- Preparation method of dicyclopropane derivative compound
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The invention provides a preparation method of a dicyclopropane derivative compound, and particularly relates to a preparation method of (1-methyl-2-((1,2,2-trimethylbicyclo[3.1.0]hex-3-yl) methyl)cyclopropyl)methanol. The preparation method comprises the following steps: S1) mixing metal zinc, metal copper or salts thereof, halogenated acylate, acidic resin and a solvent, and carrying out an activation reaction to obtain an activated reaction solution; S2) alternately dropwise adding sandalwood 194 and dihalomethane into the activated reaction solution respectively, and after dropwise adding is completed, carrying out constant-temperature reaction on the system; S3) performing acidolysis on the system after the constant-temperature reaction, filtering to obtain an organic phase, combining the organic phase with liquid caustic soda, washing, and layering to obtain an organic phase containing a reaction product on the upper layer; and S4) carrying out rectification on the organic phase containing the reaction product to obtain (1-methyl-2-((1,2,2-trimethylbicyclo[3.1.0]hex-3-yl) methyl)cyclopropyl)methanol.
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Paragraph 0052-0064
(2021/06/09)
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- Biomass- And calcium carbide-based recyclable polymers
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Biomass is a renewable source of valuable feedstock for the chemical industry of the future. A promising approach to the utilization of valuable components of biomass is the synthesis of monomers and polymers, if the overall technology is designed for a clean cycle without pollution of the environment with newly created polymers. In this work, we have developed a methodology for the recycling of polymers based on biomass and calcium carbide. First, we modified a series of biomass-derived terpene alcohols with calcium carbide followed by polymerization of the isolated vinyl ethers. Then, to study the recycling potential, the obtained polymers were subjected to pyrolysis at moderate temperatures (200-450 °C). The pyrolysis products were analyzed using TGA-MS, GC-MS, and NMR, and it was found that the polymers can be transformed quite easily. The products of the pyrolysis consisted of the starting terpenols, as well as the corresponding non-toxic ketones or aldehydes: up to 87% of the starting alcohol or up to 100% of the total sum of alcohol + aldehyde or alcohol + ketone (GC-yields). Then, the reaction mixture was hydrogenated and resulted in the formation of starting alcohol only. According to the studied pathway of polymers re-building, a terpene fragment attached to the main polyethylene chain through an oxygen atom promotes the transformation of the obtained polymers. Thus, the products of pyrolysis are environmentally friendly and can be reused in the further synthesis of monomers. The developed system has shown a unique assembling/disassembling ability and advances the concept of reusable bio-derived high value-added materials.
- Metlyaeva, Svetlana A.,Rodygin, Konstantin S.,Lotsman, Kristina A.,Samoylenko, Dmitriy E.,Ananikov, Valentine P.
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p. 2487 - 2495
(2021/04/07)
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- CYCLOPROPANATION OF SUBSTITUTED ALKENES
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Disclosed is a cyclopropanation process comprising the step of reacting an alkene compound having at least one carbon-carbon double bond with at least one dihaloalkane. The reaction is carried out in the presence of (i) particulate metal Zn, (ii) catalytically effective amount of particulate metal Cu or a salt thereof, (iii) at least one haloalkylsilane, and (iv) at least one solvent.
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Paragraph 0068
(2019/06/20)
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- CYCLOPROPANATION OF SUBSTITUTED ALKENES
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Disclosed is a cyclopropanation process comprising the step of reacting an alkene compound having at least one carbon-carbon double bond with at least one dihaloalkane. The reaction is carried out in the presence of (i) particulate metal Zn, (ii) catalytically effective amount of particulate metal Cu or a salt thereof, (iii) at least one haloalkylsilane, and (iv) at least one solvent.
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Page/Page column 10-11; 12
(2017/02/28)
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- Transition-metal-catalyzed cyclopropanation of nonactivated alkenes in dibromomethane with triisobutylaluminum
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The cyclopropanation of nonactivated alkenes with inexpensive triisobutylaluminum (TIBA), in dibromomethane as solvent and reagent, is efficiently catalyzed by FeCl3 at ambient temperature. Catalytic amounts of CuI salts, CpTiCl3, and [CpFe(CO) 2]2 are similarly effective. 2-Methylpropane, generated after quench of excess TIBA can be trapped, and excess dibromomethane can be recycled, which makes the method industrially applicable. Solvent-free DIBAH or TIBA reduction of unsaturated carbonyl compounds, followed by in situ TIBA cyclopropanation of the unsaturated aluminum alcoholates in dibromomethane give cyclopropyl alkanols. Dienols such as geraniol, linalool or nor-radjanol are selectively cyclopropanated in their distal position, which allows the synthesis of flavor and fragrance compounds such as δ-citral, cis-javanol, and 7-methyl-georgywood. Uncontrollable exothermic events are avoided due to relatively low reaction temperatures made possible by the catalysts and by the addition mode of the reagents.[1]
- Brunner, Gerhard,Elmer, Susanne,Schroeder, Fridtjof
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supporting information; experimental part
p. 4623 - 4633
(2011/10/09)
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- CYCLOPROPANATION PROCESS
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A method for the preparation of cyclopropyl carbinols by cyclopropanation of unsaturated alcoholates, utilising a reagent system selected from (A) magnesium metal and dibromomethane, and (B) dibromomethane and a tertiary Grignard reagent, the reaction being carried out in the presence of an ether solvent. The process is useful, for example, for the preparation of ingredients for the flavour and fragrance industry.
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Page/Page column 14
(2009/04/25)
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- Cyclopropanation with dibromomethane under grignard and barbier conditions
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Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnes
- Brunner, Gerhard,Eberhard, Laura,Oetiker, Juerg,Schroeder, Fridtjof
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scheme or table
p. 3708 - 3718
(2010/04/02)
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- Tandem cyclopropanation with dibromomethane under Grignard conditions
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(Chemical Equation Presented) Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH 2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from α-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.
- Brunner, Gerhard,Eberhard, Laura,Oetiker, Juerg,Schroeder, Fridtjof
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p. 7543 - 7554
(2008/12/22)
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- CYCLOPROPANATION PROCESS
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A process for the cyclopropanation of a substituted alkene, comprising the reaction of the alkene with a carbenoide, generated from dibromomethane and a tri-(C2 - C8)-alkyl aluminium compound, in the presence of a catalytic amount of a metal compound selected from the group consisting of Lewis acids, metallocenes and metal carbonyl complexes. The process advantageously uses transition metal compounds as catalysts and the dibromomethane can be recovered. The process is especially useful for the preparation of ingredients for the flavour and fragrance industry.
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Page/Page column 8; 9
(2008/06/13)
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- Odorants
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The invention relates to compounds of the general formula STR1 in which R1 to R7 are, independently, H, methyl or ethyl, R8 +R9 together form methylene (--CH2 --) or a single bond, or R1 +R2 together form --(CH2)n --, with n being 3 or 4, or R3 +R5 or R5 +R7 represent methylene or a single bond; and the presence of at least one cyclopropane ring in the molecule is compulsory and the side chain can be saturated or contains one double bond in position α,β or β, γ a process for the manufacture of these compounds, compounds used to perform the process and the use of these compounds as an odorant or as an ingredient of an odorant composition.
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- Synthesis and Structure Elucidation of a New Potent Sandalwood-Oil Substitute
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New derivatives of campholenaldehyde ( = 2-(2,2,3-trimethylcyclopent-3-enyl)ethanal) bearing two cyclopropane moieties were synthesized, and the structure of the stereoisomer responsible for its exceptionally strong, diffusive, and natural sandalwood-oil scent, ((1S,2S)-1-methyl-2-{[(1S,3R,5R)-1,2,2-trimethylbicyclo[3.1.0]hex-3- yl]methyl}cyclopropyl)methanol (13a), was elucidated.
- Bajgrowicz, Jerzy A.,Frank, Iris,Fráter, Georg,Hennig, Michael
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p. 1349 - 1358
(2007/10/03)
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