- METHOD FOR PRODUCING 3-METHYLCYCLOALKENONE COMPOUND
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The present invention relates to a method for producing a 3-methylcycloalkenone compound and a method for producing muscone. In the presence of a zirconium oxide catalyst, a diketone represented by the following general formula (1): wherein in formula (1), n represents 8, 9, 10, 11 or 12, is subjected to a vapor-phase intramolecular condensation reaction, whereby a 3-methylcycloalkenone compound can be produced with high reaction efficiency. When a 3-methylcyclopentadecenone compound produced by this method is hydrogenated in a known manner, muscone can be produced efficiently.
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- METHOD FOR CONVERTING HYDROXYL GROUP OF ALCOHOL
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The present invention relates to: a method for converting a hydroxyl group of an alcohol; and a catalyst which makes the method possible. A method for converting a hydroxyl group of an alcohol according to the present invention is characterized by producing a compound represented by CH(R1)(R2)Nu (wherein R1, R2 and Nu are as defined below) by reacting an alcohol represented by CH(R1)(R2)OH (wherein each of R1 and R2 represents a hydrogen atom, an optionally substituted alkyl group, or the like) and a compound having an active proton, which is represented by H-Nu (wherein Nu represents a group represented by —CHX1-EWG1 or —NR3R4; X1 represents a hydrogen atom or the like; EWG1 represents an electron-withdrawing group; and each of R3 and R4 represents a hydrogen atom, an optionally substituted alkyl group, or the like), with each other in the presence of a complex of a group 7-11 metal of the periodic table and at least one solid base that is selected from the group consisting of layered double hydroxides, composite oxides and calcium hydroxide.
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Paragraph 0316-0330; 0352-0355; 0482-0488
(2021/02/19)
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- Highly productive α-alkylation of ketones with alcohols mediated by an Ir-oxalamidato/solid base catalyst system
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An Ir-oxalamidato complex in combination with a solid base (e.g., magnesium aluminometasilicate/Ca(OH)2) significantly improved the catalyst productivity in α-alkylation of methyl ketones with primary alcohols. Optimization through systematic variation of the oxalamidato ligand led to a practical turnover number (TON) of 10 000.40 000.
- Maeda, Hironori,Nara, Hideki,Shimizu, Hideo
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supporting information
p. 2772 - 2779
(2020/12/29)
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- 2, 15 - 3 - And production of purification of hexadecane dione [...]
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2, 15 - Hexadecane dione [to] with high yield, high-purity purification method for purifying 2, 15 - hexadecane dione, moreover, 3 - [...] allyl, high yield production of 3 - can be [...]. The present invention is method for purifying 2, 15 - [solution] hexadecane dione, acetoacetic ester is reacted with an alkali metal salt of 1, 10 - [...] then, sulfuric acid produced by the method of purification of 2, 15 - hexadecane dione decarboxylation, 1.0 mass % or less at a rate of 10.0% by mass including water, methanol and water by using a mixed solvent, wherein 2, 15 - hexadecane dione characterized by recrystallizing. [Drawing] no
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Paragraph 0135-0142
(2019/10/11)
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- METHOD FOR PRODUCING ALKALI SALT OF ACETOACETIC ESTER AND METHOD FOR PRODUCING ALIPHATIC DIKETONE
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PROBLEM TO BE SOLVED: To provide a method for producing an alkali salt of acetoacetic ester that can produce an alkali salt of acetoacetic ester in a high yield. SOLUTION: In producing an alkali salt of acetoacetic ester represented by the formula of (CH3COCHCOOR)-M+, provided that in the formula, R is a methyl group or an ethyl group; and M is sodium or potassium, firstly a nonprotonic organic solvent optionally miscible with water and an acetoacetic ester are mixed. In a state the nonprotonic organic solvent and the acetoacetic ester being mixed, an alkali hydroxide compound is added and reacted. As the nonprotonic organic solvent optionally miscible with water, at least one kind of acetone, tetrahydrofuran and acetonitrile is preferably used. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0070-0083
(2018/08/09)
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- Synthesis method of long-chain diketone
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The invention discloses a synthesis method of long-chain diketone. The method comprises the following steps: by taking alpha, omega-diol as an alkylating agent, under the catalysis of a metal carriedby a carrier and a metal oxide, alkylating acetone, thus obtaining a long-chain diketone product. According to the synthesis method, a ruthenium-sodium oxide catalyst carried by silicon oxide is used,and the catalyst also has the catalytic activities such as dehydrogenation, aldol condensation and hydrogenization, so that the synthesis of the diketone is realized by one step; no extra alkali is added into the system; the catalyst is high in activity and can be recycled and reused. Compared with a known synthesis method, the synthesis method disclosed by the invention is simple and efficient in reaction by taking the alpha, omega-diol and the acetone which are low in cost as starting raw materials, and only water which is a byproduct is produced, so that the synthesis method is economical,environmentally friendly and suitable for scale-up synthesis of the long-chain diketone.
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Paragraph 0049; 0050; 0051; 0052; 0053; 0054-0058
(2018/05/16)
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- METHOD FOR PRODUCING 3-METHYL CYCLOPENTADECENONES
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PROBLEM TO BE SOLVED: To provide a method for producing 3-methyl cyclopentadecenones in which the 3-methyl cyclopentadecenones can efficiently be produced. SOLUTION: The 3-methylcyclopentadecenones is produced by an intramolecular condensation reaction of 2,15-hexadecanedione represented by the chemical formula of CH3CO(CH2)12 COCH3. And, in the intramolecular condensation reaction, by using a catalyst having a BET specific surface area of 10 m2/g or less, a decrease in yield due to an increase of the intermolecular condensation reaction on the catalyst can be suppressed as well as, because the deterioration of catalyst can be suppressed, 3-methylcyclopentadecenones can efficiently be produced by the intramolecular condensation reaction. Further, the catalyst is preferably at least one of magnesium oxide, calcium oxide and zinc oxide. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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- RUBBER COMPOSITION, TIRE, AMINE COMPOUND, AND ANTI-AGING AGENT
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Provided is a rubber composition that has better weather resistance than conventional rubber compositions and can inhibit surface discoloration of a rubber article. The rubber composition contains at least one rubber component selected from natural rubber and diene-based synthetic rubbers and, blended therewith, at least one amine compound represented by formula (I) shown below. In formula (I), R1 and R2 each represent, independently of one another, an alkyl group having a carbon number of 1-10, an aralkyl group, or a phenyl group, and A represents an alkylene group having a carbon number of 6-30 that may include an interposed phenylene group.
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Paragraph 0123
(2017/07/06)
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- PROCESS FOR PRODUCTION OF 3-METHYL-CYCLOPENTADECENONE, PROCESS FOR PRODUCTION OF R/S-MUSCONE, AND PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE MUSCONE
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By intramolecular condensation reaction of 2,15-hexadecanedione in a gaseous phase with a compound of a Group II element of the Periodic Table as a catalyst, 3-methyl-cyclopentadecenones is generated. Magnesium oxide, calcium oxide, or zinc oxide is desirable as the catalyst for the intramolecular condensation reaction. (R)- and (S)-muscone is generated by subjecting 3-methyl-cyclopentadecenones obtained as above to hydrogenation by using a catalyst. Palladium catalyst is desirable as the hydrogenation catalyst. Optically active muscone is generated by separating 3-methyl-cyclopentadecenones into respective components thereof by means of precision distillation and subsequently subjecting the separated 3-methyl-cyclopentadecenones to asymmetric hydrogenation by using an optically active ruthenium complex catalyst. The production methods described above enable easy and economical production of 3-methyl-cyclopentadecenones, (R)-and (S)-muscone, and optically active muscone.
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- METHOD FOR PRODUCING 3-METHYL-CYCLOPENTADECENONES, METHOD FOR PRODUCING (R)- AND (S)- MUSCONE, AND METHOD FOR PRODUCING OPTICALLY ACTIVE MUSCONE
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By intramolecular condensation reaction of 2,15-hexadecanedione in a gaseous phase with a compound of a Group II element of the Periodic Table as a catalyst, 3-methyl-cyclopentadecenones is generated. Magnesium oxide, calcium oxide, or zinc oxide is desirable as the catalyst for the intramolecular condensation reaction. (R)- and (S)-muscone is generated by subjecting 3-methyl-cyclopentadecenones obtained as above to hydrogenation by using a catalyst. Palladium catalyst is desirable as the hydrogenation catalyst. Optically active muscone is generated by separating 3-methyl-cyclopentadecenones into respective components thereof by means of precision distillation and subsequently subjecting the separated 3-methyl-cyclopentadecenones to asymmetric hydrogenation by using an optically active ruthenium complex catalyst. The production methods described above enable easy and economical production of 3-methyl-cyclopentadecenones, (R)- and (S)-muscone, and optically active muscone.
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Page/Page column 5
(2011/08/03)
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- A practical synthesis of (rac)-muscone and (R)-(-)-muscone
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A practical synthesis of (rac)-muscone in three steps is described, using commercially available 1,10-dibromodecane as the starting material. In the first step, an aldol reaction of 1,10-dibromodecane with ethyl acetoacetate affords the important intermediate 2,15-hexadecanedione in 70% yield. A cyclisation reaction in the second step aided by propyl zinc iodide gives dehydro-muscone in 84% yield. Hydrogenation of dehydro-muscone with Pd-C completes the synthesis of (rac)-muscone. Furthermore, (R)-(-)-muscone is enantioselectively prepared via the formation of a ketal intermediate from dehydro-muscone and 1,4-di-O-benzyl-D-threitol.
- Cheng, Chuanjie,Ding, Wei,Ding, Shaomin
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experimental part
p. 195 - 197
(2011/07/30)
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- Synthesis of ω-hydroxy carboxylic acids and α,ωdimethyl ketones using α,ω-diols as alkylating agents
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"Chemical equation presented" Synthesis of ω-hydroxy carboxylic acids and α,ω-dimethyl diketones was successfully achieved by using α,ω-diols as alkylating agents under the influence of an iridium catalyst. For example, the alkylation of butyl cyanoacetate with 1,13-tridecanediol in the presence of [IrCl(cod)]2 or [rrCl(coe) 2]2 gave rise to butyl 2-cyano-15-hydroxypentadecanoate in good yield which is easily converted to cyclopentadecanolide (CPDL). In addition, the alkylation of acetone with 1,10-decanediol in the presence of [IrCl(cod)]2 and KOH resulted in an important muscone precursor, 2,15-hexadecanedione (HDDO), in good yield.
- Iuchi, Yosuke,Hyotanishi, Megumi,Miller, Brittany E.,Maeda, Kensaku,Obora, Yasushi,Ishii, Yasutaka
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experimental part
p. 1803 - 1806
(2010/05/17)
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- OPTICALLY ACTIVE MUSCONE COMPOSITION AND FRAGRANCES OR COSMETICS CONTAINING THE SAME
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(Problem) The object of the invention relates to a development of a new musk-feeling fragrance material which is a highly scenting musk-feeling fragrance, and is to provide a fragrance composition which, when added to fragrances or cosmetics, can improve the fixative property and express a high performance and excellent musky aromatic quality. (Means for Resolution) A fragrance composition is prepared using, as the active ingredient, a mixture of (R)-form of optically active muscone with (S)-form of optically active muscone with the mixing ratio thereof within the range of from 90:10 to 95:5 (weight ratio) in terms of weight ratio, or a mixture of (R)-form of optically active muscone with (S)-form of optically active muscone with the mixing ratio thereof within the range of from 75:25 to 80:20 (weight ratio) in terms of weight ratio.
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- Synthesis of new heterocycles containing more than one 1,2,3-thia or selenadiazole rings
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(Chemical Equation Presented) The diketones 2a-d with different alkyl chain length are used for the synthesis of di-1,2,3-thia or selenadiazole derivatives 4a-d and 5a-d. The diketones 2a-d where prepared by a unique method through the reaction between the corresponding dibromoalkanes 1a-d and ethyl acetoacetate, which are transformed into the corresponding semicarbazone derivatives 3a-d. The di-1,2,3-thia or selenadiazole derivatives 4a-d and 5a-d were prepared from the semicarbazones derivatives 3a-d on oxidative cyclization with thionyl chloride and selenium dioxide respectively in high yield.
- Al-Smadi, Mousa
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p. 915 - 918
(2008/04/05)
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- METHOD FOR THE PRODUCTION OF 1.7-OCTADIENE AND USE THEREOF
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The invention relates to a method for the production of 1.7 octadiene by reacting metathesis of cyclohexene with ethylene. The invention also relates to the production of 1.10-decandiol by hydroformulating 1.7 octadiene produced according to said method. The invention further relates to a method for the production of muscone or olefinically unsaturated analogs thereof using 1.10 decandiol which is obtainable in said manner.
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Page/Page column 74-75
(2010/02/11)
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- Direct, practical, and powerful crossed aldol additions between ketones and ketones or aldehydes utilizing environmentally benign TiCl4-Bu3N reagent
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An efficient TiCl4-Bu3N - (cat. TMSCl)-promoted aldol addition between ketones and ketones or aldehydes was performed. This environmentally benign method is advantageous from a green chemical viewpoint with regard to yield, substrate
- Tanabe, Yoo,Matsumoto, Noriaki,Higashi, Takahiro,Misaki, Tomonori,Itoh, Tomotaka,Yamamoto, Misako,Mitarai, Kumi,Nishii, Yoshinori
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p. 8269 - 8280
(2007/10/03)
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- A novel synthetic method for (R)- and (S)-muscones by enantioselective hydrogenation of (E)- and (Z)-3-methyl-2-cyclopentadecen-1-ones catalyzed by p-tolyl-BINAP-Ru(II) complexes
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A novel and practical synthesis of (R)- and (S)-muscones by the asymmetric hydrogenation of (E)- and (Z)-3-methyl-2-cyclopentadecen-1-ones catalyzed by p-tolyl-BINAP-Ru(II) complexes has been achieved in nearly complete enantioselectivity.
- Yamamoto, Takeshi,Ogura, Miharu,Kanisawa, Tsuneyoshi
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p. 9209 - 9212
(2007/10/03)
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- Synthesis of 2,15-hexadecanedione as a precursor of muscone
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Muscone is a precious fragrant compound, which is scarce in nature, many synthetic attempts for this unique natural product have been carried out. A new synthetic method for 2,15-hexadecanedione, a precursor of muscone, from imidazalium salt and di-Grignard reagent is reported. Imidazalium salt was used as tetrahydrofolate coenzyme model at formic acid oxidation level and di-Grignard reagent as nucleophile to which one-carbon unit was transferred, the biomimetic synthesis of 2,15-hexadecanedione was successfully accomplished by using the addition-hydrolysis reaction of imidazolium salt with di-Grignard reagent. A novel method for preparing muscone is provided.
- Bai,Lu,Shi,Yang
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p. 544 - 546
(2007/10/03)
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- Intercalation of multiple carbon atoms between the carbonyls of α-diketones
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The reaction of open-chain or cyclic α-diketones with specific ω-alkenyl organometallics leads readily under the proper conditions to 1,2-diols bonded to terminal olefinic chains. With 1-phenyl-1,2-propanedione, biacetyl, and cyclohexane-1,2-dione, allylindation in aqueous THF proceeds readily at both adjacent carbonyls. For cyclododecane-1,2-dione, recourse must be made to allylmagnesium bromide for completing the second-stage condensation. Grignard reagents have also served well as reactants for biacetyl monoadducts. In contrast, monoallylated camphorquinone is reluctant to couple to Grignard reagents and reacts only when Barbier-type alkyllithium reactions are applied. The ring closing metatheses of these products have been examined. Where six-membered ring formation operates, cyclization can be performed directly on diols. When larger rings are involved, the diols will react only if structural preorganization capable of facilitating mutual approach of the two double bonds is at play. For this purpose, the prior conversion to a cyclic carbonate holds considerable utility. In the latter setting, saponification must precede the diol cleavage step which has been performed with lead tetraacetate. The latter reagent also exhibits the very beneficial effect of facilitating removal of ruthenium and phosphorus byproducts generated during the metathesis step. This chemistry conveniently lends itself to the controlled intercalation of multiple methylene groups between the carbonyl carbons of readily available α-diketones to deliver linear or cyclic products.
- Balskus,Mendez-Andino,Arbit,Paquette
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p. 6695 - 6704
(2007/10/03)
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- cis/trans-Ozonides of Cycloolefins
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Ozonolyses in pentane of the unsubstituted cycloolefins having eleven-, twelve-, fourteen- and sixteen-membered rings (1b-e) and of cyclohexadecen-8-one (12) gave the corresponding cis- (2b-e; cis-15a) and trans-ozonides (3b-e; trans-15a), whereas cyclodecene (1a) gave only the corresponding cis-ozonide (2a).Ozonolyses on polyethylene of the dimethyl-substituted cycloolefins bearing fourteen- and sixteen-membered rings (7b,c) also afforded cis- and trans-isomeric ozonides (8, 9), whereas from the twelve-membered ring (7a) only the corresponding cis-ozonide (8a) was formed. - Keywords: Ozonides; Cycloolefins
- Griesbaum, Karl,Ball, Volker,Beck, Johannes,McCullough, Kevin
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p. 1993 - 2000
(2007/10/03)
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- Acylation of unsaturated halides, alcohols, esters and ketones
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Treatment of the title compounds with acyl halide and Lewis acid affords unsaturated ketones (mainly α-β with aluminium chloride, selectively β-γ with silver tetrafluoroborate). Reduction of the alkenyl group gives polyfunctional ketones.
- Barbry,Faven,Ajana
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p. 2647 - 2658
(2007/10/02)
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- One-step synthesis of 1,n-dicarbonyl compounds from carboxylic acid derivatives and di-Grignard reagents in the presence of transition metal catalysts
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The transition metal catalyzed cross-coupling reaction of alkane di-Grignard reagents with carboxylic acid derivatives provides a convenient one-step synthesis of symmetrical 1,n-diketones (n8) and long-chain dicarboxylic thiol esters.
- Babudri, F.,D'Ettole, A.,Fiandanese, V.,Marchese, G.,Naso, F.
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- A Convenient Synthesis of Diketones via Alkylation of Alkyl Methyl Ketone Dimethylhydrazones
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Symmetrical diketones were prepared by the reaction of the lithium salts of alkyl methyl metone dimethylhydrazones with dibromoalkanes.
- Yamashita, Masakazu,Matsumiya, Kaoru,Morimoto, Hiroko,Suemitsu, Rikisaku
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p. 1668 - 1670
(2007/10/02)
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- Synthesis and Application of Imidazole Derivatives: Preparation of Various Diketones from 1,n-Bis(1-methyl-1H-imidazol-2-yl)alkane-1,n-diones
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Reaction of 1,n-bis(1-methyl-1H-imidazol-2-yl)alkane-1,n-dione (8) with an excess of Grignard reagent was examined.In the cases of n = 4 and 5, precursors (14) for synthesis of various asymmtric 1,4- and 1,5-diketones (12: R1 R2), respectively, were obtained in good yields by treating 8 with an excess of methylmagnesium iodide in ether followed by trimethylsilylation.In the case of n >/= 8, the two carbonyl groups of 8 were both attacked by the Grignard reagent, and the products (11: R1=R2=CH3) were convertible to symmetrical diketones (12: R1=R2=CH3) in good yields.In cases of n = 6 and 7, the mode of the Grignard reaction was transitional between the two types.Keywords - 2-acyl-1H-imidazole; 1,n-bis(1-methyl-1H-imidazol-2-yl)-1,n-alkanedione; diketone synthesis; asymmetric diketone; symmetric diketone; Grignard reaction; dihydrojasmone; cis-jasmone; muscone; 2-(1-hydroxy-1-alkyl)-1-methyl-1H-imidazole
- Hayakawa, Satoshi,Baba, Junko,Okamoto, Masao,Ohta, Shunsaku
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- SYNTHESES OF DIKETONIC INTERMEDIATES FOR THE TOTAL SYNTHESES OF DIHYDROJASMONE, cis-JASMONE AND dl-MUSCONE STARTING FROM 1,n-DI(1-METHYL-1H-IMIDAZOL-2-YL)-1,n-ALKANEDIONE
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2,15-Dihydroxy-2,15-di(1-methyl-1H-imidazol-2-yl)hexadecane (3) was obtained by treating 1,14-(1-methyl-1H-imidazol-2-yl)-1,14-tetradecadione (2b) with an excess of CH3MgI, while 1,4-di(1-methyl-1H-imidazol-2-yl)-4-trimethylsilyloxy-2-pentanone (6; R1 = TMS) was obtained by the similar treatment of 1,4-(1-methyl-1H-imidazol-2-yl)-1,4-butadione (2a) followed by trimethylsilylation.These products (3 and 6) were convertible into the known diketonic intermediates for the synthesis of dl-muscone, dihydrojasmone and cis-jasmone.
- Ohta, Shunsaku,Hayakawa, Satoshi,Tamai, Yoshimi,Yuasa, Teruyuki,Okamoto, Masao
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p. 141 - 146
(2007/10/02)
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- CHEMISTRY OF ORGANOSILICON COMPOUNDS CLXXXVIII. REACTION OF ORGANODISILANES WITH DIENES CATALYZED BY TRANSITION METAL COMPLEXES. PREPARATION OF 1,8-BIS(TRIMETHYLSILYL)OCTA-2,6-DIENE AND ITS USE IN THE SYNTHESIS OF dl-MUSCONE
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Organodisilanes, Me3-nXnSiSiXnMe3-n (X = Cl and MeO, n = 0, 1, 2) undergo efficient 1:2 addition reactions with butadiene and isoprene in the presence of a catalytic amount of a suitable palladium complex.One of the products, the title compound, was used as a starting material for a short synthesis of dl-muscone.
- Sakurai, Hideki,Eriyama, Yuichi,Kamiyama, Yoshiyasu,Nakadaira, Yasuhiro
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p. 229 - 238
(2007/10/02)
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- One-step Synthesis of Long-chain Aliphatic α,ω-Dicarboxylic Acids Utilizing the Copper-catalyzed Reaction of β-Propiolactone with α,ω-Di-Grignard Reagents
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Copper-catalyzed reaction of β-propiolactone with α,ω-di-Grignard reagents, followed by esterification gave six-carbon homologated α,ω-dicarboxylic acid esters in good yields.
- Fujisawa, Tamotsu,Sato, Toshio,Kawara, Tatsuo,Tago, Hideyuki
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p. 345 - 346
(2007/10/02)
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