CN115784836A - High-selectivity method for preparing trans-menthyl-2,8-diene-1-alcohol - Google Patents
High-selectivity method for preparing trans-menthyl-2,8-diene-1-alcohol Download PDFInfo
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- CN115784836A CN115784836A CN202211582718.7A CN202211582718A CN115784836A CN 115784836 A CN115784836 A CN 115784836A CN 202211582718 A CN202211582718 A CN 202211582718A CN 115784836 A CN115784836 A CN 115784836A
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- menthyl
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- limonene
- dien
- diene
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- 238000000034 method Methods 0.000 title claims abstract description 20
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 claims abstract description 18
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 18
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940099369 (+)- limonene Drugs 0.000 claims abstract description 8
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229930007453 limonene-1,2-epoxide Natural products 0.000 claims description 4
- CCEFMUBVSUDRLG-UHFFFAOYSA-N limonene-1,2-epoxide Chemical compound C1C(C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QHMBSVQNZZTUGM-UHFFFAOYSA-N Trans-Cannabidiol Natural products OC1=CC(CCCCC)=CC(O)=C1C1C(C(C)=C)CCC(C)=C1 QHMBSVQNZZTUGM-UHFFFAOYSA-N 0.000 description 4
- QHMBSVQNZZTUGM-ZWKOTPCHSA-N cannabidiol Chemical compound OC1=CC(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 QHMBSVQNZZTUGM-ZWKOTPCHSA-N 0.000 description 4
- 229950011318 cannabidiol Drugs 0.000 description 4
- ZTGXAWYVTLUPDT-UHFFFAOYSA-N cannabidiol Natural products OC1=CC(CCCCC)=CC(O)=C1C1C(C(C)=C)CC=C(C)C1 ZTGXAWYVTLUPDT-UHFFFAOYSA-N 0.000 description 4
- PCXRACLQFPRCBB-ZWKOTPCHSA-N dihydrocannabidiol Natural products OC1=CC(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)C)CCC(C)=C1 PCXRACLQFPRCBB-ZWKOTPCHSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CYQFCXCEBYINGO-UHFFFAOYSA-N THC Natural products C1=C(C)CCC2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3C21 CYQFCXCEBYINGO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical compound C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 description 2
- 229960004242 dronabinol Drugs 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000008697 Cannabis sativa Nutrition 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000000049 anti-anxiety effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 208000028329 epileptic seizure Diseases 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 230000003400 hallucinatory effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing trans-menthyl-2,8-diene-1-alcohol with high selectivity, which comprises the following steps: step 1: adding (+) -limonene into pure water, adding a catalyst benzyltrimethylammonium hydroxide, dropwise adding hydrogen peroxide, and performing an oxidation reaction at room temperature to obtain trans-1,2-epoxy limonene; step 2: under the protection of inert gas, diphenyl disulfide and a polar solvent are mixed, sodium borohydride is added to reduce the mixture into thiophenol, and then the thiophenol and trans-1,2-epoxy limonene are subjected to ring-opening addition reaction to obtain 1S,2S, 4R) -1-methyl-2-thiophenyl-4-propylene-2-cyclohexane-1-ol. The method has high chiral selectivity, can obtain the final product trans-menthyl-2,8-diene-1-alcohol with high chiral purity, and meets the actual requirement. In addition, the method has the advantages of low price of used raw materials, easy acquisition in the market, low synthesis cost and suitability for large-scale production.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing trans-menthyl-2,8-diene-1-alcohol with high selectivity.
Background
Cannabidiol (CBD) is the main chemical component of medicinal plant cannabis sativa, is extracted from female cannabis sativa plant, is a non-addictive component of cannabis sativa, and has pharmacological effects of anti-spasm, anti-anxiety, anti-inflammatory, and relieving pain. CBD can not only help control the consumption of GABA neurotransmitter, inhibit cerebral excitation, reduce epileptic seizure, but also help improve the curative effect of other antiepileptic drugs. Even the hallucinogenic effects of Tetrahydrocannabinol (THC) on humans can be effectively abolished and are known as "anti-drug compounds".
Trans-menthyl-2,8-diene-1-ol is one of the important intermediates for preparing CBD, and the traditional preparation method usually takes D-limonene as a raw material to obtain (trans-menthyl-2,8-diene-1-ol through four steps of epoxidation, addition (selective ring opening), oxidation and elimination, and expensive selective ring opening catalysts such as zirconyl sulfate oxide and the like are usually adopted in earlier literature reports, so that the preparation cost is high, and the industrial production is not facilitated.
Therefore, a synthetic method which is simple in preparation process and suitable for industrial production is developed.
Disclosure of Invention
1. The technical problem to be solved is as follows:
aiming at the technical problems, the invention provides a method for preparing trans-menthyl-2,8-diene-1-alcohol with high selectivity.
2. The technical scheme is as follows:
a method for preparing trans-menthyl-2,8-diene-1-alcohol with high selectivity comprises the following synthetic route:
the method specifically comprises the following steps:
step 1: adding (+) -limonene into pure water, adding benzyl trimethyl ammonium hydroxide as a catalyst, dropwise adding hydrogen peroxide, and performing an oxidation reaction at room temperature to obtain trans-1,2-epoxy limonene;
and 2, step: under the protection of inert gas, diphenyl disulfide and a polar solvent are mixed, sodium borohydride is added to reduce the mixture into thiophenol, and then the thiophenol and trans-1,2-epoxy limonene are subjected to ring-opening addition reaction to obtain 1S,2S, 4R) -1-methyl-2-thiophenyl-4-propylene-2-cyclohexane-1-ol;
and 3, step 3: oxidizing 1S,2S, 4R) -1-methyl-2-thiophenyl-4-propen-2-cyclohexan-1-ol to 1S,2S, 4R-1-methyl-2-phenylsulfinyl-4-propen-2-cyclohexan-1-ol by Oxone reagent;
and 4, step 4:1S,2S, 4R-1-methyl-2-phenylsulfinyl-4-propene-2-cyclohexane-1-ol is heated to 100 to 130 ℃ under the alkaline condition, and elimination reaction is carried out to obtain trans-menthyl-2,8-diene-1-ol.
Furthermore, the concentration of the hydrogen peroxide in the step 1 is 30%, and the volume mass ratio of the hydrogen peroxide to the (+) -limonene is 0.9-1.2.
Furthermore, the adding amount of the benzyl trimethyl ammonium hydroxide is 0.1-1% of the adding amount of the (+) -limonene.
Further, the polar solvent of step 2 is anhydrous ethanol or anhydrous tetrahydrofuran.
Further, the molar ratio of diphenyl disulfide to 1,2-epoxylimonene in step 2 is 0.55 to 1.8, and the molar ratio of sodium borohydride to diphenyl disulfide is 2:1 to 3:1.
Furthermore, the mol ratio of the Oxone reagent to 1,2-epoxylimonene in the step 3 is 1.1-2.2.
Further, in step 4, the base is piperidine or pyridine.
Further, the reaction solvent of step 4 is preferably DMF or DMSO.
3. Has the advantages that:
the method has high chiral selectivity, can obtain the final product trans-menthyl-2,8-diene-1-alcohol with high chiral purity, and meets the actual requirement. In addition, the method has the advantages of low price of used raw materials, easy acquisition in the market, low synthesis cost and suitability for large-scale production.
Detailed Description
The present invention will be described in detail below.
Example 1:
a highly selective process for the preparation of trans-menthyl-2,8-dien-1-ol comprising the steps of:
step 1: adding 100g of (+) -limonene into 400ml of pure water, adding 1ml of 25% benzyl trimethyl ammonium hydroxide aqueous solution, slowly dropwise adding 95ml of 30% hydrogen peroxide, reacting for 2 hours after dropwise adding, adding sodium sulfite aqueous solution to quench reaction, extracting with ethyl acetate, separating twice, combining organic phases, washing the organic phases with saturated saline solution, concentrating, and distilling under reduced pressure to obtain 65g of trans-1,2-epoxy limonene, wherein the yield is 58.2% and the purity is 93.3%.
Step 2: under the protection of nitrogen, 43g of diphenyl disulfide and 350ml of absolute ethyl alcohol are mixed, the temperature is reduced to 5 ℃ in an ice-water bath, 16g of sodium borohydride is slowly added, the temperature is controlled to be not higher than 10 ℃, stirring is continued for 1h, 150ml of ethanol solution of 50g of trans-1,2-epoxy limonene obtained in the step 1 is dropwise added, the temperature is raised to 65 ℃, reaction is continued for 5h, and the reaction is stopped.
And step 3: the reaction solution in step 2 was cooled to 0 ℃, 300ml of water was added to the reaction solution in step 2, 300g of Oxone reagent was added thereto, and the reaction was stirred at room temperature for 3 hours. Adding ethyl acetate for extraction, combining organic phases, washing the organic phases by using a sodium sulfite solution, washing the organic phases by using a saturated sodium chloride solution, and concentrating to obtain a crude product of 1S,2S, 4R-1-methyl-2-phenylsulfinyl-4-propylene-2-cyclohexane-1-ol (87 g).
And 4, step 4:
adding 87g of crude product of 1S,2S, 4R-1-methyl-2-phenylsulfinyl-4-propylene-2-cyclohexane-1-ol into 500ml of DMF, adding 34g of piperidine, heating to 120 ℃, stirring for reaction for 6h, concentrating to remove most of DMF, adding ethyl acetate, washing an organic phase with diluted hydrochloric acid, washing with saturated saline solution, drying with anhydrous sodium sulfate, concentrating, and distilling under reduced pressure to obtain 32g of trans-menthyl-2,8-diene-1-ol with the purity of 99.4%; ee% is more than 99%; the total yield of the steps 2-4 is 64%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A method for preparing trans-menthyl-2,8-diene-1-alcohol with high selectivity is characterized in that the synthetic route of the method is as follows:
the method specifically comprises the following steps:
step 1: adding (+) -limonene into pure water, adding a catalyst benzyltrimethylammonium hydroxide, dropwise adding hydrogen peroxide, and performing an oxidation reaction at room temperature to obtain trans-1,2-epoxy limonene;
step 2: under the protection of inert gas, diphenyl disulfide and a polar solvent are mixed, sodium borohydride is added to reduce the mixture into thiophenol, and then the thiophenol and trans-1,2-epoxy limonene are subjected to ring-opening addition reaction to obtain 1S,2S, 4R) -1-methyl-2-thiophenyl-4-propylene-2-cyclohexane-1-ol;
and step 3: oxidizing 1S,2S, 4R) -1-methyl-2-thiophenyl-4-propen-2-cyclohexan-1-ol to 1S,2S, 4R-1-methyl-2-phenylsulfinyl-4-propen-2-cyclohexan-1-ol by Oxone reagent;
and 4, step 4:1S,2S, 4R-1-methyl-2-phenylsulfinyl-4-propene-2-cyclohexane-1-ol is heated to 100 to 130 ℃ under the alkaline condition, and elimination reaction is carried out to obtain trans-menthyl-2,8-diene-1-ol.
2. The method for preparing trans-menthyl-2,8-dien-1-ol with high selectivity according to claim 1, wherein the concentration of hydrogen peroxide in step 1 is 30%, and the volume mass ratio of hydrogen peroxide to (+) -limonene is 0.9.
3. The method for preparing trans-menthyl-2,8-dien-1-ol with high selectivity as claimed in claim 1, wherein the amount of benzyltrimethyl ammonium hydroxide added is 0.1-1% of the amount of (+) -limonene added.
4. The highly selective method for preparing trans-menthyl-2,8-dien-1-ol according to claim 2 or 3, wherein the polar solvent of step 2 is absolute ethanol or absolute tetrahydrofuran.
5. The highly selective process for preparing trans-menthyl-2,8-dien-1-ol according to claim 4 wherein the molar ratio of diphenyl disulfide to 1,2-epoxylimonene in step 2 is 0.55 to 1 to 0.8 and the molar ratio of sodium borohydride to diphenyl disulfide is 2:1 to 3:1.
6. The highly selective process for preparing trans-menthyl-2,8-dien-1-ol as claimed in claim 5, wherein the molar ratio of Oxone reagent to 1,2-epoxylimonene in step 3 is 1.1-2.2.
7. The method for preparing trans-menthyl-2,8-dien-1-ol with high selectivity according to claim 6, wherein the base in step 4 is piperidine or pyridine.
8. The method for preparing trans-menthyl-2,8-dien-1-ol with high selectivity according to claim 7, wherein the reaction solvent of step 4 is DMF or DMSO.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070072939A1 (en) * | 2005-06-16 | 2007-03-29 | Euro-Celtique, S.A. | Cannabinoid active pharmaceutical ingredient for improved dosage forms |
| US20090298930A1 (en) * | 2004-11-22 | 2009-12-03 | Gutman Arie L | Methods For Purifying Trans-(-) Delta9-Tetrahydrocannabinol And Trans-(+)-Delta9-Tetrahydrocannabinol |
| US20120022063A1 (en) * | 2008-02-08 | 2012-01-26 | Nektar Therapeutics | Oligomer-Cannabinoid Conjugates |
| CN109734554A (en) * | 2019-02-25 | 2019-05-10 | 江苏暨明医药科技有限公司 | A kind of synthesis technology of trans--menthyl -2,8- diene -1- alcohol |
| CN110790690A (en) * | 2019-11-18 | 2020-02-14 | 湖南师范大学 | Synthetic method of 3, 4-difluoro-2- ((phenylthio) methyl) benzoic acid |
| CN112062750A (en) * | 2020-07-22 | 2020-12-11 | 和鼎（南京）医药技术有限公司 | Process for preparing a Barosavir intermediate and intermediate obtained by this process |
-
2022
- 2022-12-08 CN CN202211582718.7A patent/CN115784836A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090298930A1 (en) * | 2004-11-22 | 2009-12-03 | Gutman Arie L | Methods For Purifying Trans-(-) Delta9-Tetrahydrocannabinol And Trans-(+)-Delta9-Tetrahydrocannabinol |
| US20070072939A1 (en) * | 2005-06-16 | 2007-03-29 | Euro-Celtique, S.A. | Cannabinoid active pharmaceutical ingredient for improved dosage forms |
| US20120022063A1 (en) * | 2008-02-08 | 2012-01-26 | Nektar Therapeutics | Oligomer-Cannabinoid Conjugates |
| CN109734554A (en) * | 2019-02-25 | 2019-05-10 | 江苏暨明医药科技有限公司 | A kind of synthesis technology of trans--menthyl -2,8- diene -1- alcohol |
| CN110790690A (en) * | 2019-11-18 | 2020-02-14 | 湖南师范大学 | Synthetic method of 3, 4-difluoro-2- ((phenylthio) methyl) benzoic acid |
| CN112062750A (en) * | 2020-07-22 | 2020-12-11 | 和鼎（南京）医药技术有限公司 | Process for preparing a Barosavir intermediate and intermediate obtained by this process |
Non-Patent Citations (2)
| Title |
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| A´IDA LUZ VILLA DE P., 等: "Kinetics of limonene epoxidation by hydrogen peroxide on PW-Amberlite", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 185, pages 270 - 271 * |
| KATARZYNA A. MALTBY, 等: "Selective Catalytic Synthesis of 1, 2- and 8, 9-Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes", CHEM. EUR. J., vol. 26 * |
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