TW201339129A - 製造厚樸酚及其衍生物之方法 - Google Patents
製造厚樸酚及其衍生物之方法 Download PDFInfo
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- TW201339129A TW201339129A TW101148200A TW101148200A TW201339129A TW 201339129 A TW201339129 A TW 201339129A TW 101148200 A TW101148200 A TW 101148200A TW 101148200 A TW101148200 A TW 101148200A TW 201339129 A TW201339129 A TW 201339129A
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- biphenyl
- diol
- dimethoxy
- diallyl
- magnolol
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- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 18
- OYAQUBKYAKSHOA-UHFFFAOYSA-N 2-(2-hydroxy-5-propylphenyl)-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C=2C(=CC=C(CCC)C=2)O)=C1 OYAQUBKYAKSHOA-UHFFFAOYSA-N 0.000 claims abstract description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- VGMKUVCDINAAFC-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyphenyl)benzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1OC VGMKUVCDINAAFC-UHFFFAOYSA-N 0.000 claims description 4
- YAJRLSQAVCETBJ-UHFFFAOYSA-N 4-bromo-2-(5-bromo-2-methoxyphenyl)-1-methoxybenzene Chemical group COC1=CC=C(Br)C=C1C1=CC(Br)=CC=C1OC YAJRLSQAVCETBJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- CQGQGUJHGHXQHF-UHFFFAOYSA-N 1-propyl-3-(3-propylphenyl)benzene Chemical group CCCC1=CC=CC(C=2C=C(CCC)C=CC=2)=C1 CQGQGUJHGHXQHF-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000001035 methylating effect Effects 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FCTQSFVLYRQKTR-UHFFFAOYSA-N 4-bromo-2-(5-bromo-2-hydroxyphenyl)phenol Chemical compound OC1=CC=C(Br)C=C1C1=CC(Br)=CC=C1O FCTQSFVLYRQKTR-UHFFFAOYSA-N 0.000 description 2
- 241000218378 Magnolia Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001335 demethylating effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- LPLLWKZDMKTEMV-UHFFFAOYSA-N 1-bromo-3-(3-bromophenyl)benzene Chemical group BrC1=CC=CC(C=2C=C(Br)C=CC=2)=C1 LPLLWKZDMKTEMV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/003—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by hydrogenation of an unsaturated part
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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Abstract
本發明係關於用於製造厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇)及四氫厚樸酚(5,5’-二丙基-聯苯基-2,2’-二醇)之高產量方法。
Description
本發明係關於用於製造厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇)及四氫厚樸酚(5,5’-二丙基-聯苯基-2,2’-二醇)之高產量方法。
使用於口腔護理組成物中之安全有效的抗細菌劑及抗發炎劑仍有需要。已知厚樸萃出物含有具抗細菌及/或抗發炎特性之化合物，且此等化合物於口腔護理組成物使用上業已是相當大的興趣焦點。此等化合物用於口腔護理組成物中係說明於，例如WO 2001/085116、WO 2011/106492及WO 2011/106493中，該申請案之內容係合併於本文中參考。合成厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇)之方法係於例如WO 2011/106003中揭示。具有其他烷基替代烯丙基之厚樸萃出物
之多種組份的合成非天然類似物亦已知具有抗細菌活性，但該化合物於某些情況中昂貴或難以合成。
目前用於厚樸酚之合成方法涉及昂貴的試劑且產量非常低。其係想要較便宜、較高產量之合成方法用來製造厚樸酚及相關化合物。
先前製造厚樸酚之合成方法一般係用聯苯基-2,2’-二醇進行溴化作用起始而得到該5,5’-二溴-聯苯基-2,2’-二醇，接著用甲基或其他O-保護基進行O-保護作用，與烯丙基溴化物進行反應而得到保護形式之厚樸酚，且予以去保護而得到厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇，有時稱為4,4’-二烯丙基-2,2’雙酚)。吾等業已發現於大規模上，該5,5’-二溴-聯苯基-2,2’-二醇之O-保護步驟之效率低且緩慢。吾等業已發現於溴化步驟之前進行O-保護步驟將導致更有效的反應及較高的產量。
於現有的方法中，去保護步驟為另一個昂貴且產量有限的步驟。所報導之用於去甲基化的方法經常昂貴且有時需要非常低的溫度(-78℃，使用BBr3)，且有時需要回流條件。該反應混合物總是難以分離及純化，導致厚樸酚之產量低。吾人業已發現使用氯化鋁/硫脲絡合物進行去保護作用不需要極端溫度或昂貴試劑且可導致高的產量。
本發明之某些具體例係提供用於厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇)之簡單、相對高產量的合成法，其包括：(i)使用硫酸二甲酯將聯苯基-2,2’-二醇予以甲基化而得到2,2’-二甲氧基-聯苯基；(ii)將該2,2’-二甲氧基-聯苯基予以溴化而得到2,2’-二甲氧基-5,5’-二溴-聯苯基；(iii)將該2,2’-二甲氧基-5,5’-二溴-聯苯基與烯丙基溴化物進行烷基化作用而得到2,2’-二甲氧基-5,5’-二烯丙基-聯苯基；(iv)藉著與氯化鋁及硫脲進行反應而將該2,2’-二甲氧基-5,5’-二烯丙基-聯苯基去甲基化；且(v)將如此所得到之5,5’-二烯丙基-聯苯基-2,2’-二醇回收。
於某些具體例中，本發明進一步提供用於生產四氫厚樸酚(5,5’-二丙基-聯苯基-2,2’-二醇)之方法，其包括氫化前述方法的該5,5’-二烯丙基-聯苯基-2,2’-二醇產物，例如，於鈀或鎳催化劑存在下。
本發明之適用性的其他領域可由下文所提供之詳細說明而變得顯而易見。應瞭解當指明本發明之較佳具體例時，該詳細說明及特定實例意欲僅用於闡明之目的且並非意欲限制本發明之範圍。
本發明因此係提供用於製造厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇)之方法(方法1)，其包括：(i)使用硫酸二甲酯將聯苯基-2,2’-二醇予以甲基化而得到2,2’-二甲氧基-聯苯基；(ii)將該2,2’-二甲氧基-聯苯基予以溴化而得到2,2’-二甲氧基-5,5’-二溴-聯苯基；(iii)將該2,2’-二甲氧基-5,5’-二溴-聯苯基與烯丙基溴化物進行烷基化作用而得到2,2’-二甲氧基-5,5’-二烯丙基-聯苯基；(iv)藉著與氯化鋁及硫脲進行反應而將該2,2’-二甲氧基-5,5’-二烯丙基-聯苯基去甲基化；且(v)將如此所得到之5,5’-二烯丙基-聯苯基-2,2’-二醇回收。
1.1.方法1，其中步驟(i)係於水介質中，於無機鹼例如氫氧化鈉或氫氧化鉀存在下進行。
1.2.任何前述之方法，其中步驟(iii)係於極性非質子性溶劑例如四氫呋喃(THF)中進行。
1.3.任何前述之方法，其中該去甲基化作用步驟(iv)係於溫度於30℃及60℃間進行。
一般反應圖示如下：
如全文中所使用者，範圍係以簡略方式使用來說明該範圍內之各個及每一個數值。於該範圍內之任何數值可選擇作為該範圍之終點。此外，本文中所引證之所有的參考，其等之全部內容合併於本文中參考。萬一於本發明揭示內容中之定義與所引證之參考者發生衝突，則對照(controls)本發明之揭示內容。
除非另有指明，應瞭解於本文中及於本說明書中任何地方所表達之所有的百分比及量係指重量百分比。所給定之量係以該物質之活性重量計。
將2,2’-雙酚與硫酸二甲酯於氫氧化鈉中進行反應達1-2小時而得到2,2’-二苯甲醚(95%產率)。將固體分離，用水清洗且於60-65℃乾燥。
將2,2’-二苯甲醚予以有效地溴化而得到4,4’-二溴-2,2’-二苯甲醚，然後將其與烯丙基溴化物於THF中進行反應而得到4,4’-二烯丙基-2,2’-二苯甲醚。
將該4,4’-二烯丙基-2,2’-二苯甲醚於50℃於3小時期間緩緩加至含有氯化鋁、硫脲及1,2-二氯乙烷之混合物。將溫度及攪拌保持達另外3-4小時。將反應混合物冷卻且加至HCl且將各相分離。將該有機相加至木炭，過濾且將該溶劑蒸餾，而得到該標的化合物。
Claims (5)
- 一種用於製造厚樸酚(5,5’-二烯丙基-聯苯基-2,2’-二醇)或四氫厚樸酚(5,5’-二丙基-聯苯基-2,2’-二醇)之方法，其包括：i)使用硫酸二甲酯將聯苯基-2,2’-二醇予以甲基化而得到2,2’-二甲氧基-聯苯基；ii)將該2,2’-二甲氧基-聯苯基予以溴化而得到2,2’-二甲氧基-5,5’-二溴-聯苯基；iii)將該2,2’-二甲氧基-5,5’-二溴-聯苯基與烯丙基溴化物進行烷基化作用而得到2,2’-二甲氧基-5,5’-二烯丙基-聯苯基；iv)藉著與氯化鋁及硫脲進行反應而將該2,2’-二甲氧基-5,5’-二烯丙基-聯苯基去甲基化；v)將如此所得到之5,5’-二烯丙基-聯苯基-2,2’-二醇回收；且vi)將該5,5’-二烯丙基-聯苯基-2,2’-二醇於金屬催化劑存在下任意地氫化，且將如此所得到之5,5’-二丙基-聯苯基-2,2’-二醇回收。
- 如申請專利範圍第1項之方法，其中步驟(i)係於水介質中，於無機鹼存在下進行。
- 如前述申請專利範圍中任一項之方法，其中步驟(iii)係於極性非質子性溶劑中進行。
- 如前述申請專利範圍中任一項之方法，其中步驟(iv)係於溫度介於30℃及60℃間進行。
- 如前述申請專利範圍中任一項之方法，其包括任意之步驟(vi)。
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|---|---|---|---|
| PCT/US2011/066045 WO2013095361A1 (en) | 2011-12-20 | 2011-12-20 | Processes for making magnolol and derivatives thereof |
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| TW201339129A true TW201339129A (zh) | 2013-10-01 |
| TWI504585B TWI504585B (zh) | 2015-10-21 |
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| ZA (1) | ZA201404277B (zh) |
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| EP2948220B1 (en) | 2013-01-23 | 2018-07-04 | Colgate-Palmolive Company | Processes for making magnolol derivatives |
| CN105622603A (zh) * | 2015-05-28 | 2016-06-01 | 广州牌牌生物科技有限公司 | 多核化合物、其制备方法以及其应用 |
| CN109053387B (zh) * | 2018-09-19 | 2021-07-09 | 九江学院 | 一种厚朴酚的合成方法 |
| US12311044B2 (en) | 2018-12-18 | 2025-05-27 | Conopco, Inc. | Antimicrobial composition |
| CN113717683B (zh) * | 2021-09-27 | 2023-05-09 | 武汉纺织大学 | 一种光固化水下生物基抗菌胶粘剂及其制备方法 |
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| US5959157A (en) * | 1995-06-26 | 1999-09-28 | Alliedsignal, Inc. | Process for making hydroxy-substituted ethynylated biphenyl compounds |
| CN1106391C (zh) | 1999-04-12 | 2003-04-23 | 李安荣 | 厚朴酚系列化合物及其合成方法和以该化合物为活性成分的药物组合物 |
| US6500409B1 (en) | 2000-05-10 | 2002-12-31 | Colgate Palmolive Company | Synergistic antiplaque/antigingivitis oral composition |
| JP4851940B2 (ja) | 2004-11-19 | 2012-01-11 | 宮城県 | がんまたは糖尿病治療のための医薬組成物 |
| CA2580877C (en) | 2004-12-08 | 2011-09-06 | Richter Gedeon Vegyeszeti Gyar Rt. | A new process for the preparation of phenolic hydroxy-substituted compounds |
| JP4757911B2 (ja) | 2005-05-30 | 2011-08-24 | コリア インスティテュート オブ オリエンタル メディシン | マグノリアの皮質又はマグノリアの根からのマグノロールの大量分離方法 |
| EP2040696B1 (en) | 2006-07-14 | 2017-01-25 | DSM IP Assets B.V. | Compositions and use thereof for the treatment, co-treatment or prevention of inflammatory disorders |
| CN101293816B (zh) | 2008-06-24 | 2011-09-28 | 江南大学 | 厚朴酚的合成方法 |
| JP5265282B2 (ja) * | 2008-09-19 | 2013-08-14 | 花王株式会社 | 皮膚化粧料 |
| TWI422382B (zh) | 2010-02-24 | 2014-01-11 | Colgate Palmolive Co | 加強木蘭活性物之溶解度及傳送的組成物 |
| TWI459957B (zh) | 2010-02-24 | 2014-11-11 | Colgate Palmolive Co | 口腔保健組成物 |
| ES2507615T3 (es) | 2010-02-25 | 2014-10-15 | Colgate-Palmolive Company | Síntesis de magnolol y sus compuestos análogos |
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| BR112014014255A2 (pt) | 2017-06-13 |
| AR089310A1 (es) | 2014-08-13 |
| EP2794534B1 (en) | 2016-11-30 |
| WO2013095361A1 (en) | 2013-06-27 |
| TWI504585B (zh) | 2015-10-21 |
| CN103987684A (zh) | 2014-08-13 |
| EP2794534A1 (en) | 2014-10-29 |
| ZA201404277B (en) | 2016-05-25 |
| RU2014129826A (ru) | 2016-02-10 |
| US9000231B2 (en) | 2015-04-07 |
| US20140357902A1 (en) | 2014-12-04 |
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