- Method for preparing hinokitiol
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The invention discloses a method for preparing hinokitiol. The method includes the steps of conducting an addition reaction on bromoform and an initial raw material compound, namely cyclohexene, to obtain a first compound, namely 7,7-dibromo bicyclo[4.1.0]heptane; the first compound is subjected to an oxidization reaction to obtain a second compound, namely 3,7,7-tribromo bicyclo[4.1.0]heptyl-2-ketone; the second compound is subjected to a substitution reaction to obtain a third compound, namely 7,7-dibromo-3-hydroxy bicyclo[4.1.0] heptyl-3-alkene-2-ketone; the third compound is subjected to aring enlargement reaction to obtain a fourth compound, namely 4-bromo-2-hydroxy cycloheptyl-2,4,6-triene-1-ketone; the fourth compound is subjected to an alkylation reaction to obtain hinokitiol.
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- Preparation method of beta-thujaplicine
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The invention belongs to the technical field of drug synthesis, and particularly relates to a preparation method of beta-thujaplicine. The preparation method comprises the steps that tri-n-propylamine, glacial acetic acid and water serve as reaction reagents, and a ring enlargement reaction occurs by 7,7-dichloro-3-isopropylbicycle[3.2.0]heptyl-2-ene-6-one (the compound structure is shown in formula 2).
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Paragraph 0028; 0029; 0030; 0031; 0032; 0035; 0036
(2018/11/03)
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- Method for preparing high-purity hinokitiol and coordination complex thereof
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The invention belongs to the technical field of synthesis of pharmaceutical intermediates, and relates to a method for preparing high-purity hinokitiol and a coordination complex thereof. The method comprises the steps that 1-perchlorocyclopentadiene is generated by using cyclopentadiene, sodium hydroxide and NCS and reacts with dichloracetyl chloride, barium hydroxide is added, dilute sulphuric acid and chloroform are added after the reaction, and 1-chloro cyclopentadiene 4,4-dichloro cyclobutyl5-ketone is obtained through a final reaction; 1-chloro cyclopentadiene 4,4-dichloro cyclobutyl5-ketone is mixed with a mixed solution of acetic acid, acetone and water, then barium hydroxide is added, and 2-hydroxyl-4-chloro-2,4,6-cycloheptatrien-1-ketone is obtained through a final reaction; 2-hydroxyl-4-chloro-2,4,6-cycloheptatrien-1-ketone is added to THF, potassium phosphate and isopropylboronic acid are added, and the mixture after the reaction is added to a mixed solution of methanol, HCl/1 and 4-dioxane to obtain hinokitiol at last. The method has the advantages that the process is simple, the cost is low, and the product purity is high.
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- A high-purity chinese juniper methyl alcohol of preparation method (by machine translation)
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The invention discloses a method for preparing high-purity chinese juniper methyl alcohol, cyclopentadiene activated reagent after activation with isopropyl bromine instead should be containing various isomers of the isopropyl cyclopentadiene, then in the isomer conversion catalyst under the action of the isomerization reaction to obtain 1 - isopropyl cyclopentadiene; 1 - isopropyl cyclopentadiene and [...] react 1 - isopropyl cyclopentadiene and 4, 4 - [...] 5 - one; 1 - isopropyl cyclopentadiene and 4, 4 - [...] 5 - ketone with triethylamine heating reflux generating ring enlargement reaction to obtain the target product chinese juniper methyl alcohol. The invention raw materials used are cheap and easily obtained, and the step A through the isomer of a hydrocarbon conversion catalyst in use significantly reduces the by-product 2 - isopropyl cyclopentadiene and 5 - isopropyl cyclopentadiene generation, improves the yield of products, and Ru (Ac)3 - ZSM - 5 can be repeatedly used for four times still maintains good catalytic activity; step B by adjusting reaction solution in glacial acetic acid, effectively prevent the emergence of the diketone by-product. (by machine translation)
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- SUBSTITUTED TROPOLONE DERIVATIVES AND METHODS OF USE
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The compositions and methods described herein relate generally to substituted tropolone derivatives, which, among other features, are useful as histone deacetylase (HDAC) inhibitors.
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Page/Page column 21-23
(2014/01/09)
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- The furan route to tropolones: Probing the antiproliferative effects of β-thujaplicin analogs
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A direct route to analogs of the naturally occurring tropolone β-thujaplicin has been developed in just four steps from furan. Using this method, a series of derivatives were synthesized and evaluated. Several of these compounds demonstrated very high levels of potency against bacterial and fungal pathogens with good selectivity over mammalian cells.
- Zachary Oblak,Bolstad, Erin S. D.,Ononye, Sophia N.,Priestley, Nigel D.,Kyle Hadden,Wright, Dennis L.
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p. 8597 - 8604
(2013/01/15)
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- Regioselective synthesis of β- and γ-thujaplicins
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β-Thujaplicin (hinokitiol) 1 and γ-thujaplicin 2, as the first naturally occurring monocyclic tropolone, were regioselectively synthesized from (R)-(+)-limonene, by using different dienyl silyl ether intermediates, 7 and 10, in 18% overall yield via 11 steps and 22% overall yield via 10 steps, respectively. (C) 2000 Elsevier Science Ltd.
- Soung, Min-Gyu,Matsui, Masanao,Kitahara, Takeshi
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p. 7741 - 7745
(2007/10/03)
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- Stereo- and regiocontrolled hydroxylation of oxyallyl [4+3] cycloadducts. A concise synthesis of hinokitiol
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Stereo- and regioselective hydroxylation of 8-oxabicyclo[3.2.1]oct-6-en-3-ones was achieved by the action of (diacetoxyiodo)benzene in methanolic potassium hydroxide (the Moriarty oxidation). Subsequent double elimination afforded a convenient preparation of substituted tropolones, as exemplified in a three-step synthesis of hinokitiol (1).
- Lee, Jae Chol,Cho, Sung Yun,Cha, Jin Kun
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p. 7675 - 7678
(2007/10/03)
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- The Palladium-Mediated Cross Coupling of Bromotropolones with Organostannanes or Arylboronic Acids: Applications to the Synthesis of Natural Products and Natural Product Analogues
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The bromotropolones (4), (5) and (10) undergo palladium-mediated cross coupling with a wide range of organostannanes to produce alkenyl-, alkyl- and aryl-substituted tropolones.The methodology has been applied to the synthesis of the monoterpenes β-dolabrin (11), β-thujaplicin (12), 4-isopropyl-7-methoxytropolone (13) and β-thujaplicinol (14).Cross coupling of bromotropolones (4), (5) and (10) with various aryltrimethylstannanes or arylboronic acids has permitted the preparation of the bicyclic colchicine analogues (30)-(43) which have been tested for tubulin-binding activity.The X-ray crystal structure of the most active of these systems, compound (38), is reported.
- Banwell, Martin G.,Cameron, Jennifer M.,Collis, Maree P.,Crisp, Geoffrey T.,Gable, Robert W.,'et al.
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p. 705 - 728
(2007/10/02)
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- The Palladium-mediated Cross-coupling of Bromotropolones with Organostannanes; Application to Concise Syntheses of β-Dolabrin, β-Thujaplicin, 7-Methoxy-4-isopropyltropolone, and β-Thujaplicinol
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The bromotropolones (1), (2), and (3) cross-couple with organostannanes in the presence of palladium(O) to produce alkyl, alkenyl, or aryl substituted tropolones; the methodology has been applied to the synthesis of the monoterpenes β-dolabrin (4), β-thujaplicin (5), 7-methoxy-4-isopropyltropolone (7), and β-thujaplicinol (8).
- Banwell, Martin G.,Collis, Maree P.,Crisp, Geoffrey T.,Lambert, John N.,Reum, Monica E.,Scoble, Judith A.
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p. 616 - 617
(2007/10/02)
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- NATURAL PRODUCT SYNTHESIS VIA THE POLYBROMO KETONE-IRON CARBONYL REACTION
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Application of the polybromo ketone-iron carbonyl reaction to natural product synthesis is summarized.The general synthesis of tropane alkaloids has been achieved via the reductive cyclocoupling of sym-tetrabromoacetone with N-methoxycarbonylpyrrole as the key step.Ready availability of 8-oxabicyclooct-6-en-3-one from the tetrabromoacetone and furan has opened a new, efficient entry to natural C-nucleosides including pseudouridine, pseudocytidine, and showdomycin.The artificial analogues such as 2-thiopseudouridine, 6-azapseudouridine, pseudoisocytidine, etc., are also obtainable.The oxabicyclic ketones bearing an isopropyl substituent at the appropriate position serve as intermediates for the synthesis of naturally occurring troponoids, nezukone, α-thujaplicin, and hinokitiol (β-thujaplicin).Carbocamphenilone and camphenic acid have been prepared through the reaction of 1,1,3-tribromo-3-methylbutan-2-one and cyclopentadiene.The cyclocondensation of α,α'-dibromo ketone and a styrene derivative leads to the single-step synthesis of α-cuparenone. 1,3-Dibromo-3,7-dimethyloct-6-en-2-one derived from nerol (or geraniol) undergoes the biogenetic-type double cyclization.The iron carbonyl-assisted intramolecular cyclocoupling gives camphor accompanied by other monoterpenic ketones.A mixture of campherenone and epicampherenone has been obtained from related dibromo ketone prepared from farnesols.The hetero reaction by use of dibromo ketones and N,N-dimethylcarboxamides, forming 3 (2H)-furanones, is employable for the preparation of muscarine alkaloid derivatives.
- Noyori, R.,Hayakawa, Y.
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p. 5879 - 5886
(2007/10/02)
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- A VERSATILE NEW STRATEGY FOR THE SYNTHESIS OF TROPOLONES
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Swern-type oxidation of various 7-halogenobicycloheptane-2,3- or -3,4-diols affords the corresponding bicyclic diketones which undergo in situ ring expansion and loss of hydrogen halide to give α-tropolones in high yield.The quantitative conversion of the isolable 1,4-diketone 26 into the γ-tropolone acetate 27 has been achieved.
- Banwell, Martin G.,Onrust, Rene
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p. 4543 - 4546
(2007/10/02)
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- Stereospecific trans-elimination of 2-alkoxy- and 2-cycloalkoxytropones to alkenes and cycloalkenes
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The title compounds undergo thermal fragmentation to tropolones and alkenes and cycloalkenes.Product distribution and kinetic analyses of specifically labelled deuterio compounds establish the process to be a concerted electrocyclic reaction.
- Takeshita, Hitoshi,Mametsuka, Hiroaki
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p. 2035 - 2040
(2007/10/02)
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- Dissociation of μ-Oxo-bis and μ-Oxo-bis in Chlorobenzene
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Dissociation of dimeric vanadium(V) complexes with 8-quinolinol(Hox) and 4-isopropyltropolone(Hipt), V2O3(ox)4 and V2O3(ipt)4, in organic solvents was studied spectrophotometrically.The equilibrium is found to be V2O3L4 + H2O 2VO2L + 2HL with the foll
- Yuchi, Akio,Muranaka, Hiroshi,Yamada, Shinkichi,Tanaka, Motoharu
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p. 1560 - 1563
(2007/10/02)
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