WO2022223117A1 - Verfahren zur herstellung von cedrendiol - Google Patents
Verfahren zur herstellung von cedrendiol Download PDFInfo
- Publication number
- WO2022223117A1 WO2022223117A1 PCT/EP2021/060525 EP2021060525W WO2022223117A1 WO 2022223117 A1 WO2022223117 A1 WO 2022223117A1 EP 2021060525 W EP2021060525 W EP 2021060525W WO 2022223117 A1 WO2022223117 A1 WO 2022223117A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cedrene
- alpha
- water
- particularly preferably
- weight ratio
- Prior art date
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- IRAQOCYXUMOFCW-UHFFFAOYSA-N di-epi-alpha-cedrene Natural products C1C23C(C)CCC3C(C)(C)C1C(C)=CC2 IRAQOCYXUMOFCW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 36
- -1 cedrene diol Chemical class 0.000 title claims description 6
- IRAQOCYXUMOFCW-OSFYFWSMSA-N cedr-8-ene Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1C(C)=CC2 IRAQOCYXUMOFCW-OSFYFWSMSA-N 0.000 claims abstract description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 33
- 239000003586 protic polar solvent Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002585 base Substances 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 7
- 150000003333 secondary alcohols Chemical class 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000019439 ethyl acetate Nutrition 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010627 cedar oil Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940045348 brown mixture Drugs 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- DJYWGTBEZVORGE-CVWWDKSYSA-N cedr-8(15)-en-9-ol Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1C(=C)C(O)C2 DJYWGTBEZVORGE-CVWWDKSYSA-N 0.000 description 1
- HZRFVTRTTXBHSE-VJOISMJWSA-N cedrene epoxide Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)C1C1(C)OC1C2 HZRFVTRTTXBHSE-VJOISMJWSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/76—Ring systems containing bridged rings containing three rings containing at least one ring with more than six ring members
- C07C2603/78—Ring systems containing bridged rings containing three rings containing at least one ring with more than six ring members containing seven-membered rings
Definitions
- Cedrenediols are important starting materials for the production of high-quality fragrances. Because of its outstanding odor properties as an acetonide, c/s-cedrenediol is of particular interest.
- the production of c/s-cedrenediol usually takes place from cedrene in a two-stage process. First, cedrene is oxidized to the cedrene epoxide and this epoxide is then opened to the diol. However, by-products (cedralone, trans-cedrenediol) are also formed when the epoxide is opened.
- the object is achieved by a process for preparing c/s-cedrenediol comprising the steps: i) providing alpha-cedrene in a solvent comprising or consisting of water and at least one other protic solvent, preferably selected from the group consisting of secondary and tertiary alcohols, particularly preferably selected from the group consisting of fe/f-butanol and isopropanol, ii) adding potassium permanganate and a base to the solution from step i), and, optionally iii) removing the further protic solvent from the reaction mixture from step ii).
- Cedrenediol-Mn0 4 complex Scheme 3 Elimination of manganese from the cedrenediol-Mn0 4 complex.
- a protic solvent is to be understood as meaning any solvent which has a functional group from which hydrogen can be split off as a proton. Since water can dissociate into H + and OH-, it is also a protic solvent.
- Other protic solvents are primary, secondary and tertiary alcohols and carboxylic acids. Alkanes, ethers, esters, ketones and aldehydes, on the other hand, do not represent protic solvents within the meaning of the present invention.
- a base is to be understood as meaning a compound which forms hydroxide ions in aqueous solution.
- Suitable bases for use in step ii) are described further below.
- Secondary and tertiary alcohols and very particularly fe/f-butanol and isopropanol have proven to be advantageous. Secondary and tertiary alcohols dissolve cedrene well and phase separation does not occur when an aqueous solution of potassium permanganate is added. These solvents are also largely inert under the reaction conditions so that they are not oxidized by the potassium permanganate and thus the need for a larger amount of oxidizing agent can be avoided.
- the process described above additionally comprises the steps: iv) extracting the c/s-cedrenediol formed from the reaction mixture from step iii), and v) removing the extractant from step iv) and obtaining cis-cedrenediol.
- the resulting c/s-cedrenediol can be obtained by extraction.
- the further protic solvent is removed as completely as possible so that it does not disturb the phase separation in the subsequent extraction. Suitable extraction agents are described below.
- step i) the alpha-cedrene has a purity of at least 70%, preferably at least 80%, particularly preferably at least 90% and/or wherein the alpha-cedrene is distilled before step i). .
- cedar oil in which approximately 70% alpha-cedrene is present. If the alpha-cedrene, for example in the form of cedar oil, is distilled before step i), a purity of over 90% can be achieved. If less pure alpha-cedrene is used, more potassium permanganate and base are required and it has to be dosed at a lower temperature.
- the alpha-cedrene in a weight ratio of 1:5 to 1:10 alpha-cedrene to the further protic solvent, preferably in a weight ratio of 1:6 to 1: 9 alpha-cedrene to the further protic solvent, particularly preferably in a weight ratio of 1: 7 to 1: 8 alpha-cedrene to the further protic solvent and / or in step i) the alpha-cedrene in a weight ratio of 1: 1 to 1:6 alpha-cedrene to water, preferably in a weight ratio of 1:2 to 1:5 alpha-cedrene to water, more preferably in a weight ratio of 1:3 to 1:4 alpha-cedrene to water.
- the base is an inorganic base, preferably selected from the group of alkali metal and alkaline earth metal hydroxides and alkali metal and alkaline earth metal carbonates, particularly preferably selected from NaOH, KOH, K2CO3 and CaCOs.
- step ii) the potassium permanganate is added in an amount of 0.8 to 5 equivalents based on the alpha-cedrene provided in step i), preferably in an amount of 1 to 3 equivalents, particularly preferably in an amount of 1.2 to 1.5 equivalents and/or the base being added in an amount of 0.5 to 3 equivalents based on the alpha-cedrene provided in step i), preferably in an amount of 1 to 1.5 equivalents, particularly preferably in an amount of 1.2 to 1.3 equivalents.
- a mixture containing or consisting of potassium permanganate, base and water is added to the solution from step i) in step ii), preferably the mixture is stirred continuously during the addition and/or it becomes a gas passed through the mixture.
- the water is preferably present in a weight ratio of 1:5 to 1:20 potassium permanganate to water, preferably 1:10 to 1:15 potassium permanganate to water , particularly preferably 1: 12 to 1: 14 potassium permanganate to water.
- the alpha-cedrene is provided in the solvent at a temperature in the range from 5 to 40 °C, preferably 15 to 30 °C, particularly preferably 18 to 22 °C and/or in Step ii) the potassium permanganate and the base are added at a temperature of 10 to 40°C, preferably 15 to 30°C, particularly preferably 20 to 24°C.
- the method according to the invention can be carried out in a relatively large temperature range, in particular also at temperatures around room temperature, so that no heating or cooling is necessary. If dosing at higher temperatures, the GC purity of the end product decreases. Dosing at a lower temperature (approx. 10 °C) also works, but does not improve the result of the reaction.
- the further protic solvent is removed in step iii) by means of distillation.
- step iii) it is important for the purification of the product by means of extraction that the further protic solvent is removed as completely as possible in step iii) so that the phase separation is not disturbed. Removal by distillation gives particularly good results.
- fe/f-butanol is used as a further protic solvent, it is preferably distilled off as an azeotrope containing from 10 to 30% of water, particularly preferably as an azeotrope containing from 15 to 25% of water.
- an aprotic extraction agent is used as the extraction agent in step iv), preferably selected from the group consisting of ethers and esters, particularly preferably selected from the group consisting of ethyl acetate and methyl fe/f-butyl ether.
- an aprotic solvent is to be understood as meaning a solvent which does not have a functional group from which hydrogen can be split off as a proton. Examples of aprotic solvents are aliphatic or aromatic alkanes or alkenes, esters, ethers, ketones or aldehydes.
- the extractant is preferably used in a weight ratio of 1: 2 to 1: 20 of the alpha-cedrene provided in step i) to the extractant, preferably in a weight ratio of 1: 5 to 1: 12 of the alpha-cedrene provided in step i) to extractant, particularly preferably in a weight ratio of 1:8 to 1:9.5 of the alpha-cedrene provided in step i) to extractant.
- cedrenediol may already be precipitated, which can be redissolved by further addition of extraction agent or by increasing the temperature.
- the aqueous phase can then be separated and the extraction repeated with a further portion of extractant.
- soda and water By adding soda and water, the last residues of sulfuric acid can be removed or neutralized from the organic phase.
- no traces of acid should remain in the cedrenediol.
- it can be washed with sodium chloride/water to ensure that no acid residues remain in the cedrenediol and the resulting cedrenediol solution is approximately neutral.
- the present invention also relates to the use of a mixture comprising or consisting of water and at least one further protic solvent, preferably selected from the group consisting of secondary and tertiary alcohols, particularly preferably selected from the group consisting of fe/f-butanol and isopropanol Solvent in the oxidation of alpha-cedrene with potassium permanganate, preferably in a process as described above.
- a further protic solvent preferably selected from the group consisting of secondary and tertiary alcohols, particularly preferably selected from the group consisting of fe/f-butanol and isopropanol Solvent in the oxidation of alpha-cedrene with potassium permanganate, preferably in a process as described above.
- Trace heating is set to 80 °C. A total of about 910 g of distillate are obtained. The fe/f-butanol obtained in this way can be used again for the reaction.
- cedrenediol partially precipitates on cooling. If the solvent is removed, about 102 g of cedrenediol of the formula (I) are obtained (purity according to GC about 93%, about 0.40 mmol, about 87% yield). Other substances included according to GC are: cedrene ( ⁇ 1%), cedralon ( ⁇ 1%), cedrenol (approx. 1%) and the isomer of formula (II) ( ⁇ 1%).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21721479.0A EP4326699A1 (de) | 2021-04-22 | 2021-04-22 | Verfahren zur herstellung von cedrendiol |
CN202180097273.0A CN117222614A (zh) | 2021-04-22 | 2021-04-22 | 雪松烯二醇的制备方法 |
PCT/EP2021/060525 WO2022223117A1 (de) | 2021-04-22 | 2021-04-22 | Verfahren zur herstellung von cedrendiol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2021/060525 WO2022223117A1 (de) | 2021-04-22 | 2021-04-22 | Verfahren zur herstellung von cedrendiol |
Publications (1)
Publication Number | Publication Date |
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WO2022223117A1 true WO2022223117A1 (de) | 2022-10-27 |
Family
ID=75674827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2021/060525 WO2022223117A1 (de) | 2021-04-22 | 2021-04-22 | Verfahren zur herstellung von cedrendiol |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP4326699A1 (de) |
CN (1) | CN117222614A (de) |
WO (1) | WO2022223117A1 (de) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0857723A1 (de) * | 1997-02-06 | 1998-08-12 | Dragoco Gerberding & Co Aktiengesellschaft | Cyclische Cedren-Acetale, ihre Herstellung und ihre Verwendung |
-
2021
- 2021-04-22 WO PCT/EP2021/060525 patent/WO2022223117A1/de active Application Filing
- 2021-04-22 EP EP21721479.0A patent/EP4326699A1/de active Pending
- 2021-04-22 CN CN202180097273.0A patent/CN117222614A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0857723A1 (de) * | 1997-02-06 | 1998-08-12 | Dragoco Gerberding & Co Aktiengesellschaft | Cyclische Cedren-Acetale, ihre Herstellung und ihre Verwendung |
Non-Patent Citations (3)
Title |
---|
F. W. SEMMLER ET AL: "Zur Kenntnis der Bestandteile ätherischer öle (Untersuchungen über das Sesquiterpen Cedren)", BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, vol. 40, no. 3, 1 June 1907 (1907-06-01), DE, pages 3521 - 3528, XP055722403, ISSN: 0365-9496, DOI: 10.1002/cber.190704003137 * |
WIBERG KENNETH B. ET AL: "The Mechanisms of Permanganate Oxidation. IV. Hydroxylation of Olefins and Related Reactions", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 79, no. 11, 1 June 1957 (1957-06-01), pages 2822 - 2824, XP055877157, ISSN: 0002-7863, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/ja01568a042> DOI: 10.1021/ja01568a042 * |
WIBERGSAEGEBARTH, J. AM. CHEM. SOC., vol. 79, no. 11, 1957, pages 2822 - 2824 |
Also Published As
Publication number | Publication date |
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CN117222614A (zh) | 2023-12-12 |
EP4326699A1 (de) | 2024-02-28 |
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