- Highly efficient catalysts in directed oxygen-transfer processes: Synthesis, structures of novel manganese-containing heteropolyanions, and applications in regioselective epoxidation of dienes with hydrogen peroxide
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A series of novel manganese(II)-substituted polyoxometalates, [(M(II)(H2O)3)2(WO2)2(BiW9O33)2] 10-(1), [(Mn(II)(H2O))3(SbW9O33)2]12- (2), and [(Mn(II)(H2O)3)2(Mn(II)(H2O)2)2(TeW9O33)2]8- (3), were synthesized and characterized by X-ray structure analyses. The use of these oxidatively and solvolytically stable heteropolyanions as homogeneous catalysts for the epoxidation of dienes was investigated by gas chromatography/mass spectrometry, IR spectroscopy, UV-visible studies, and cyclic voltammetric measurements. The catalytic performance is exemplified by the model substrate (R)-(+)-limonene, at ambient temperatures in a biphasic system, with excellent regioselectivities, >99%, and very high turnovers even with only a small molar excess of hydrogen peroxide.
- B?sing, Michael,N?h, Andreas,Loose, Ina,Krebs, Bernt
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Read Online
- Stereoselective Synthesis of Nonpsychotic Natural Cannabidiol and Its Unnatural/Terpenyl/Tail-Modified Analogues
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Here, we report a three-step concise and stereoselective synthesis route to one of the most important phytocannabinoids, namely, (-)-cannabidiol (-CBD), from inexpensive and readily available starting material R-(+)-limonene. The synthesis involved the diastereoselective bifunctionalization of limonene, followed by effective elimination leading to the generation of key chiral p-mentha-2,8-dien-1-ol. The chiral p-mentha-2,8-dien-1-ol on coupling with olivetol under silver catalysis provided regiospecific (-)-CBD, contrary to reported ones which gave a mixture. The newly developed approach was further extended to its structural analogues cannabidiorcin and other tail/terpenyl-modified analogues. Moreover, its opposite isomer (+)-cannabidiol was also successfully synthesized from S-(-)-limonene.
- Anand, Radhika,Cham, Pankaj Singh,Gannedi, Veeranjaneyulu,Sharma, Sumit,Kumar, Mukesh,Singh, Rohit,Vishwakarma, Ram A.,Singh, Parvinder Pal
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p. 4489 - 4498
(2022/04/07)
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- Preparation method of (1S, 4R)-1-methyl-4-(1-methylvinyl)-2-cyclohexene-1-ol
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The invention relates to a preparation method of (1S, 4R)-1-methyl-4-(1-methylvinyl)-2-cyclohexene-1-ol, and belongs to the technical field of organic solvents. The preparation method comprises the following steps: reacting limonene with a halogenating reagent to obtain an intermediate shown in a formula (1), then reacting the intermediate shown in the formula (1) with a tertiary amine compound to obtain an intermediate shown in a formula (2), and finally carrying out a pyrolysis elimination reaction on the intermediate shown in the formula (2) to obtain (1S, 4R)-1-methyl-4-(1-methylvinyl)-2-cyclohexene-1-ol. The preparation method has the advantages of mild conditions, no need of an oxidation process of hydrogen peroxide with high preparation condition requirements and high safety risk, no need of an expensive catalyst, high yield, high product purity, simple steps, and suitableness for industrial production.
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- CANNABINOID DERIVATIVES, PRECURSORS AND USES
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The present disclosure relates to new cannabinoid derivatives and precursors and processes for their preparation. The disclosure also relates to pharmaceutical and analytical uses of the new cannabinoid derivatives.
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- Preparation method of (1S, 4R)-1-methyl-4-(1-methyl vinyl)-2-cyclohexene-1-alcohol
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The invention discloses a preparation method of (1S, 4R)-1-methyl-4-(1-methyl vinyl)-2-cyclohexene-1-alcohol, which comprises the following steps: by using D-limonene as a raw material, carrying out double bond addition and hydroxyl protection to obtain an intermediate compound; and carrying out elimination reaction and continuing deprotection to finally prepare the product. The method has the advantages of two-step continuous reaction, short process route and few byproducts, the obtained product has high chiral selectivity, and the yield is up to 70% or above and is greatly improved comparedwith the existing process.
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Paragraph 0051-0053
(2021/01/15)
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- A trans - menthyl - 2, 8 - diene -1 - alcohol synthesis process
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The invention belongs to the trans - menthyl - 2, 8 - diene - 1 - ol preparation technology field, in particular to a trans - menthyl - 2, 8 - diene - 1 - ol synthesis process. The synthesizing process comprises the following steps: (1) in order to limonene as raw materials, in order to lipase catalytic oxidation to obtain the 1, 2 - epoxy limonene; (2) the 1, 2 - epoxy limonene in the presence of sodium borohydride and diphenyl [...] open-loop formed limonene selenide; (3) the limonene selenide in under the action of the oxidizing agent forms the selenium oxide then undergo elimination reaction trans - menthyl - 2, 8 - diene - 1 - ol. The invention through the material and a prepared selective lipase catalyzed the situation that the 1, 2 - epoxy limonene, the need for complex purification process can increase the purity of the reaction intermediate, thereby improving the final product trans - menthyl - 2, 8 - diene - 1 - ol of chiral purity.
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- Activated vs. pyrolytic carbon as support matrix for chemical functionalization: Efficient heterogeneous non-heme Mn(II) catalysts for alkene oxidation with H2O2
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Two types of heterogeneous catalytic materials, MnII-L3imid@Cox and MnII-L3imid@PCox, have been synthesized and compared by covalent grafting of a catalytically active [MnII-L3imid] complex on the surface of an oxidized activated carbon (Cox) and an oxidized pyrolytic carbon from recycled-tire char (PCox). Both hybrids are non-porous bearing graphitic layers intermixed with disordered sp2/sp3 carbon units. Raman spectra show that (ID/IG)activatedcarbon > (ID/IG)pyrolyticcarbon revealing that oxidized activated carbon(Cox) is less graphitized than oxidized pyrolytic carbon (PCox). The MnII-L3imid@Cox and MnII-L3imid@PCox catalysts were evaluated for alkene oxidation with H2O2 in the presence of CH3COONH4. Both showed high selectivity towards epoxides and comparing the achieved yields and TONs, they appear equivalent. However, MnII-L3imid@PCox catalyst is kinetically faster than the MnII-L3imid@Cox (accomplishing the catalytic runs in 1.5 h vs. 5 h). Thus, despite the similarity in TONs MnII-L3imid@PCox achieved extremely higher TOFs vs. MnII-L3imid@Cox. Intriguingly, in terms of recyclability, MnII-L3imid@Cox could be reused for a 2th run showing a ~20% loss of its catalytic activity, while MnII-L3imid@PCox practically no recyclable. This phenomenon is discussed in a mechanistic context; interlinking oxidative destruction of the Mn-complex with high TOFs for MnII-L3imid@PCox, while the low-TOFs of MnII-L3imid@Cox are preventive for the oxidative destruction of the Mn-complex.
- Simaioforidou,Papastergiou,Margellou,Petrakis,Louloudi
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p. 516 - 525
(2016/12/16)
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- Oligomer-cannabinoid conjugates
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The invention relates to (among other things) oligomer-cannabinoid conjugates and related compounds. A conjugate of the invention, when administered by any of a number of administration routes, exhibits advantages over previously administered un-conjugated cannabinoid compounds.
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Page/Page column 43
(2015/11/09)
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- Continuous flow photooxygenation of monoterpenes
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Photooxygenation of monoterpenes was conducted in two continuous flow reactors. The first, suitable for lab-scale research, had a maximum yield of 99.9%, and the second, focused on industrial applications, showed a daily output that was 270.0-fold higher than that in batch systems. The use of sunlight instead of an LED lamp gave 68.28% conversion.
- Park, Chan Yi,Kim, Young Joon,Lim, Hyo Jin,Park, Jeong Hyeon,Kim, Mi Jin,Seo, Seung Woo,Park, Chan Pil
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p. 4233 - 4237
(2015/02/19)
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- Improved accessibility to the desoxy analogues of Δ9- tetrahydrocannabinol and cannabidiol
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Desoxy analogues of Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD) have been reported to provide a novel mode of analgesia whilst avoiding the psychotropic side effects associated with most cannabinoid drugs. A detailed and improved synthesis of desoxy THC, desoxy CBD and didesoxy CBD is reported here. The key improvements include a concentration-dependent boron trifluoride mediated electrophilic aromatic substitution which was used to synthesize both THC and CBD analogues. The synthetic route is general and could be applied to the development of a library of modified desoxy THC and desoxy CBD analogues.
- Wilkinson, Shane M.,Price, Jason,Kassiou, Michael
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supporting information
p. 52 - 54
(2013/02/22)
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- Influence of the Br?nsted and Lewis acid sites on the catalytic activity and selectivity of Fe/MCM-41 system
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The system Fe2O3/MCM-41, with high iron dispersion, was synthesized in order to introduce Lewis acid sites into the MCM-41 structure. Two calcination atmospheres (inert and oxidant) were used to produce iron nanoclusters with different structural properties. Besides, a silylation treatment was realized on both solids with the aim of neutralizing the Br?nsted acidity associated with the MCM-41 silanol groups. The samples were characterized by atomic absorption spectroscopy, X-ray diffraction at low angles, N2 adsorption, temperature-programmed reduction, Fourier transform infrared spectroscopy, nuclear magnetic resonance of 29Si, and M?ssbauer spectroscopy. The influence of the structural changes of the nanoclusters and the effect of the simultaneous presence of Lewis and Br?nsted acid sites were evaluated studying the product distribution from the α-pinene oxide isomerization reaction. It was determined that the Br?nsted acidity of the Fe/MCM-41 system has not the sufficient acid strength to modify the product distribution which is mainly governed by the Lewis sites.
- Fellenz,Bengoa,Marchetti,Gervasini
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scheme or table
p. 187 - 196
(2012/10/08)
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- Selective photosensitized oxidation and its catalytic regulation of monoterpene with molecular oxygen in different reaction media
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The photo-catalytic oxidation of α-pinene, β-pinene and limonene with molecular oxygen sensitized by tetrachlorotetraiodo-fluorescein sodium salt (RB) has been studied in different reaction media under green light irradiation. Simple and efficient photosensitized oxidation equipment was employed successfully to improve the efficiency of the photosensitized reaction. The results indicate that the photosensitized oxidation products can be directly obtained without after-treatment by reductive reagent. Furthermore, it was found that the product distributions are remarkably affected by reaction media, and that N,N-dimethylformamide (DMF) can regulate the selectivity to products. In particular, the good selectivity (85%) to the main product (myrtenal) and the excellent conversion (99%) were obtained in the absence of any other catalysts when DMF was used as reaction solvent in the photosensitized oxidation of β-pinene. Moreover, the possible photosensitized oxidation reaction mechanism in different media was suggested in the present work.
- You, Kuiyi,Yin, Dulin,Mao, Liqiu,Liu, Pingle,Luo, He'An
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experimental part
p. 321 - 325
(2011/10/13)
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- Exploring the substituent effects on a novel series of C1′-dimethyl-aryl Δ8-tetrahydrocannabinol analogs
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The synthesis and characterization of novel C1′-phenyl-substituted Δ8-THC analogs were previously reported by our laboratory. Within this small series of compounds, the C1′-dimethyl phenyl group was found to impart 13.5-fold selectivity for the CB2 receptor with a Ki 0.91 nM. The current study expands on the previous report by evaluating the effects of aromatic ring substitution on CB1 and CB2 receptor subtype binding and selectivity. The ring substituents synthesized in this study include aliphatic, halogen, nitrile, and acetamido functional groups. In addition, the isosteric replacement of the phenyl group by thiophene was evaluated. The anti-glioma activities of selected compounds were evaluated in vitro and compared to the lead compound 2.
- Krishnamurthy, Mathangi,Gurley, Steven,Moore II, Bob M.
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p. 6489 - 6500
(2008/12/21)
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- Abnormal Cannabidiols as agents for lowering intraocular pressure
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The present invention provides a method of treating glaucoma or ocular hypertension which comprises applying to the eye of a person in need thereof an amount sufficient to treat glaucoma or ocular hypertension of a compound of formula I wherein Y, Q, Z, R, R1 and R2 are as defined in the specification. The present invention further comprises pharmaceutical compositions, e.g. ophthalmic compositions, including said compound of formula I.
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Page/Page column 9
(2008/06/13)
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- Total synthesis of (+)-β-himachalene
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An enantioselective synthesis of (+)-β-himachalene (2) was accomplished starting from (1S,2R)-1,2-epoxy-p-menth-8-ene (3) in 15 or 16 steps with an overall yield of ca. 6% (Schemes 3, 5, and 6). Key transformations include an Ireland-Claisen rearrangement, a Corey oxidative cyclization, and a ring expansion.
- Ho, Tse-Lok,Chein, Rong-Jie
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p. 231 - 239
(2007/10/03)
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- Trypanocidal terpenoids from Laurus nobilis L.
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Trypanocidal constituents of dried leaves of Laurus nobilis L. (Lauraceae) were examined. Activity-guided fractionation of the methanol extract resulted in the isolation of two guaianolides, dehydrocostus lactone (1) and zaluzanin D (2), and a new p-menthane hydroperoxide, (1R,4S)-1-hydroperoxy-p-menth-2-en-8-ol acetate (3). The minimum lethal concentrations of these compounds against epimastigotes of Trypanosoma cruzi were 6.3, 2.5, and 1.4 μM, respectively.
- Uchiyama, Nahoko,Matsunaga, Keiji,Kiuchi, Fumiyuki,Honda, Gisho,Tsubouchi, Akiko,Nakajima-Shimada, Junko,Aoki, Takashi
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p. 1514 - 1516
(2007/10/03)
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- A Novel Cyclization of Geraniol and Nerol Initiated by Tris(p-bromophenyl)ammoniumyl Radical Cation
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Geraniol (1) and nerol (2) undergo a novel cyclization to cis-p-mentha-2,8-dien-1-ol (4) by reaction with tris(pbromophenyl)ammoniumyl radical cation (3) and the reaction mechanism is discussed.
- Wang, Wei,Liu, You-Cheng
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- A New Synthesis of (-)-Furodysin
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A synthesis of furodysin from trans-limonene oxide involves transformation into the phenylcarbamate of 2,8-menthadien-1-ol, allylic displacement with lithium di(β-furylmethyl)cuprate, and cyclization.
- Ho, Tse-Lok,Lee, Kwang-Yuan
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p. 947 - 948
(2007/10/02)
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- Synthetic Chemistry with Fullerenes. Photooxygenation of Olefins
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Under irradiation with visible or UV (>290 nm) light in the presence of molecular oxygen and a minute amount of fullerenes, olefins and dienes undergo ene and Diels-Alder reactions with singlet oxygen to give photooxygenation products.The regio- and stereoselectivities of the photooxygenation of β-myrcene, (+)-pulegone, 4-methylpent-3-en-2-ol, and (+)-limonene were very similar to those observed in known singlet oxygen reactions, indicating that the fullerene-sensitized reaction generates free singlet oxygen.The efficiency of fullerenes and conventional sensitizers was qualitatively examined by using the Diels-Alder reaction between 1O2 and furan-2-carboxylic acid as a probe.Among those examined, C70 was found to be the most effective.The reaction was the fastest and completed with as little as 0.0001 equiv of C70.C60 and hematoporphyrin were found to be of similar efficiency.The methanofullerene 13, which lacks one olefinic conjugation in the C60 core, was as good as C60 itself, but the aminofullerene 14, lacking six double bonds, was quite inferior.The fullerene carboxylic acid 15, which was previously shown to show considerable biochemical activity, was found to be capable of generating singlet oxygen in aqueous DMSO.
- Tokuyama, Hidetoshi,Nakamura, Eiichi
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p. 1135 - 1138
(2007/10/02)
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- Photosensitized Oxygenation of Olefins with Zinc Tetraphenylporphine-1,4-Diazabicyclooctane Complex
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In the presence of a proper amount of amines such as 1,4-diazabicyclooctane (DABCO) and piperidine, zinc tetraphenylporphine (ZnTPP) works as a not only apparently more effective but also more photoresistant sensitizer for singlet-oxygen oxygenation of olefins than in the absence of the amines.This is ascribed to the facts that ZnTPP forms a 1:1 complex with DABCO, and that DABCO coordinated to ZnTPP has no ability to quench singlet oxygen, as revealed by detection of singlet oxygen phosphorescence and product distributions in oxygenation of d-limonene, 1,2-dimethylcyclohexene, and 1-phenylcyclobutene.
- Sakuragi, Masako,Ichimura, Kunihiro,Sakuragi, Hirochika
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p. 1944 - 1949
(2007/10/02)
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- Process for the preparation of (+)-p-mentha-2,8-dien-1-ol
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Multistep process for preparing (+)-p-mentha-2,8-dien-1-ol from (+)-(R)-limonene. New compounds useful as intermediates in said process.
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- Stereoselective Cyclization assisted by the Selenyl Group. Biogenetic-type Synthesis in the p-Menthane Series
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Acid-catalysed cyclization of the β-hydroxyselenide (3), derived from linalyl acetate (1), afforded the trans-p-menthanes (4) and (5), the structures of which were confirmed by their transformation into (6), (11), (8), and (13), and alternative syntheses of these compounds.The structure determination of some products obtained by the reaction of limonene and α-terpineol epoxides with phenylselenium anion was also carried out.
- Kametani, Tetsuji,Kurobe, Hiroshi,Nemoto, Hideo
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p. 756 - 760
(2007/10/02)
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- Studies on the stereochemical course of selenium-assisted cyclisation: Biogenetic-type synthesis in the p-menthan series
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Acid-catalysed cyclisation of the β-hydroxy selenide (3) denved from linalyl acetate (1) afforded the trans-p-methans (4) and (5), the structures of which were confirmed by their transformation into (6), (8), (9), and (11) and by alternative synthesis of these compounds.
- Kametani, Tetsuji,Kurobe, Hiroshi,Nemoto, Hideo
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p. 762 - 763
(2007/10/02)
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