CN111620766A - Method for preparing cypress oleyl alcohol metal compound and compound - Google Patents
Method for preparing cypress oleyl alcohol metal compound and compound Download PDFInfo
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- CN111620766A CN111620766A CN202010546503.4A CN202010546503A CN111620766A CN 111620766 A CN111620766 A CN 111620766A CN 202010546503 A CN202010546503 A CN 202010546503A CN 111620766 A CN111620766 A CN 111620766A
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- water
- solution
- cypress
- cypress oil
- oil alcohol
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- 241000218691 Cupressaceae Species 0.000 title claims abstract description 113
- 229940055577 oleyl alcohol Drugs 0.000 title claims abstract description 69
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- -1 oleyl alcohol metal compound Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 title claims description 59
- 239000000243 solution Substances 0.000 claims abstract description 125
- 239000010639 cypress oil Substances 0.000 claims abstract description 111
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012047 saturated solution Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 28
- 238000010008 shearing Methods 0.000 claims description 26
- 229920000858 Cyclodextrin Polymers 0.000 claims description 17
- 239000001116 FEMA 4028 Substances 0.000 claims description 17
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 17
- 229960004853 betadex Drugs 0.000 claims description 17
- 238000000265 homogenisation Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 229920001661 Chitosan Polymers 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 3
- 239000004368 Modified starch Substances 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010418 carrageenan Nutrition 0.000 claims description 3
- 239000000679 carrageenan Substances 0.000 claims description 3
- 229920001525 carrageenan Polymers 0.000 claims description 3
- 229940113118 carrageenan Drugs 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 235000019426 modified starch Nutrition 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims 1
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 4
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 abstract description 4
- 229930007845 β-thujaplicin Natural products 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 75
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 102000003425 Tyrosinase Human genes 0.000 description 3
- 108060008724 Tyrosinase Proteins 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical group 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- QXIFTVATZNKETC-KHPPLWFESA-N (z)-henicos-12-en-2-one Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(C)=O QXIFTVATZNKETC-KHPPLWFESA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 244000301850 Cupressus sempervirens Species 0.000 description 2
- 208000032612 Glial tumor Diseases 0.000 description 2
- 206010018338 Glioma Diseases 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 208000003351 Melanosis Diseases 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000000840 anti-viral effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009920 food preservation Methods 0.000 description 2
- 230000005714 functional activity Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 108020004999 messenger RNA Proteins 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 210000000130 stem cell Anatomy 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 108020002663 Aldehyde Dehydrogenase Proteins 0.000 description 1
- 102100032145 Carbohydrate sulfotransferase 10 Human genes 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010008570 Chloasma Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010009944 Colon cancer Diseases 0.000 description 1
- 108010009540 DNA (Cytosine-5-)-Methyltransferase 1 Proteins 0.000 description 1
- 102100036279 DNA (cytosine-5)-methyltransferase 1 Human genes 0.000 description 1
- 102100024739 E3 ubiquitin-protein ligase UHRF1 Human genes 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 101000775595 Homo sapiens Carbohydrate sulfotransferase 10 Proteins 0.000 description 1
- 101000760417 Homo sapiens E3 ubiquitin-protein ligase UHRF1 Proteins 0.000 description 1
- 101000653360 Homo sapiens Methylcytosine dioxygenase TET1 Proteins 0.000 description 1
- 101000588302 Homo sapiens Nuclear factor erythroid 2-related factor 2 Proteins 0.000 description 1
- 101000898871 Homo sapiens Protein BTG4 Proteins 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 102100025825 Methylated-DNA-protein-cysteine methyltransferase Human genes 0.000 description 1
- 102100030819 Methylcytosine dioxygenase TET1 Human genes 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 102100031701 Nuclear factor erythroid 2-related factor 2 Human genes 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010041925 Staphylococcal infections Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 208000029742 colonic neoplasm Diseases 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003779 hair growth Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-L malate(2-) Chemical compound [O-]C(=O)C(O)CC([O-])=O BJEPYKJPYRNKOW-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 1
- 108040008770 methylated-DNA-[protein]-cysteine S-methyltransferase activity proteins Proteins 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229940080313 sodium starch Drugs 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940086735 succinate Drugs 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides a method for preparing a cypress oil alcohol metal compound or an ammonium cypress oil alcohol compound, comprising: dissolving cypress oil alcohol in a water-soluble organic solvent to obtain a cypress oil alcohol solution with the cypress oil alcohol concentration of 6-25 mol/L; fully mixing the obtained cypress oil alcohol solution with an aqueous solution of water-soluble metal salt or ammonium salt at room temperature for reaction, wherein the water-soluble metal salt is selected from metal salt with solubility not lower than 35g/100ml at normal temperature, or the concentration of the aqueous solution of the water-soluble metal salt or ammonium salt is not lower than 25% at normal temperature; the water solution of the water-soluble metal salt or the ammonium salt is preferably a saturated solution of the water-soluble metal salt at the temperature of 30-50 ℃; controlling the molar ratio of the water-soluble metal salt or ammonium salt to the cypress oleyl alcohol to be 1: 0.9-5, and preparing the cypress oil alcohol metal compound or cypress oil alcohol ammonium compound solution. The method of the invention can radically improve the unstable characteristic of the hinokitiol which is easy to decompose in light, and avoid the environmental pollution load of the waste water and the treatment cost thereof caused by using acid solution.
Description
Technical Field
The invention relates to a preparation method of an organic compound, in particular to a method for preparing a cypress oleyl alcohol metal compound and a compound.
Background
Cupressol, also known as Hinokitiol or Hinokitiol (Hinokitiol), has excellent broad-spectrum antibacterial property, moisture retention property and pest repellent effect, and is a highly safe raw material component for preparing antibacterial agents and insect repellents. The cypress oleyl alcohol has the functions of broad-spectrum antibiosis and mildew resistance, inhibiting ALDH activity and self-renewal capacity in glioma stem cells, inhibiting in vitro carcinogenicity, inhibiting tyrosinase, inhibiting ethylene generation by plants, endowing cell activity and the like, and is applied to the development of various products such as medicine development, sanitary products, cosmetics, hair nourishing and hair growth, food preservation and the like.
The minimum inhibitory concentration of the cypress oleyl alcohol to bacteria is 10-100ppm, and the cypress oleyl alcohol has fragrant smell and good effect. The cypress oleyl alcohol can kill bacteria and mould in the air, prevent pathogenic bodies from invading human bodies, inhibit pathogenic infection of the human bodies and has remarkable inhibition effect on staphylococcus aureus (MRSA).
Recent research results show that cypress oleyl alcohol can reduce Nrf2 expression in glioma stem cells in a dose-dependent manner, inhibit colon cancer cell growth, also can reduce mRNA and protein expression of DNMT1 and UHRF1, increase TET1 expression by enhancing 5hmC levels in HCT-116 cells, and can reduce methylation status and restore mRNA expression of MGMT, CHST10 and BTG4 genes. In addition, cypress oil alcohol has attracted much attention in the field of inhibiting viral activity and antiviral action.
Cupressol has strong inhibiting effect on tyrosinase diphenol enzyme, and with dopa as substrate, 0.3 μmol/l Cupressol concentration (IC 50) can reduce enzyme activity by 50%, so as to inhibit freckle, chloasma, and cyasma. It has the function activity of inhibiting tyrosinase activity without causing permanent enzyme inactivation, and is applied to the aspects of beauty and whitening.
The molecular formula of the cypress oleyl alcohol is C10H12O2Molecular weight is 164.20, melting point is 51-52 ℃, white or light yellow crystal is obtained by distillation refining or absolute ethyl alcohol recrystallization,is difficult to dissolve in water, is easy to decompose when meeting light, is corrosive to metal, is not high temperature resistant, is easy to decompose after melting, and has special odor. The strong antibacterial and antiviral activity of the cypress oleyl alcohol enables the cypress oleyl alcohol to be widely applied to the fields of medicines, cosmetics, food preservation and the like. But the convenience of the wide application is seriously influenced by the properties of visible light decomposition, heat instability, difficult water dissolution, strong corrosiveness to metal and the like.
In the prior art, japanese patent No. 1569370 (a method for producing easily water-soluble cypress oleyl alcohol) discloses a method for producing a easily water-soluble cypress oleyl alcohol composition, which is a heterogeneous combination of an organic acid salt and cypress oleyl alcohol, and although it is easily soluble in water, the unstable property of cypress oleyl alcohol that is easily decomposed by light is not fundamentally improved. Further, both CN101396021A and JP Hei 1-53855 disclose that the problem of easy decomposition and low temperature resistance to light is solved by preparing a metal compound from cypress oil alcohol by a specific method. Among them, japanese laid-open patent JP hei 1-53855 (a method for producing water-soluble cypress oleyl alcohol) prepared by dropping cypress oleyl alcohol dissolved in lower alcohol into a powdery salt compound which is continuously stirred and mixed improves the unstable characteristic of cypress oleyl alcohol which is easily decomposed by exposure to light to a certain extent, but does not sufficiently suspend and uniformly disperse a cypress oleyl alcohol organic solvent solution, resulting in a large difference in the amount of substances when cypress oleyl alcohol is dropped into the powdery salt compound, and thus the difference in the uniform characteristics of the product is greatly affected by stirring and mixing and the fine grinding of the powdery salt compound, so that the cypress oleyl alcohol and the metal ions cannot be uniformly and sufficiently combined, and the characteristic of easily decomposed by exposure to light is not fundamentally improved. In CN101396021A, an acid solution is used in the preparation process of the cypress oil alcohol metal compound, which causes the cost of wastewater treatment, environmental load and the like, and is not beneficial to industrial popularization.
In view of the above problems, there is a need for a cypress oil alcohol compound or composition, which is more environmentally friendly and efficient, and can fundamentally improve the physicochemical instability of cypress oil alcohol and the uniformity of the substance, and a method for preparing the stable composition thereof, which provide convenience for the wide application of cypress oil alcohol.
Disclosure of Invention
The invention aims to provide a preparation method of a cypress oleyl alcohol metal compound, which is used for radically improving the unstable characteristic that cypress oleyl alcohol is easy to decompose when meeting light and avoiding the environmental pollution load of waste water and the treatment cost caused by using an acid solution.
The above object of the present invention is achieved by the following technical solutions:
first, there is provided a method for preparing a cypress oil alcohol metal compound or an ammonium cypress oil alcohol compound, comprising:
1) dissolving cypress oleyl alcohol in a water-soluble organic solvent to obtain a cypress oleyl alcohol solution;
2) fully mixing and reacting the cypress oil alcohol solution obtained in the step 1) with an aqueous solution of water-soluble metal salt or ammonium salt at room temperature, and controlling the molar ratio of the water-soluble metal salt or ammonium salt to the cypress oil alcohol to be 1: 0.9-5, and preparing the cypress oil alcohol metal compound or cypress oil alcohol ammonium compound solution.
In order to improve the uniformity of the cypress oil alcohol solution participating in the combination reaction and improve the efficiency of the combination reaction, in a preferable scheme of the invention, 1) the cypress oil alcohol is dissolved in a water-soluble organic solvent, and then deionized water is further added for mixing and fully dispersing, so that the obtained cypress oil alcohol solution is a cypress oil alcohol suspension self-emulsifying solution.
In order to improve the stability of the cypress oil alcohol solution participating in the combination reaction, in another preferable scheme of the invention, 1) the cypress oil alcohol is dissolved in a water-soluble organic solvent, and then a viscosity auxiliary substance aqueous solution with the concentration of 0.01-5% is further added for full dispersion, so that the obtained cypress oil alcohol solution is a cypress oil alcohol suspension self-emulsifying solution.
The viscosity auxiliary substance is preferably selected from 1 or more than 2 of sodium alginate, polysaccharide, beta-cyclodextrin, sodium carboxymethylcellulose (CMC-Na) (modified cellulose), starch sodium phosphate (modified starch), chitosan, xanthan gum, arabic gum, sesbania gum and carrageenan.
In order to enable the cypress oil alcohol and the metal ion to be evenly and fully combined, in the preferable scheme of the invention, 2) the full mixing reaction is that the cypress oil alcohol solution and the water solution of the water-soluble metal salt or the ammonium salt are quickly mixed and then continuously subjected to shearing homogenization; more preferably, the shearing is continued for 20 to 60 minutes.
In order to further improve the uniformity and sufficiency of the combination reaction, in a more preferred embodiment of the present invention, the rapid mixing is mixing the two solutions under a high shear homogeneous state, or by relative spray mixing.
In a preferred embodiment of the present invention, 1) the cypress oleyl alcohol is dissolved in a water-soluble organic solvent, and then added with ionized water to be mixed and fully dispersed, so that the obtained cypress oleyl alcohol solution is a stable cypress oleyl alcohol suspension self-emulsifying solution; 2) the full mixing reaction is to rapidly mix the cypress oil alcohol solution obtained in the step 1) with the water solution of the water-soluble metal salt or the ammonium salt in a high-speed shearing and homogenizing state, and then continuously shear and homogenize for 20-60 minutes.
In another preferred embodiment of the present invention, 1) the cypress oleyl alcohol is dissolved in a water-soluble organic solvent, and then a viscosity auxiliary substance aqueous solution with a concentration of 0.01% to 5% is added to fully disperse, so as to obtain the cypress oleyl alcohol solution which is a suspension self-emulsifying solution of cypress oleyl alcohol; 2) the full mixing reaction is to rapidly mix the cypress oil alcohol solution obtained in the step 1) with the water solution of the water-soluble metal salt or the ammonium salt in a high-speed shearing and homogenizing state, and then continuously shear and homogenize for 20-60 minutes.
In still another preferred embodiment of the present invention, 1) cypress oleyl alcohol is dissolved in a water-soluble organic solvent to obtain a cypress oleyl alcohol solution; 2) the fully mixing reaction is to perform relative spraying and mixing on the cypress oil alcohol solution obtained in the step 1) and the water solution of the water-soluble metal salt or the ammonium salt, and then continuously shear and homogenize the solution obtained after spraying for 20-60 minutes.
In a preferable scheme of the invention, the method further comprises the steps of cooling and crystallizing the cypress oil alcohol metal compound or the cypress oil alcohol ammonium compound solution in the step 2) at the temperature of-2-5 ℃, washing and drying the separated crystal with deionized water at the temperature of 0-5 ℃ to obtain the cypress oil alcohol metal compound crystal or the cypress oil alcohol ammonium compound crystal.
On this basis, the present invention also provides a method for producing a compound containing a cypress oil alcohol compound, comprising:
dissolving cypress oleyl alcohol in a water-soluble organic solvent to obtain a cypress oleyl alcohol solution;
fully mixing and reacting the obtained cypress oil alcohol solution and a water solution of water-soluble metal salt or ammonium salt at room temperature, and controlling the molar ratio of the water-soluble metal salt or ammonium salt to the cypress oil alcohol to be 1: 0.9-5 to prepare a cypress oil alcohol compound solution; performing conventional crystallization, separation, cleaning and drying to obtain cypress oil alcohol compound crystals;
and thirdly, physically coating and modifying the crystal of the cypress oil alcohol compound obtained in the step two by using a water-soluble viscosity auxiliary substance to obtain a compound containing the cypress oil alcohol compound.
In the preferable preparation method of the compound, in order to improve the uniformity of the cypress oil alcohol solution participating in the combination reaction and improve the efficiency of the combination reaction, the cypress oil alcohol is dissolved in the water-soluble organic solvent, and then the deionized water is further added for mixing and fully dispersing, so that the obtained cypress oil alcohol solution is a cypress oil alcohol suspension self-emulsifying solution.
In the preferable preparation method of the compound, in order to improve the stability of the cypress oil alcohol solution participating in the chemical combination reaction, firstly, the cypress oil alcohol is dissolved in a water-soluble organic solvent, and then, a viscosity auxiliary substance aqueous solution with the concentration of 0.01-5% is further added for full dispersion, so that the obtained cypress oil alcohol solution is a cypress oil alcohol suspension self-emulsifying solution.
In the preferable preparation method of the compound, in order to enable the cypress oil alcohol and the metal ions to be uniformly and fully combined, the fully mixing reaction is that the cypress oil alcohol solution and the water solution of the water-soluble metal salt or ammonium salt are quickly mixed and then continuously sheared and homogenized; more preferably, the shearing is continued for 20 to 60 minutes.
In the preferred method for preparing the compound of the present invention, in order to further improve the uniformity and sufficiency of the combination reaction, the rapid mixing is that the two solutions are mixed under a high-speed shearing homogeneous state or are mixed by relative spraying.
In the method for preparing the compound, the physical coating modification is to improve the instability of the cypress oil alcohol compound in light decomposition and high temperature resistance, improve the water-soluble dispersion of the cypress oil alcohol compound, and endow the cypress oil alcohol metal compound with slow release functional activity by utilizing the coating absorption effect of water-soluble viscosity auxiliary substances. The method can be specifically completed in any one of the following modes:
and uniformly mixing the viscosity auxiliary substance water solution and the cypress oil alcohol compound crystal, wherein the weight ratio of the viscosity auxiliary substance to the cypress oil alcohol compound crystal is 0.01-1.2: 30, and then recrystallizing, cleaning and drying to obtain the cypress oil alcohol compound-containing compound.
Or,
and cleaning the cypress oil alcohol compound crystal by using 0.01% -5% viscosity auxiliary substance aqueous solution at 0-5 ℃ to obtain the compound containing the cypress oil alcohol compound.
The viscosity auxiliary substance is used for ensuring the stability of the cypress oleyl alcohol turbid solution and promoting the water solubility of the cypress oleyl alcohol metal compound, and is preferably any combination of 1 or more than 2 of sodium alginate, polysaccharide, beta-cyclodextrin, sodium carboxymethylcellulose (CMC-Na) (modified cellulose), sodium starch phosphate (modified starch), chitosan, xanthan gum, arabic gum, sesbania gum and carrageenan, and is not limited to the selection of the raw materials.
In a preferable scheme of the invention, the water-soluble metal salt is selected from metal salts with solubility not lower than 35g/100ml at normal temperature, or the concentration of the water-soluble metal salt or the aqueous solution of ammonium salt is not lower than 25% at normal temperature; the water solution of the water-soluble metal salt or the ammonium salt is preferably a saturated solution of the water-soluble metal salt at a temperature of 30-50 ℃.
In a preferred embodiment of the present invention, the water-soluble metal salt is selected from inorganic acid metal salts or organic acid metal salts having high water solubility, and the inorganic acid metal salt is selected from a combination of one or more of nitrate, chloride, sulfate, sulfite, phosphate, phosphite, hypophosphite, citrate and carbonate; the organic acid metal salt is selected from one or a composition of more than two of formate, acetate, propionate, succinate, tartrate or malate; and do not constitute a limitation on the choice of starting materials for the salt compounds.
In a more preferred embodiment of the present invention, the metal salt is a salt compound of one or more of Na, Ni, K, Mg, Ca, Cu, Zn, Ag, Mn, Fe having a valence of 2 or 3, Li, Be, Ba, Cr, Co, Mo, Pt, or Pd.
In a preferred embodiment of the present invention, the water-soluble organic solvent is selected from any one of ethanol, methanol, and acetone;
in the preferable scheme of the invention, the cypress oil alcohol is dissolved in a cypress oil alcohol solution obtained by a water-soluble organic solvent, and the concentration of the cypress oil alcohol is 6-25 mol/L; the concentration of the water-soluble metal salt or ammonium salt aqueous solution is 5.4-125 mol/L.
Compared with the prior art, the method for preparing the cypress oil alcohol metal compound or the cypress oil alcohol ammonium compound greatly reduces the use amount of the organic solvent and the water used in the combination process, and further can effectively reduce the separation loss caused by difficult crystallization of the cypress oil alcohol metal compound in the combination solution. In the preferable scheme of the invention, the combination process of directly mixing the high-concentration water-soluble organic solvent solution of the cypress oleyl alcohol and the aqueous solution of the metal salt or the ammonium salt in a spraying mode is adopted, so that the water for suspension self-emulsification and dispersion of the cypress oleyl alcohol is reduced, the cypress oleyl alcohol metal crystalline compound can be quickly obtained, the separation loss caused by difficult crystallization is greatly reduced, and meanwhile, the technical support is provided for recycling the organic solvent and reducing energy consumption. In addition, in the method for preparing the compound, the instability of light decomposition and non-high temperature resistance of the cypress oil alcohol metal compound can be further improved by compounding the water-soluble viscosity auxiliary substance, the water-soluble dispersion of the cypress oil alcohol metal compound is improved, and the slow-release functional activity is endowed to the cypress oil alcohol metal compound by utilizing the wrapping and holding effect of the water-soluble viscosity auxiliary substance. In addition, the preparation method does not use inorganic acid and organic acid solution in the chemical combination process, thereby avoiding the environmental problems of acid solution wastewater treatment, pollution load and the like.
Detailed Description
The method for producing the cypress oleyl alcohol metal compound of the present invention is described in the following preferred examples.
Example 1:
weighing 5.8 g of NaCl and 16ml of water to prepare a saturated or high-concentration aqueous solution with the solution temperature of 35-50 ℃, dissolving 16.4 g of cypress oleyl alcohol in 5-15 ml of acetone, weighing 1/4 volume of deionized water in the NaCl solution, rapidly adding the weighed deionized water into the cypress oleyl alcohol acetone solution under the condition of high-speed shearing homogenization, fully dispersing to form a stable suspension self-emulsifying solution, rapidly adding the high-concentration NaCl solution under the condition of continuous rapid shearing homogenization, continuously shearing homogenization and fully combining for 20-60 minutes, cooling at the temperature of-2-5 ℃ to promote the rapid crystallization of cypress oleyl alcohol-Na, wherein the molar mass ratio of NaCl to cypress oleyl alcohol is 1:1. Centrifugally separating the cypress oleyl alcohol-Na crystal compound, and washing the cypress oleyl alcohol-Na crystal compound by using deionized water at the temperature of 0-5 ℃ to prepare the cypress oleyl alcohol-Na crystal compound.
Further, in order to improve the water solubility of the cypress oleyl alcohol-Na crystalline compound, sodium alginate is weighed according to the weight of anhydrous substances to prepare 0.08-3.0% aqueous solution, the weight ratio of water for dissolving sodium alginate to the cypress oleyl alcohol-Na crystalline compound is 1-2: 1, the sodium alginate and the sodium alginate are uniformly mixed, dispersed and recrystallized, and the sodium alginate composite crystalline compound of the cypress oleyl alcohol-Na is prepared by centrifugation, so that the water solubility can be improved by 5-22%.
Example 2:
weighing 11.1 g of CaCl2Preparing a saturated or high-concentration aqueous solution with 10ml of water at the solution temperature of 35-50 ℃, dissolving 24.6 g of cypress oil alcohol in 10-20 ml of ethanol, measuring CaCl2Deionized water of solution volume 1/3, the measured amount of deionized water was added rapidly to the filaments under high shear homogenization conditionsFully dispersing in the asphalt alcohol ethanol solution to form a stable suspension self-emulsifying solution, and rapidly adding high-concentration CaCl under the condition of continuous rapid shearing and homogenization2Continuously shearing, homogenizing and fully combining the solution for 20-60 minutes, cooling at the temperature of-2-5 ℃ to promote the cypress oleyl alcohol-Ca to be rapidly crystallized and separated out, wherein CaCl2And cypress oleyl alcohol in a molar mass ratio of 1: 1.5. Centrifugally separating the cypress oleyl alcohol-Ca crystal compound, and washing the cypress oleyl alcohol-Ca crystal compound by using deionized water at the temperature of 0-5 ℃ to prepare the cypress oleyl alcohol-Ca crystal compound.
Further, in order to improve the water solubility of the cypress oleyl alcohol-Ca crystal compound, beta-cyclodextrin is weighed according to the weight of anhydrous substances to prepare 0.01-1.2% aqueous solution, the weight ratio of water consumption for dissolving the beta-cyclodextrin to the cypress oleyl alcohol-Ca crystal compound is 1-2: 1, the beta-cyclodextrin compound crystal compound of the cypress oleyl alcohol-Ca is prepared by uniformly mixing, dispersing and recrystallizing and centrifuging, and the water solubility can be improved by 9-30%.
Example 3:
16.2 g FeCl was weighed3Preparing a saturated or high-concentration aqueous solution with 10ml of water at the solution temperature of 35-50 ℃, dissolving 49.2 g of cypress oleyl alcohol in 20-30 ml of acetone, measuring FeCl3Adding the deionized water into the Cupressus Sempervirens oleyl acetone solution under high-speed shearing homogenization, dispersing to form stable suspension self-emulsifying solution, and adding high-concentration FeCl under continuous high-speed shearing homogenization3Continuously shearing, homogenizing and fully combining the solution for 20-60 minutes, cooling the solution at the temperature of-2-5 ℃ to promote the cypress oleyl alcohol-Fe to be rapidly crystallized and separated out, wherein FeCl3And cypress oleyl alcohol in a molar mass ratio of 1: 3. Centrifugally separating the cypress oleyl alcohol-Fe crystal compound, and further washing with deionized water at the temperature of 0-5 ℃ to prepare the cypress oleyl alcohol-Fe crystal compound.
Further, in order to improve the water solubility of the cypress oleyl alcohol-Fe crystalline compound, beta-cyclodextrin is weighed according to the weight of anhydrous substances to prepare 0.05% -0.8% aqueous solution, the weight ratio of water consumption for dissolving the beta-cyclodextrin to the cypress oleyl alcohol-Fe crystalline compound is 1-2: 1, the beta-cyclodextrin composite crystalline compound of the cypress oleyl alcohol-Fe is prepared by uniformly mixing, dispersing and recrystallizing and centrifuging, and the water solubility can be improved by 10-29%.
Example 4:
18.7 g Cu (NO) was weighed3)2Preparing a saturated or high-concentration aqueous solution with 12ml of water at a solution temperature of 35-50 ℃, dissolving 14.8 g of cypress oil alcohol in 10ml of acetone, and measuring Cu (NO)3)21/3 ionized water with solution volume, adding 0.05 g β -cyclodextrin for fully dissolving, rapidly adding β -cyclodextrin water solution into Cupressus Sempervirens oleyl acetone solution under high-speed shearing homogenization condition, fully dispersing to form stable suspension self-emulsifying solution, and rapidly adding high-concentration Cu (NO) under continuous rapid shearing homogenization condition3)2Continuously shearing, homogenizing and fully combining the solution for 20-60 minutes, cooling at the temperature of-2-5 ℃ to promote the cypress oleyl alcohol-Cu to be rapidly crystallized and separated out, wherein Cu (NO)3)2The molar mass ratio of the compound to the cypress oleyl alcohol is 1:0.9, the cypress oleyl alcohol-Cu crystal compound is centrifugally separated, and the cypress oleyl alcohol-Cu crystal compound is further cleaned by β -cyclodextrin water solution with the concentration of 0.08% at the temperature of 0-5 ℃ to prepare the β -cyclodextrin composite crystal compound of the cypress oleyl alcohol-Cu, so that the water solubility can be improved by 12-25%.
Example 5:
13.6 g of ZnCl was weighed2Preparing a saturated or high-concentration aqueous solution with 30ml of water at a solution temperature of 35-50 ℃, dissolving 82.1 g of cypress oil alcohol in 30ml of acetone, and measuring and mixing ZnCl2Adding deionized water with the same volume as the solution, adding β -cyclodextrin 0.6 g, dissolving completely, rapidly adding β -cyclodextrin water solution into Cupressol acetone solution under high-speed shearing homogenization condition, dispersing completely to form stable suspension self-emulsifying solution, and rapidly adding high-concentration ZnCl under continuous rapid shearing homogenization condition2Continuously shearing, homogenizing and fully combining the solution for 20-60 minutes, cooling the solution at the temperature of-2-5 ℃ to promote the cypress oleyl alcohol-Zn to be rapidly crystallized and separated out, wherein ZnCl2And cypress oleyl alcohol at a molar mass ratio of 1:5, centrifugally separating the cypress oleyl alcohol-Zn crystalline compound, and further washing with 0.1% aqueous solution of β -cyclodextrin at a temperature of 0 to 5 DEG CThe β -cyclodextrin compound crystal of cypress oleyl alcohol-Zn is prepared, and the water solubility can be improved by 15-29%.
Example 6:
weighing 7.5 g of KCl and 20ml of water to prepare a saturated or high-concentration water solution with the solution temperature of 35-50 ℃, dissolving 16.4 g of cypress oleyl alcohol in 5-15 ml of ethanol, controlling the molar mass ratio of KCl to cypress oleyl alcohol to be 1:1, carrying out double-solution opposite-spraying mixing combination, further carrying out shearing homogenization on the solution subjected to spraying mixing combination for 20-60 minutes, cooling at the temperature range of-2-5 ℃ to promote the cypress oleyl alcohol-K to be rapidly crystallized and separated out, wherein the molar mass ratio of KCl to cypress oleyl alcohol is 1:1. Centrifugally separating the cypress oleyl alcohol-K crystal compound, and washing the cypress oleyl alcohol-K crystal compound by using deionized water at the temperature of 0-5 ℃ to prepare the cypress oleyl alcohol-K crystal compound.
Further, in order to improve the water solubility of the cypress oleyl alcohol-K crystalline compound, chitosan is weighed according to the weight of anhydrous substances to prepare 0.01-1.2% aqueous solution, the weight ratio of water consumption for dissolving the chitosan to the cypress oleyl alcohol-K crystalline compound is 1-2: 1, the chitosan and the cypress oleyl alcohol-K crystalline compound are uniformly mixed, dispersed and recrystallized, and the chitosan composite crystalline compound of the cypress oleyl alcohol-K is prepared by centrifugation, so that the water solubility can be improved by 15-28%.
Example 7:
weighing 7.7 g CH3COONH4Preparing a saturated or high-concentration aqueous solution with 5ml of water at a solution temperature of 35-50 ℃, dissolving 24.6 g of cypress oil alcohol in 10-20 ml of ethanol, and controlling CH3COONH4Spraying amount of the solution and cypress oleyl alcohol is 1:1.5, double-solution spraying mixing combination is carried out, the solution after spraying mixing combination is further sheared and homogenized for 20-60 minutes, and cooling is carried out at the temperature of-2-5 ℃ to promote cypress oleyl alcohol-NH4Is rapidly crystallized out, wherein, CH3COONH4And cypress oleyl alcohol in a molar mass ratio of 1: 1.5. Centrifugal separation of cypress oleyl alcohol-NH4Crystallizing the compound, and washing with deionized water at 0-5 deg.C to obtain cypress oil alcohol-NH4The compound is crystallized.
Further, for improving cypress oil alcohol-NH4Water solubility of the crystalline compound, measured as anhydrous by weightPreparing aqueous solution with concentration of 0.05-1.0% by using chitosan, and dissolving water consumption of chitosan and cypress oil alcohol-NH4The weight ratio of the crystallized compound is 1:1, the crystallized compound is evenly mixed, dispersed and recrystallized, and the cypress oil alcohol-NH is prepared by centrifugation4The chitosan composite crystalline compound can improve the water solubility by 15-32%.
Example 8:
weighing 17.0 g AgNO3Preparing a saturated or high-concentration aqueous solution with 10ml of water at a solution temperature of 35-50 ℃, dissolving 32.8 g of cypress oil alcohol in 10-20 ml of acetone, and controlling AgNO3Spraying amount of the solution and cypress oleyl alcohol in a molar mass ratio of 1:2, carrying out double-solution opposite-spraying mixing combination, further shearing and homogenizing the solution after the spraying mixing combination for 20-60 minutes, cooling at the temperature of-2-5 ℃ to promote the cypress oleyl alcohol-Ag to be rapidly crystallized and separated out, wherein AgNO is3And cypress oleyl alcohol in a molar mass ratio of 1: 2. Centrifugally separating the cypress oleyl alcohol-Ag crystal compound, and washing the cypress oleyl alcohol-Ag crystal compound by using deionized water at the temperature of 0-5 ℃ to prepare the cypress oleyl alcohol-Ag crystal compound.
Further, in order to improve the water solubility of the cypress oleyl alcohol-Ag crystalline compound, the chitosan is weighed according to the weight of anhydrous substances to prepare 0.06% -1.5% aqueous solution, the weight ratio of the water consumption for dissolving the chitosan to the cypress oleyl alcohol-Ag crystalline compound is 1:1, the chitosan and the aqueous solution are uniformly mixed, dispersed and recrystallized, and the chitosan composite crystalline compound of the cypress oleyl alcohol-Ag is prepared by centrifugation, so that the water solubility can be improved by 12% -31%.
Claims (10)
1. A method of preparing a cypress oil alcohol metal compound or an ammonium cypress oil alcohol compound, comprising:
1) dissolving cypress oil alcohol in a water-soluble organic solvent to obtain a cypress oil alcohol solution with the cypress oil alcohol concentration of 6-25 mol/L;
2) fully mixing the cypress oil alcohol solution obtained in the step 1) with an aqueous solution of water-soluble metal salt or ammonium salt at room temperature for reaction, wherein the water-soluble metal salt is selected from metal salts with solubility not lower than 35g/100ml at normal temperature, and the concentration of the aqueous solution of the water-soluble metal salt or ammonium salt is 5.4-125 mol/L; the water solution of the water-soluble metal salt or the ammonium salt is preferably a saturated solution of the water-soluble metal salt at the temperature of 30-50 ℃; controlling the molar ratio of the water-soluble metal salt or ammonium salt to the cypress oil alcohol to be 1: 0.9-5, and preparing to obtain a cypress oil alcohol metal compound or a cypress oil alcohol ammonium compound solution.
2. The method of claim 1, wherein 2) said intimately mixing is by subjecting said solution of cypress oil alcohol to shear homogenization after rapidly mixing with said aqueous solution of water-soluble metal or ammonium salt; more preferably, the continuous shearing and homogenizing are carried out for 20-60 minutes; preferably, the rapid mixing is mixing of the two solutions under high shear homogenization, or via relative spray mixing.
3. The method of claim 1, wherein 1) said cypress oleyl alcohol is dissolved in a water-soluble organic solvent, then mixed with ionized water and dispersed thoroughly to obtain said cypress oleyl alcohol solution as a stable cypress oleyl alcohol suspension self-emulsifying solution; 2) the full mixing reaction is to rapidly mix the cypress oil alcohol solution obtained in the step 1) with the water solution of the water-soluble metal salt or the ammonium salt in a high-speed shearing and homogenizing state, and then continuously shear and homogenize for 20-60 minutes.
4. The method of claim 1, wherein 1) said cypress oleyl alcohol is dissolved in a water-soluble organic solvent, then 0.01% to 5% of a viscous auxiliary substance aqueous solution is added and fully dispersed, and the obtained cypress oleyl alcohol solution is a cypress oleyl alcohol suspension self-emulsifying solution; 2) the full mixing reaction is to rapidly mix the cypress oil alcohol solution obtained in the step 1) with the water solution of the water-soluble metal salt or the ammonium salt in a high-speed shearing and homogenizing state, and then continuously shear and homogenize for 20-60 minutes.
5. The method of claim 1, wherein 1) the step of dissolving cypress oleyl alcohol in a water-soluble organic solvent to obtain a cypress oleyl alcohol solution; 2) the fully mixing reaction is to perform relative spraying and mixing on the cypress oil alcohol solution obtained in the step 1) and the water solution of the water-soluble metal salt or the ammonium salt, and then continuously shear and homogenize the solution obtained after spraying for 20-60 minutes.
6. A method of making a compound containing a cypress oil alcohol compound, comprising:
dissolving cypress oleyl alcohol in a water-soluble organic solvent to obtain a cypress oleyl alcohol solution with the cypress oleyl alcohol concentration of 6-25 mol/L;
fully mixing and reacting the cypress oil alcohol solution obtained in the step one with an aqueous solution of water-soluble metal salt or ammonium salt at room temperature, wherein the water-soluble metal salt is selected from metal salts with the solubility of not less than 35g/100ml at normal temperature, and the concentration of the aqueous solution of the water-soluble metal salt or ammonium salt is 5.4-125 mol/L; the water solution of the water-soluble metal salt or the ammonium salt is preferably a saturated solution of the water-soluble metal salt at the temperature of 30-50 ℃; controlling the molar ratio of the water-soluble metal salt or ammonium salt to the cypress oleyl alcohol to be 1: 0.9-5, preparing a cypress oil alcohol compound solution; performing conventional crystallization, separation, cleaning and drying to obtain cypress oil alcohol compound crystals;
thirdly, physically coating and modifying the crystal of the cypress oil alcohol compound obtained in the second step by using a water-soluble viscosity auxiliary substance to obtain a compound containing the cypress oil alcohol compound; the viscosity auxiliary substance is selected from 1 or more than 2 of sodium alginate, polysaccharide, beta-cyclodextrin, sodium carboxymethylcellulose (CMC-Na) (modified cellulose), starch sodium phosphate (modified starch), chitosan, xanthan gum, arabic gum, sesbania gum and carrageenan.
7. The method of any one of claims 1 or 6, wherein said cypress oil alcohol solution is a suspended self-emulsifying solution of cypress oil alcohol, which is obtained by dissolving the cypress oil alcohol in a water-soluble organic solvent, further adding deionized water, mixing and fully dispersing.
8. The method of any one of claims 1 or 6, wherein said cypress oil alcohol is dissolved in a water-soluble organic solvent, and then a 0.01% to 5% aqueous solution of a viscosity auxiliary substance is further added thereto and sufficiently dispersed, so that said cypress oil alcohol solution is a cypress oil alcohol suspension self-emulsifying solution.
9. The method of claim 6 wherein (c) said intimately mixing is carried out by rapidly mixing said solution of cypress oil alcohol with said aqueous solution of water-soluble metal or ammonium salt followed by continuous shear homogenization; more preferably, the continuous shearing and homogenizing are carried out for 20-60 minutes; preferably, the rapid mixing is mixing of the two solutions under high shear homogenization, or via relative spray mixing.
10. The method of claim 6, wherein said physical encapsulation modification is accomplished by any one of:
uniformly mixing the viscosity auxiliary substance water solution and the cypress oil alcohol compound crystal, wherein the weight ratio of the viscosity auxiliary substance to the cypress oil alcohol compound crystal is 0.01-1.2: 30, and then recrystallizing, cleaning and drying to obtain the compound containing the cypress oil alcohol compound;
or,
and cleaning the cypress oil alcohol compound crystal by using 0.01% -5% viscosity auxiliary substance aqueous solution at 0-5 ℃ to obtain the compound containing the cypress oil alcohol compound.
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| WO2022247696A1 (en) * | 2021-05-28 | 2022-12-01 | 中国科学院上海药物研究所 | Co-crystal of hinokitiol and tert-butylhydroquinone, preparation method therefor, and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022247696A1 (en) * | 2021-05-28 | 2022-12-01 | 中国科学院上海药物研究所 | Co-crystal of hinokitiol and tert-butylhydroquinone, preparation method therefor, and use thereof |
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