- A mild method for the replacement of a hydroxyl group by halogen: 3. the dichotomous behavior of α-haloenamines towards allylic and propargylic alcohols
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A study of the deoxyhalogenation of allylic and propargylic alcohols with tetramethyl-α-halo-enamines is reported. Primary allylic and primary and secondary propargylic alcohols gave the corresponding halides in high yields. Secondary allylic and propargylic alcohols yielded the corresponding secondary halides but the reaction also produced some rearranged primary halides (I > Br > Cl). The reactions with tertiary allylic and tertiary propargylic alcohols gave several products and was therefore of little synthetic value. However, the addition of triethylamine to the reaction mixture or the use of lithium alkoxide instead of alcohol brought about a major change of the course of the reaction which led to amides carrying an allyl or an allenyl group at C2. This was shown to result from a Claisen-Eschenmoser rearrangement of an intermediate α-allyloxy- or propargyloxy-enamine.
- Munyemana, Fran?ois,Patiny, Luc,Ghosez, Léon
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- N - (4 - alkyl - 5 - benzyl thiazole - 2 - yl) amide and its preparation method and application
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The invention relates to N-(4-alkyl-5-benzyl thiazole-2-base) enoyl-amine or salt thereof, shown as a chemical structure formula I, wherein in the formula I, R is selected from C1-C2 alkyl, C3-C4 straight chains or C3-C4 branched alkyl; Y1 and Y3 are selected from hydrogen, methyl, ethyl, hydroxyl, methoxyl, ethoxyl, fluorine, chlorine, bromine or iodine; Y2 and Y4 are selected from hydrogen, methyl and ethyl; n is selected from 1,2,3,4,5,6 or 7; z is selected from hydrogen, methyl or phenyl; salt is selected from hydrochloride, hydrobromide, sulphate, phosphate, mesylate, benzene sulfonate and itramine tosylate. The invention provides the application of the N-(4-alkyl-5-benzyl thiazole-2-base) enoyl-amine or the salt thereof in preparation of anticancer drugs.
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-
Paragraph 0020; 0021
(2017/08/25)
-
- A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
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α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
- Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
-
p. 420 - 430
(2015/12/31)
-
- α-Selective Allylation of Isatin Imines Using Metallic Barium
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The Barbier-type allylation of isatin imines with allylic chlorides was achieved by using metallic barium as the promoter. Various α-allylated 3-amino-2-oxindoles were synthesized from the corresponding allylic chlorides and isatin imines. The double-bond geometry of allylic chlorides was retained throughout the reaction. An arylic bromide or iodide functionality of the products was robust to metalation under the optimum reaction conditions.
- Yanagisawa, Akira,Yamafuji, Seiya,Sawae, Toshiki
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supporting information
p. 2019 - 2023
(2016/08/09)
-
- Catalytic Asymmetric Crotylation of Aldehydes: Application in Total Synthesis of (-)-Elisabethadione
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A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective crotylation of unsaturated aldehydes with E- and Z-crotyltrichlorosilanes has been developed. The method was employed as a key step in a novel asymmetric synthesis of bioactive serrulatane diterpene (-)-elisabethadione. Other strategic reactions for setting up the stereogenic centers included anionic oxy-Cope rearrangement and cationic cyclization. The synthetic route relies on simple, high yielding reactions and avoids use of protecting groups or chiral auxiliaries.
- O'Hora, Paul S.,Incerti-Pradillos, Celia A.,Kabeshov, Mikhail A.,Shipilovskikh, Sergei A.,Rubtsov, Aleksandr E.,Elsegood, Mark R. J.,Malkov, Andrei V.
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supporting information
p. 4551 - 4555
(2015/03/18)
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- ISOPRENE OLIGOMER, POLYISOPRENE, PROCESSES FOR PRODUCING THESE MATERIALS, RUBBER COMPOSITION, AND PNEUMATIC TIRE
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The invention relates to an isoprene oligomer that contains a trans structural moiety and a cis structural moiety, which can be represented by the following formula (1), wherein at least 1 atom or group in the trans structural moiety is replaced by another atom or group. The invention also relates to a polyisoprene, which is biosynthesized using the isoprene oligomer and isopentenyl diphosphate. Further, this invention provides a rubber composition comprising the isoprene oligomer and/or the polyisoprene, and a pneumatic tire, including tire components (e.g., treads and sidewalls) formed from the rubber composition. wherein n represents an integer from 1 to 10; m represents an integer from 1 to 30; and Y represents a hydroxy group, a formyl group, a carboxy group, an ester group, a carbonyl group, or a group represented by the following formula (2):
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Paragraph 265
(2014/06/25)
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- Identification of a valuable kinetic process in copper-catalyzed asymmetric allylic alkylation
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Copper bottomed: The application of a previously described process of dynamic kinetic asymmetric transformation to acyclic substrates allowed the identification of a relevant kinetic process in the title reaction (see scheme; CuTC= copper(I) thiophencarboxylate, Naphth= naphthyl). The optimization of the reaction conditions and generality of the method, as well as mechanistic considerations are disclosed.
- Langlois, Jean-Baptiste,Alexakis, Alexandre
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supporting information; experimental part
p. 1877 - 1881
(2011/04/16)
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- Cross-coupling of aromatic bromides with allylic silanolate salts
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The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85°C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher γ-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial γ-transmetalation followed by direct reductive elimination or σ-π isomerization can rationalize all of the observed trends.
- Denmark, Scott E.,Werner, Nathan S.
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scheme or table
p. 16382 - 16393
(2009/05/08)
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- One-pot synthesis of heterocyclic compounds initiated by chemoselective addition to β-acyl substituted unsaturated aldehydes with nucleophilic tin complexes
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β-Acyl substituted unsaturated aldehydes 1 were revealed to be good precursors for the synthesis of various heterocyclic compounds by the combination with tin nucleophiles. Various 2-monosubstituted pyrroles were prepared in an one-pot procedure via the reductive amination of formyl groups of 1 by using Bu2SnIH-HMPA complex. One-pot synthesis of heterocycles was carried out initiated by chemoselective reduction of 1 with Bu3SnH-HMPA complex and the subsequent reaction with heterocumulenes. Furthermore, the one-pot synthesis of nitrogen heterocyclic compounds accompanying chemo-, regio- and diastereoselective carbon-carbon bond formation in side chain moieties was effectively accomplished initiated by the regio- and diastereoselective allylation of the formyl group of 1 with allylic tin species.
- Shibata, Ikuya,Kato, Hirofumi,Yasuda, Makoto,Baba, Akio
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p. 604 - 619
(2008/02/06)
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- Asymmetric, anti-selective scandium-catalyzed Sakurai additions to glyoxyamide. Applications to the syntheses of N-Boc D-alloisoleucine and D-isoleucine
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An enantio- and diastereoselective Sakurai-Hosomi reaction, catalyzed by chiral scandium pyridyl-bis(oxazoline) (pybox) complexes, has been developed. Both alkyl- and aryl-substituted allylsilanes are effective coupling partners with N-phenylglyoxamide. Applications of this reaction to the asymmetric syntheses of N-Boc D-alloisoleucine and D-isoleucine are described.
- Evans, David A.,Aye, Yimon,Wu, Jimmy
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p. 2071 - 2073
(2007/10/03)
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- Alpha- haloenamine reagents
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The present invention describes immobilized haloenamine reagents, immobilized tertiary amides, methods for their preparation, and methods of use.
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- Method for preparing a benzylic-type ether
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The invention concerns a method for preparing a benzylic-type ether from an aromatic compound. The inventive method for preparing a benzylic-type ether from an aromatic compound is characterised in that it consists in: in a first step, acylating an aromatic compound by reacting said aromatic compound with an acylating agent, in the presence of an efficient amount of zeolite or a Friedel-Crafts catalyst leading to a ketonic compound; in a second step, reducing the carbonyl group into carbinol leading to a benzylic alcohol; in a third step, etherifying the hydroxyl group, by reacting the benzylic alcohol with another alcohol, in the presence of an efficient amount of zeolite.
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- Process for functionalising a phenolic compound carrying an electron-donating group
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The invention concerns a method for functionalizing a phenolic compound bearing an electron-donor group, in said group para position, inter alia a method for the amidoalkylation of a phenolic compound bearing an electron-donor group, and more particularly, a phenolic compound bearing an electron-donor group preferably, in the hydroxyl group ortho position. The method for functionalizing in para position with respect to an electron-donor group carried by a phenolic compound is characterised in that the phenolic compound bearing an electron-donor group is subjected to the following steps: a first step which consists of protecting the hydroxyl group in the form of a sulphonic ester function; a second step which consists in reacting the protected phenolic compound with an electrophilic reagent; optionally, a third step deprotecting the hydroxyl group.
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- Process facilitating the regeneration of a catalyst based on a zeolite used in an acylation reaction, catalyst and use
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The present invention relates to a process facilitating the regeneration of a catalyst based on a zeolite, employed in an acylation reaction. Another subject of the invention is a process for acylation of an aromatic ether, comprising, in a preferred alternative form, an additional stage of regeneration of the catalyst. The process of the invention, which makes it possible to regenerate more easily a catalyst based on a zeolite, employed in an acylation reaction, is characterized in that the zeolite is modified by addition of an effective quantity of at least one metallic element M chosen from the elements of group 8 of the Periodic Classification of the elements.
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- Long-acting, chemical-resistant skin emollients, moisturizers, and strengtheners
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The present invention relates to compounds that are two-part molecules, and compositions containing such compounds, in which one part is designed to become covalently bonded to the skin (bonding agent) and the other part (a characteristic use agent) is designed to impart some characteristic use, such as emolliency, moisturizing effect, anti-acne, anti-wrinkle, anti-pain, antimicrobial, antifungal, antiviral, anti-irritation, skin tanning and skin lightening effects, extended protection of the skin (e.g., from ultraviolet light, by incorporation of a sunscreen component; from toxic and/or irritating substances; from insects and skin parasites, by incorporation of insecticides and/or insect repellants; from free radicals or other agents, as in aging, by incorporation of antioxidants), or dyeing of hair, skin nails, wool or fuir. The covalently bonded part may also be useful to impart skin strengthening effect (e.g., from shear forces) or as wound healing agents.
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- Aromatic compound acylation method
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A method for acylating an aromatic compound, specifically an activated or deactivated aromatic compound, is disclosed. The method is suitable for preparing aromatic ketones. The preparation of a catalyst and novel bismuth compounds is also disclosed. Said aromatic compound acylation method comprises reacting said aromatic compound with an acylating agent in the presence of a catalyst, and is characterised in that the acylation reaction is performed in the presence of an effective amount of at least one bismuth salt of trifluoromethanesulphonic acid.
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- Acylation method for an aromatic compound
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The present invention concerns a process for acylation of an aromatic compound.The acylation process of the invention consists of reacting the aromatic compound with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that it consists of:mixing the aromatic compound and the acylation compound in any manner;passing said mixture over a catalytic bed comprising at least one zeolite;recirculating the reaction mixture from the catalytic bed over the catalytic bed for a number of times which is sufficient to obtain the desired degree of conversion of the substrate.
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- Process for the acylation of aromatic ethers
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The present invention concerns a process for the acylation of an aromatic ether. Preferably the invention relates to a process for the acylation of a substituted aromatic ether, in particular veratrol. The acylation process of the invention consists of reacting the ether with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that the acylation reaction is carried out in the presence of an effective quantity of a catalyst comprising a faujasite type zeolite or a Y zeolite with the following physico-chemical characteristics: an atomic ratio denoted "global Si/Me1 " between the number of atoms of the element silicon and the number of atoms of every trivalent element Me1 contained in the zeolite in the range 2.4 to 90, preferably in the range 2.4 to 75, and more preferably in the range 2.4 to 60; an Me2 alkali metal content such that the atomic ratio Me2 /Me1(IV) between the number of atoms of alkali metal Me2 and the number of atoms of every trivalent element Me1(IV) included in the zeolitic network is less than 0.2, preferably less than 0.1, and more preferably less than 0.05.
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- Aromatic thioether acylation method
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PCT No. PCT/FR96/01763 Sec. 371 Date Aug. 3, 1998 Sec. 102(e) Date Aug. 3, 1998 PCT Filed Nov. 8, 1996 PCT Pub. No. WO97/17324 PCT Pub. Date May 15, 1997The present invention relates to a process for the acylation of an aromatic thioether. In its preferred variant, the invention resides in a process for the condensation of acetic anhydride or acetyl chloride with thioanisole. The process for the acylation of an aromatic thioether according to the invention is characterised in that it consists in reacting said thioether with an acylating agent chosen from the group formed by the halides of carboxylic acids and the anhydrides of carboxylic acids, in the presence of an effective quantity of an acid zeolite.
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- Deamination of trans-2-Methyl- And trans-2-Phenylcyclopropylamines
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The deaminations of trans-2-methyl- and 2-phenylcyclopropylamine hydrochlorides in acetic acid solution have been examined. A major product in each case was an allylic chloride, and the amount of chlorides increased when the chloride ion concentration was increased. With the methyl-substituted amine, increasing the chloride ion concentration changed the major chloride product from crotyl chloride to methallyl chloride. The addition of lithium perchlorate led to a reduction in the amount of chlorides formed. These results indicate that an ion pair is involved in the reaction. The deamination of the related open chain amines gave only small amounts of chlorides. B3LYP/ 6-31G* calculations found cyclopropyldiazonium chloride to prefer to have the chloride ion over the cyclopropyl ring. The transition state was located, and when followed down to products, allyl chloride was found. Similar calculations for the methyl-substituted series led to crotyl chloride from the ion pair with one chloride ion and to methallyl chloride from the ion-triplet with two chloride ions. The deaminations of the corresponding nitrosoureas in basic methanol also were studied. The products were the expected ethers. The addition of azide ion led to azides that were largely formed by initial reaction with the diazonium ion to give a pentazene that lost nitrogen to give the azide. However, some of the azide was formed by an SN2 displacement.
- Wiberg, Kenneth B.,Oesterle, Carmen G.
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p. 7756 - 7762
(2007/10/03)
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- Esterification of carboxylic acid salts
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Mono- or polycarboxylic acid esters are prepared by reacting a salt of such carboxylic acid with an organic halocompound, e.g., a (cyclo)alkyl, (cyclo)alkenyl, aryl or aralkyl halide, in an aqueous reaction medium, in the presence of a catalytically effective amount of a phase transfer catalyst, for example an onium salt.
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- Process for the acylation of aromatic ethers
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The present invention concerns a process for the acylation of an aromatic ether. Preferably, the invention relates to a process for the acylation of an unsubstituted aromatic ether, in particular anisole. The acylation process of the invention consists of reacting the ether with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that the acylation reaction is carried out in the presence of an effective quantity of a catalyst comprising a beta zeolite with an atomic ratio denoted "global Si/Me1 " between the number of atoms of the element silicon and the number of atoms of every trivalent element Me1 contained in the zeolite of no less than 15, preferably in the range 15 to 55, and more preferably in the range 18 to 35.
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-
- Asymmetric allylation of aromatic aldehydes catalyzed by chiral phosphoramides prepared from (S)-proline
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Chiral phosphoramides prepared from (S)-proline were used to catalyze the allylation and crotylation of aromatic aldehydes with allylic trichlorosilanes in good enantioselective yields. Phosphoramides 44 and 4m gave chiral homoallylic alcohols and their enantiomers, respectively, with similar levels of enantioselectivity.
- Iseki, Katsuhiko,Kuroki, Yoshichika,Takahashi, Mie,Kishimoto, Satoshi,Kobayashi, Yoshiro
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p. 3513 - 3526
(2007/10/03)
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- Regio- and Stereoselective Substitution of Hydroxy Group in Allyl Alcohols by Halogen
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A preparative method for regio- and stereoselective substitution of the hydroxy group by halogen in allyl alcohols under the action of triphenylphosphine complexes with ethyl trichloroacetate or trichloroacetonitrile has been developed.The regio- and stereoselectivity of substitution of hydroxy group by halogen with triphenylphosphine complexes and compounds containing trichloromethyl group is compared.
- Matveeva, E. D.,Erin, A. S.,Mitroshin, D. B.,Kurts, A. L.
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p. 1019 - 1022
(2007/10/03)
-
- Facile and Highly Stereoselective Synthesis of Homoallylic Alcohols Using Organosilicon Intermediates
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Allyltrichlorosilanes regioselectively reacted with aldehydes in N,N-dimethylformamide (DMF) without a catalyst to afford the corresponding homoallylic alcohols in high yields.The reactions proceeded under neutral conditions, and syn- and anti-homoallylic alcohols were stereoselectively obtained from (Z)- and (E)-allyltrichlorosilanes, respectively.In these reactions, DMF coordinated to the silicon atom of the allyltrichlorosilanes to form hypervalent silicates, which in turn reacted with aldehydes smoothly.Solvent effects in these reactions were also examined.The reactions were applied to the one-pot synthesis of homoallylic alcohols from allylic chlorides via organosilicon intermediates.While syn-homoallylic alcohols were prepared from (Z)-allyl chlorides, anti-homoallylic alcohols were obtained from (E)-allyl chlorides.Unique regioselectivities in the reactions of 1-chloro-2,4-pentadiene were also found.Finally, the one-pot synthesis of homoallylic alcohols from 1,3-dienes is reported.
- Kobayashi, Shu,Nishio, Koichi
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p. 6620 - 6628
(2007/10/02)
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- Surface Catalyzed Hydrochlorination of 1,3-Butadiene
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The rates of disappearance of gaseous hydrogen chloride (-d/dt) and 1,3-butadiene and appearance of the gaseous products 3-chloro-1-butene and (E)- and (Z)-1-chloro-2-butene (+d/dt) in Pyrex IR cells at 295 K and total initial pressures of about 450 torr are found to be proportional to the surface-to-volume ratio (S/V) of the reaction vessel.
- Mascavage, Linda M.,Dalton, David R.
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p. 3461 - 3464
(2007/10/02)
-
- Surface-Catalyzed Hydrochlorination of Alkenes. The Reaction of the Gases Hydrogen Chloride and 1,3-Butadiene
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Mixtures of gaseous hydrogen chloride and gaseous 1,3-butadiene at total pressures less than 1 atm and at temperatures between 294 and 334 K yield mixtures of 3-chloro-1-butene and (E)- and (Z)-1-chloro-2-butene.The ratio of the product of putative 1,2-addition to those of 1,4-addition is approximately unity with only the amount of (Z)-1-chloro-2-butene increasing from ca. 2percent of the total reaction product mixture at the lower temperature to ca. 4percent at the higher temperature.Kinetic measurements have been made by observing the reaction throughout its course utilizing FT-IR spectroscopy.It is concluded that surface catalysis is required for product formation and that the reaction, which occurs at the walls, is most probably between multilayer adsorbed hydrogen chloride and gaseous or weakly adsorbed 1,3-butadiene.
- Mascavage, Linda M.,Chi, Hongji,La, Sangmoo,Dalton, David R.
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p. 595 - 601
(2007/10/02)
-
- SYNTHESIS OF ALKYL HALIDES UNDER NEUTRAL CONDITIONS
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Primary and secondary alcohols are efficiently converted to the corresponding alkyl halides under neutral conditions.
- Munyemana, Francois,Frisque-Hesbain, Anne-Marie,Devos, Alain,Ghosez, Leon
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p. 3077 - 3080
(2007/10/02)
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- REGIOSPECIFIC AND STEREOSPECIFIC SUBSTITUTION OF HYDROXYL IN ALIPHATIC ALCOHOLS BY HALOGEN
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A new system containing triphenylphosphine and trichloro- and tribromoacetic ester makes it possible to substitute the hydroxyl group in alcohols by halogen.Regiospecific and stereospecific substitution of the hydroxyl by the halogen takes place as a result of the reaction of primary and secondary aliphatic alcohols and of 2-alkenols, susceptible to isomerization processes, with this system.
- Matveeva, E. D.,Kurts, A. L.,Yalovskaya, A. I.,Nikishova, N. G.,Bundel', Yu. G.
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p. 642 - 646
(2007/10/02)
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- STEREOHOMOGENEUS SYNTHESIS OF (E)- AND (Z)-CROTYLTRIFLUOROSILANES AND HIGHLY STEREOSELECTIVE ALLYLATION OF ALDEHYDES
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Stereohomogeneus (E)- and (Z)-crotyltrifluorosilanes were prepared and used for the highly diastereoselective synthesis of threo- and erythro-β-methylhomoallyl alcohols, respectively, from aldehydes in the presence of fluoride ions.The mechanism of the reaction was discussed.
- Kira, Mitsuo,Hino, Takakazu,Sakurai, Hideki
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p. 1099 - 1102
(2007/10/02)
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- Process for production of 2,6-di-tert-alkenyl phenols
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There is disclosed a process for the production of 2,6-di-tert-alkyl-4-alkenyl phenols wherein the improvement comprises the reaction of a 2,6-di-tert-alkyl phenol with an allyl halide to yield the 2,6-di-tert-alkyl-4-alkenyl phenol through the use of a triphase or polymer bound catalyst.
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- Process for preparing amides by reaction in presence of molecular sieve
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There is provided a process for preparing amides which comprises reacting an amine, or an amide, and an acid halide, or anhydride, in suitable molecular proportions, in an inert organic diluent, in the presence of an effective amount of a molecular sieve, until the reaction is completed, separating the molecular sieve, and recovering the amide from the organic mother liquor.
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- INSECT SEX PHEROMONES. STEREOSELECTIVE SYNTHESIS OF SEVERAL (Z)- AND (E)-ALKEN-1-OLS, THEIR ACETATES, AND OF (9Z,12E)-9,12-TETRADECADIEN-1-YL ACETATE
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Several female sex pheromone components produced by moths belonging to the order of Lepidoptera, and potential attractants of Dacus oleae (Diptera:Tripetidae) have been synthesized in high chemical and stereoisomeric purity by improved acetylenic routes involving alkylation of lithium 1-alkyn-1-ides in HMPT, followed by (Z) and (E) highly stereoselective reduction of the derived internal alkynes.Particular care has been paid to optimize the parameters of the reactions used and to evaluate the chemical and isomeric purity of the reaction products.The compounds synthesized include (Z)- and (E)-5-nonen-1-ol, (Z)- and (E)-7-dodecen-1-yl acetate, (Z)- and (E)-7-teradecen-1-yl acetate, (Z)- and (E)-7-nonen-1-ol, (Z)- and (E)-9-tetradecen-1-yl acetate, (Z)- and (E)-10-tetradecen-1-yl acetate, (Z)- and (E)-11-tetradecen-1-yl acetate.Pure (Z)-6-nonen-1-ol, which is an attractant of olive fruit fly, D. oleae, and very probably, a constituent of the sex pheromone of females of this insect, has been prepared by a rather efficient copper-catalyzed reaction between (Z)-3-hexen-1-ylmagnesium bromide and oxetane. (9Z,12E)-9,12-Tetradecadien-1-yl acetate, which is the pheromone of Anagasta kuenniella, Ephestia elutella, Cadra figulella, Spodoptera exigua, S. litura, and a component of the sex pheromones of several other Lepidoptera, has been conveniently prepared by using the copper-catalyzed coupling reaction between (E)-1-chloro-2-butene and 10-tetrahydropyranyloxy-1-decenylmagnesium bromide, followed by acetylation and Z-stereoselective reduction of the derived 1,4-enyne.All syntheses have been conducted on a scale to yield less than 50 mmol of the pure sex pheromone components, but seem adaptable for much larger quantities.
- Rossi, Renzo,Carpita, Adriano,Gaudenzi, Loretta,Quirici, Maria Grazia
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p. 237 - 246
(2007/10/02)
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- 2-Acyl-3-substituted cyclopentan-1-ones and process for their preparation
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1,3-Dicarbonyl compounds useful as medicines, agricultural chemicals, perfumes, and their intermediates are prepared by reacting a specific α,β-unsaturated carbonyl compound with a specific organic copper lithium compound in the presence of an aprotic inert organic solvent, and then reacting the reaction product with an organic carboxylic acid halide or anhydride. In particular, novel 2-acyl-3-substituted cyclopentan-1-ones and 2-acyl-3-substituted cyclohexan-1-ones having important physiological activities are provided.
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- Novel indolobenzazepine derivatives, useful as tranquilizers
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Certain novel 1,2,3,4,8,9-hexahydro-3-(substituted)pyrido[4',3':2,3]indolo[1,7-ab][1]-benzazepines are useful as minor tranquilizers (anxiolytics) and/or major tranquilizers (antipsychotics). The minor tranquilizers are effective at non-ataxic doses, and are not likely to cause addiction when abused. A representative compound in this class is 3-(cyclopropylmethyl)-1,2,3,4,8,9-hexahydropyrido[4',3':2,3]indolo[1,7-ab][1]benzazepine.
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