5
200ML decane and 50g acid sulfonic acid resin (temperature resistant 150 ℃) are added into a 500mL three-neck flask with a thermometer, a reflux condenser pipe (wherein the upper end of the reflux condenser pipe is connected with an air duct to lead out isobutene gas generated in the reaction process) and a constant pressure dropping funnel, the mixed solution is slowly heated to 120 ℃, 56.1g of raspberry ketone precursor compound (2, 6-di-tert-butyl-4-hydroxybenzyl acetone) dissolved in 100mL decane is slowly dropped into a reaction liquid at 120 ℃ from the dropping funnel, at this time, isobutene gas is immediately discharged, the produced isobutene is led into a freezing steel bottle through a connecting pipe, the steel bottle is frozen by dry ice, the dropping speed is controlled according to the speed of the effluent gas, the medium gas flow rate is controlled to ensure that the reacted isobutene is totally collected into the steel bottle, the reaction is not completed until the gas overflows, the reaction liquid is cooled to room temperature for about 5h, the acid sulfonic acid resin catalyst is filtered, the reaction liquid is adjusted to have a pH value to be neutral, normal pressure, decane is recovered, and the raspberry ketone is distilled to 29.6%, the purity of 99%, the purity of which is 99% is obtained by distilling the raspberry ketone is 29.6 g). 83-84 ℃, boiling point: 176-179 ℃/4-5mmHg.
Example 6
400ML decane and 80g Nafion perfluorinated sulfonic acid resin NR50 are added into a 1000mL three-neck flask with a thermometer, a reflux condenser pipe (wherein the upper end of the reflux condenser pipe is connected with an air duct to lead out isobutene gas generated in the reaction process) and a constant pressure dropping funnel, the mixed solution is slowly heated to 100 ℃, 125.6g raspberry ketone precursor compound (2, 6-di-tert-butyl-4-hydroxybenzyl acetone) dissolved in 200mL decane is slowly dripped into a reaction solution at 100 ℃ from the dropping funnel, at the moment, isobutene gas is immediately discharged, the produced isobutene is introduced into a freezing steel bottle through a connecting pipe, the steel bottle is frozen by dry ice to ensure that the isobutene is totally condensed, the dripping speed is controlled according to the speed of the effluent gas, the medium gas flow rate is controlled to ensure that the whole isobutene which is reacted is collected into the bottle, no gas overflows immediately after the dripping is finished, the reaction solution is cooled to room temperature, the resin catalyst is filtered, the pH of the reaction solution is regulated to be neutral, the decane is distilled under reduced pressure, and the normal pressure is obtained, the yield is 67.0.91%, and the purity of the raspberry is 67.0% is obtained under normal pressure: 83-84 ℃.
The resin catalyst can be reused many times, and the resin catalyst is different from other catalysts in that only a little new resin is needed to be added until the 6 th reuse.
Example 7
A100 mL three-neck flask with a thermometer, a reflux condenser (wherein the upper end of the reflux condenser is connected with an air duct to lead out isobutene gas generated in the reaction process) and a constant pressure dropping funnel is added with 40mL decane and 2.0g trifluoromethanesulfonic acid, the mixed solution is slowly heated to 90 ℃, 12.5g of raspberry ketone precursor compound (2, 6-di-tert-butyl-4-hydroxybenzylacetone) dissolved in 20mL decane is slowly dropped into a reaction solution at 90 ℃ from the dropping funnel, at this time, isobutene gas is immediately discharged, the produced isobutene is led into a freezing steel bottle through a connecting pipe, the steel bottle is frozen by dry ice to ensure that isobutene is totally condensed, the reaction of trifluoromethanesulfonic acid is basically equivalent to that of perfluorosulfonic acid resin after the dropping is finished, the reaction solution is cooled to room temperature, the pH is adjusted to be neutral by a saturated solution of sodium carbonate, an aqueous layer is separated, an organic layer is dried by magnesium sulfate, the decane is recovered, and distilled under normal pressure, 6.4g of raspberry is obtained, the melting point is 86%, and the purity of 99% is 99% of purity is obtained: 83-84 ℃.
In summary, the synthesis method adopts a two-step method, 2, 6-di-tert-butylphenol with 2, 6-site occupation protection is taken as a raw material in examples 1-4, 100% of the alkylation reaction with butenone can be positioned at para position, and the yield of the obtained 2, 6-di-tert-butyl-4-hydroxybenzyl acetone is up to 94%; in examples 5-7, 2, 6-di-tert-butyl-4-hydroxybenzyl acetone obtained in examples 1-4 is dissolved in a solvent and then added into an acid catalyst, and the yield of raspberry ketone obtained through the tert-butyl removal process is up to 91% and the purity is up to 99%.
Finally, it should be emphasized that the foregoing description is merely illustrative of the preferred embodiments of the invention, and that various changes and modifications can be made by those skilled in the art without departing from the spirit and principles of the invention, and any such modifications, equivalents, improvements, etc. are intended to be included within the scope of the invention.
Claims (8)
1. A method for synthesizing high-purity raspberry ketone is characterized in that 2, 6-di-tert-butylphenol is used as a raw material, alkylation reaction is carried out with butenone or 4-hydroxy butanone under the catalysis of an acid catalyst a to generate 2, 6-di-tert-butyl-4-hydroxybenzyl acetone, and then tert-butyl is removed by catalysis of an acid catalyst b to obtain raspberry ketone;
The method specifically comprises the following steps:
(1) Preparation of raspberry ketone precursor compound: dissolving 2, 6-di-tert-butylphenol by using an aprotic solvent A, adding the solution into a reactor, adding an acid catalyst a, stirring and heating to 0-120 ℃, then dropwise adding butenone or 4-hydroxybutanone dissolved in the aprotic solvent A within 1-5 hours, continuing to react for 3-5 hours, cooling to room temperature, filtering, regulating the pH value of filtrate to be neutral, recovering the aprotic solvent A at normal pressure, and distilling under reduced pressure to obtain raspberry ketone precursor 2, 6-di-tert-butyl-4-hydroxybenzyl acetone;
(2) Preparation of raspberry ketone: adding an acid catalyst B and an aprotic solvent B into a reactor, mixing, heating to 90-150 ℃, then dropwise adding 2, 6-di-tert-butyl-4-hydroxybenzyl acetone dissolved in the aprotic solvent B, reacting for 1.5-5h, collecting generated isobutene gas, cooling to room temperature after the reaction is finished, filtering out a solid catalyst, regulating the pH value of filtrate to be neutral, recovering the aprotic solvent B at normal pressure, and distilling under reduced pressure to obtain raspberry ketone;
the acid catalyst a is any one of inorganic acid, organic acid, acid resin and solid acid;
The inorganic acid of the acid catalyst a is any one of sulfuric acid, phosphoric acid or hydrochloric acid; the organic acid of the acid catalyst a is any one of p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid or hexadecylsulfonic acid; the acid resin of the acid catalyst a is Amberlyst series acid resin or perfluorinated sulfonic acid resin; the solid acid of the acid catalyst a is acid diatomite or acid alumina;
The acid catalyst b is any one of organic acid or acid resin;
The organic acid of the acid catalyst b is any one of methyl benzene sulfonic acid, methyl sulfonic acid or trifluoromethyl sulfonic acid; the acid resin of the acid catalyst b is perfluorinated sulfonic acid resin.
2. The method for synthesizing high purity raspberry ketone as set forth in claim 1, further comprising:
(3) Preparation of 2, 6-di-tert-butylphenol: freezing and collecting isobutene which is a reaction product in the step (2), and reacting with phenol under the action of a catalyst to obtain the 2, 6-di-tert-butylphenol.
3. The method for synthesizing high purity raspberry ketone according to claim 1, wherein the acid catalyst a is Amberlyst series acid resin.
4. The method for synthesizing high purity raspberry ketone according to claim 1, wherein in step (1), aprotic solvent a is aromatic hydrocarbon or polar solvent a; the aromatic hydrocarbon comprises toluene, xylene, dioxane or tetraethylene glycol dimethyl ether; the polar solvent a comprises acetonitrile, N-dimethylformamide or N, N-diethylacetamide.
5. The method for synthesizing high purity raspberry ketone as claimed in claim 1, wherein the aprotic solvent a is toluene.
6. The method for synthesizing high-purity raspberry ketone according to claim 1, wherein in the step (2), the aprotic solvent B is a high boiling aromatic hydrocarbon or polar solvent B; the aromatic hydrocarbon is any one of toluene, xylene, decane or dodecane; the polar solvent b is dimethyl sulfoxide, sulfolane, N-dimethylformamide or N, N-diethylformamide.
7. The method for synthesizing high purity raspberry ketone according to claim 6, wherein the aprotic solvent B is decane or dodecane.
8. The method for synthesizing high purity raspberry ketone according to claim 2, wherein in step (3), the catalyst is an acidic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111083967.7A CN113666814B (en) | 2021-09-14 | 2021-09-14 | Synthesis method of high-purity raspberry ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111083967.7A CN113666814B (en) | 2021-09-14 | 2021-09-14 | Synthesis method of high-purity raspberry ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113666814A CN113666814A (en) | 2021-11-19 |
| CN113666814B true CN113666814B (en) | 2024-04-23 |
Family
ID=78549444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111083967.7A Active CN113666814B (en) | 2021-09-14 | 2021-09-14 | Synthesis method of high-purity raspberry ketone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113666814B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372617A (en) * | 2011-11-09 | 2012-03-14 | 山东新和成药业有限公司 | Preparation method of spice 4-(4-hydroxyphenyl)-2-butanone |
| CN106748694A (en) * | 2016-12-21 | 2017-05-31 | 山东新和成药业有限公司 | A kind of preparation method of spices raspberry ketone |
| RU2637312C1 (en) * | 2016-12-08 | 2017-12-04 | Федеральное государственное бюджетное учреждение науки Новосибирский институт органической химии им. Н.Н. Ворожцова Сибирского отделения Российской академии наук (НИОХ СО РАН) | Method for raspberry ketone production |
-
2021
- 2021-09-14 CN CN202111083967.7A patent/CN113666814B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372617A (en) * | 2011-11-09 | 2012-03-14 | 山东新和成药业有限公司 | Preparation method of spice 4-(4-hydroxyphenyl)-2-butanone |
| RU2637312C1 (en) * | 2016-12-08 | 2017-12-04 | Федеральное государственное бюджетное учреждение науки Новосибирский институт органической химии им. Н.Н. Ворожцова Сибирского отделения Российской академии наук (НИОХ СО РАН) | Method for raspberry ketone production |
| CN106748694A (en) * | 2016-12-21 | 2017-05-31 | 山东新和成药业有限公司 | A kind of preparation method of spices raspberry ketone |
Non-Patent Citations (1)
| Title |
|---|
| Bunce, Richard A.Amberlyst-15 catalyzed addition of phenols to α,β-unsaturated ketones.Synthetic Communications (1989).2006,第19卷(第5-6期),1109-1117. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113666814A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102010310B (en) | Productive technology of vanlillin by glyoxylic acid method | |
| CN110467519B (en) | Ethynylation method | |
| CN101575269B (en) | Preparation method of aromatic methyl ether compound | |
| CA2505094A1 (en) | Continuous process for producing pseudoionones and ionones | |
| CN113666814B (en) | Synthesis method of high-purity raspberry ketone | |
| CN113336629A (en) | Preparation process of 1,3 cyclohexanedione | |
| EP1945610A1 (en) | Process for the preparation of an epoxy compound and an aldehyde | |
| CN114409612B (en) | Preparation method of high-content 2-chloro-5-chloromethylthiazole | |
| CN108238875B (en) | Synthesis method of bromoisobutenyl methyl ether and application of bromoisobutenyl methyl ether in preparation of C14 aldehyde | |
| CN113563168B (en) | Method for reducing waste water in production of pseudo ionone | |
| EP0650952B1 (en) | Process for 3,5-di-tert-butylsalicylaldehyde | |
| CN111116339B (en) | Method for artificially synthesizing curcumin and derivatives thereof | |
| CN112679320B (en) | Process for preparing resorcinol and hydroquinone | |
| CN111362784A (en) | Method for preparing ethyl vanillin from sassafras oil | |
| CN110606801A (en) | Method for continuously preparing vanillin and syringaldehyde | |
| CN108840788B (en) | Preparation method of resveratrol | |
| CN107973703B (en) | Synthetic method of aryl olefin | |
| Fuson et al. | A comparison of certain dimesitylmethyl derivatives with the corresponding triarylmethyl compounds | |
| CN111662170B (en) | Method for purifying cyclopentanone | |
| JP2874281B2 (en) | Method for separating and purifying biphenyl-4,4'-diol | |
| CN112898133B (en) | Preparation method of trans-ketone intermediate | |
| CN102241575B (en) | Method for preparing protocatechuic aldehyde from vanillin | |
| CN107778155B (en) | Preparation method of aryl alkyl ketone intermediate of hydroxyl ketone photoinitiator | |
| JPH05339256A (en) | Production of reaction crude liquid containing aldoxane and paraldol as main ingredients | |
| JP2501603B2 (en) | Method for producing α-methylstyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |