WO2014073003A1 - Procédé en une étape pour la préparation d'aryloléfines - Google Patents

Procédé en une étape pour la préparation d'aryloléfines Download PDF

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WO2014073003A1
WO2014073003A1 PCT/IN2013/000688 IN2013000688W WO2014073003A1 WO 2014073003 A1 WO2014073003 A1 WO 2014073003A1 IN 2013000688 W IN2013000688 W IN 2013000688W WO 2014073003 A1 WO2014073003 A1 WO 2014073003A1
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group
prop
benzene
step process
aryl
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Hanumant Bapurao Borate
Supriya Hanumant GAIKWAD
Ananda Shahaji KUDALE
Subhash Prataprao Chavan
Shrikant Ganpat PHARANDE
Vitthal Dattatraya WAGH
Vikram Shahaji SAWANT
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Council Of Scientific & Industrial Research
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes

Definitions

  • the present invention relates to the single step process for the synthesis of aryl olefins of Formula 1.
  • process for synthesis of compound of formula 1 comprises, reaction of aryl aldehyde with aliphatic aldehyde in presence of malononitrile and acid or base or salt, optionally in presence of solvent to afford aryl olefin compounds of formula 1 in good yield with trans selectivity.
  • Aryl olefins are useful intermediates in organic synthesis as well as medicinal chemistry. Further the aryl olefins were studied for various biological activities such as hypolipidemic and antiplatelet activities of aryl olefins particularly a-asarone is reported in J. Med. Chem., 2000, 43 (20), pp 3671-3676 by Janusz Poplawski et al.; whereas anticonvulsant activity of aryl olefins is disclosed in Biological & Pharmaceutical Bulletin. 10/2012 by Qi-Xiong Chen et al. Various metal catalyzed processes for the synthesis of aryl olefins or alkenes are reported in the state of arts.
  • US4965361 (Edgar Kevin et al.) relates to the preparation of 4-substituted aryl olefins by contacting a 4-substituted aryl iodide with an olefin in an ester solvent in the presence of a catalyst system comprising a palladium compound and a Bronsted base.
  • US7282618 (David Milstein et al.) describes a method for the production of an aryl alkene, comprising reacting an arene with an olefin in the presence of a Ru or Os compound as catalyst, such that an aryl alkene is produced.
  • US3674884 (Ichiro Moritani et al.) discloses process for the preparation of aromatic hydrocarbon compounds containing monoethylenically unsaturated radicals, which comprises reacting a monoethylenically unsaturated compound with an aromatic hydrocarbon compound in the presence of a palladium salt. Further cobalt (I)-catalyzed stereoselective olefmation of alkylzinc reagents with aldehydes is reported by J.-X. Wang et al., in SYNTHESIS, 2003, 1506-1510.
  • the process of the current invention involves the reaction of easily available aldehydes as such to obtain the substituted olefins in single-step without any need of special catalyst so the efforts were made to increase the yield of aryl olefins with significant trans selectivity.
  • the main object of the present invention is to provide a process for the synthesis of aryl olefins of Formula 1 by reacting aryl aldehydes with alkyl aldehydes in presence of malononitrile and an acid or a base or a salt, optionally in presence of solvent.
  • Another object of the present invention is to provide novel aryl olefin compounds of Formula- 1.
  • the present invention provides, a single-step process for the synthesis of aryl olefins of Formula 1, wherein the process comprising the step of reacting of aryl aldehydes with alkyl aldehydes, at temperature in between -10 tol50°C in presence of malononitrile and acid or base or salt,
  • 'Ar' is selected from the group consisting of (un)substituted phenyl, naphthyl, anthracenyl or heteroaryl ring, substituted with (un)protected hydroxyl group, halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, nitro or cyano group, linear or branched chain of 1 to 20 carbon atoms;
  • n 0-20 and;
  • the single-step process is optionally carried out in presence of organic solvent selected from the group consisting of acetonitrile, dimethyl formamide, 1,4-dioxane, ethanol, methanol, dimethyl sulfoxide, toluene or combinations thereof, preferably solvent is acetonitrile.
  • organic solvent selected from the group consisting of acetonitrile, dimethyl formamide, 1,4-dioxane, ethanol, methanol, dimethyl sulfoxide, toluene or combinations thereof, preferably solvent is acetonitrile.
  • the aryl aldehyde is selected from the group consisting of 3,4,5-trimethoxybenzaldehyde, anisaldehyde, 1 -naphthaldehyde, thiophene-2-carboxaldehyde, 4-nitrobenzaldehyde, 4-cyanobenzaldehyde, 4-allyloxy benzaldehyde, 4-prop-2-yn- 1 -yloxybenzaldehyde, 4-(methoxybenzyloxy) benzaldehyde, anthracene-9-carboxaldehyde, 4-fluorobenzaldehyde, 2,4-dichlorobenzaldehyde, and 4- methoxybenzaldehyde .
  • the molar concentration of aryl aldehyde is in the range of 2- 15 mmole.
  • the alkyl aldehyde or aliphatic aldehyde is selected from the group consisting of propanal, hexanal, heptanal, octanal, dodecyl aldehyde.
  • the molar concentration of alkyl aldehyde is in the range of 2-20 mmole.
  • the molar ratio of aryl aldehyde to alkyl aldehyde is in the range of 1 : 1.0 to 1 : 1.6.
  • the acid is selected from the group consisting of acetic acid, propionic acid, formic acid, p-toluenesulfonic acid, hydrochloric acid, proline, alanine.
  • the base is selected from the group consisting of morpholine, triethyl amine, pyrrolidine, piperidine, pyridine, potassium carbonate, potassium hydroxide, sodium methoxide, and the salt is selected from the group consisting of ammonium acetate, ammonium formate.
  • the acid or base or salt is present either alone or combination thereof.
  • the acid-base/salt combination is acetic acid and ammonium acetate.
  • the molar ratio of acid and base/salt combination used in the reaction is between 1 : 1 to 2: 1.
  • the molar concentration of malononitrile ranges from 3 to 40 mmole, preferably 5 to 35 mmole.
  • the aryl olefin compounds of Formula- 1 are selected from the group consisting of;
  • novel aryl olefin compounds of formula- 1 are selected from, the group consisting of
  • the present invention provides the single-step process for synthesis of aryl olefins of Formula 1 , which comprises reacting aryl aldehydes with aliphatic/alky aldehydes at suitable temperature, in presence of malononitrile and acid or base or salt, optionally in presence of solvent, as depicted in Scheme 2.
  • 'Ar' represents (un)substituted phenyl, naphthyl, anthracenyl or heteroaryl ring, substituted with (un)protected hydroxyl group, halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, nitro or cyano group, linear or branched chain of 1 to 20 carbon atoms;
  • n 0-20 and; ⁇ .
  • the aryl aldehyde is selected from the group consisting of 3,4,5-trimethoxybenzaldehyde, anisaldehyde, 1 -naphthaldehyde, thiophene-2-carboxaldehyde, 4-nitrobenzaldehyde, 4- cyanobenzaldehyde, 4-allyloxybenzaldehyde, 4-prop-2-yn-l-yloxybenzaldehyde, 4- (methoxybenzyloxy) benzaldehyde, anthracene-9-carboxaldehyde, 4-fluorobenzaldehyde, 2,4-dichlorobenzaldehyde, and 4-methoxybenzaldehyde.
  • the aryl aldehyde employed in the present invention is not limited to the aldehydes mentioned above.
  • alkyl aldehyde or aliphatic aldehyde employed in the invention is selected from but not limited to propanal, hexanal, heptanal, octanal, dodecyl aldehyde.
  • the molar ratio of aryl aldehyde to alkyl aldehyde is in the range of 1 : 1 to 1 :2, preferably 1 : 1.1 to 1 : 1.4.
  • the acid or base or salt used in the reaction is either alone or combinations thereof, where acid is selected from the group consisting of acetic acid, propionic acid, formic acid, p-toluenesulfonic acid, hydrochloric acid, proline, alanine, and base is selected from the group consisting of morpholine, triethyl amine, pyrrolidine, piperidine, pyridine, potassium carbonate, potassium hydroxide, sodium methoxide and salt is selected from the group consisting of ammonium acetate, ammonium formate or combinations thereof, preferably combination of acetic acid and ammonium acetate.
  • the instant reaction is essentially carried out in presence of malononitrile.
  • the molar ratio of aryl aldehyde to malononitrile is in the range of 1 :2 to 1 : 3 preferably 1 :2.5.
  • the solvent used in the reaction is selected from the group consisting of acetonitrile, dimethyl formamide, 1,4-dioxane, ethanol, methanol, dimethyl sulfoxide, toluene or combinations thereof, preferably solvent is acetonitrile.
  • solvent is optional, where the reaction can be carried out in absence of organic solvent by stirring the reaction mixture of reactants at suitable temperature (-10°C to 150°C) preferably 80°C but corresponding Knoevenagel product is obtained in substantial amount.
  • the volume of solvent used depends on concentration of reactants.
  • the reaction mixture is stirred at -10 °C to 150 °C preferably 70°- 80 °C or subjected to microwave irradiation.
  • the process leads to synthesis of trans isomers or (E) isomers of compounds of Formula 1.
  • the aryl olefins obtained by the instant process have trans selectivity and cis isomer is undetectable.
  • the invention provides library of novel aryl olefin compounds of Formula 1 , prepared by the novel process of the invention.
  • Table 1 enlists the compounds prepared by the novel process of the invention and the yields of the products.
  • aAcid-base-salt used: A— Acetic acid, ammonium acetate; B— Alanine, ammonium acetate; C— Proline, ammonium acetate.
  • B Alanine, ammonium acetate
  • C Proline, ammonium acetate.
  • the yields are given for the isolated desired products.
  • the corresponding Knoevenagel products and dicyanoanilines were isolated in minor amounts in varying yields.
  • the process of the invention led to novel aryl olefin compounds of formula- 1 selected from, but not limited to (E)-5 -(dodec- 1 -en- 1-yl)- 1 ,2,3- trimethoxybenzene [1-h], (E)-l -(dodec- 1 -en- l-yl)-4-nitrobenzene [1-k], (E)-4-(dodec-l-en- l-yl)benzonitrile [1-n], (E)-l-(prop-l-en-l-yl)-4-(prop-2-yn-l-yloxy)benzene [1-p] and (£)- 2,4-dichloro- 1 -(hept- 1 -en- 1 -yl)benzene [1-t] .
  • the obtained compounds of formula- 1 are characterized by spectral techniques such as IR, 13 C NMR spectroscopy, 1H NMR spectroscopy, High- resolution mass spectrometry HRMS as exemplified herein. Further the aryl olefins of Formula- 1 are useful as intermediates for the synthesis of active and new molecules.
  • the present invention provides a pharmaceutical composition
  • a pharmaceutical composition comprising aryl olefins of formula- 1 or its pharmaceutically acceptable salts, along with pharmaceutically acceptable excipients or carriers, to decrease platelet aggregation or for the treatment of hyperlipidemias.
  • the composition may be formulated into preparations like solid, semi-solid, liquid or gaseous forms, such as tablets, capsules, powders, granules, ointments, syrup, solutions, injections, gels and microspheres etc.
  • the dosage ⁇ forms can also be prepared as sustained, controlled, modified and immediate dosage forms.
  • the present invention relates to administering 'an effective amount' of the 'composition of invention' to the subject suffering from cardiovascular disesase.
  • compound of the invention and pharmaceutical compositions containing them may be administered using any amount, any form of pharmaceutical composition via any route of administration effective for treating the disease.
  • Typical routes of administering such pharmaceutical compositions include, without limitation, oral, topical, transdermal, inhalation, parenteral, sublingual, buccal, rectal, vaginal, and intranasal.
  • excipients or carriers are selected from the group such as diluents, disintegrants, crosslinked polymers, binders, glidants, surfactants, sweetners, lubricants, coatings layer.
  • This compound was prepared from anisaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from anisaldehyde and hexyl aldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from anisaldehyde and dodecyl aldehyde following procedure similar to the one described in Example 1.
  • This compound was prepared from 1 -naphthaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from thiophene-2-carboxaldehyde and dodecyl aldehyde following the procedure similar to the one described in Example 1. Colorless liquid; Yield: 39%; IR (chloroform): 1464, 1687, 2853, 2924, 3070 cm "1 .
  • This compound was prepared from 3,4,5-trimethoxybenzaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 3,4,5-trimethoxybenzaldehyde and dodecyl aldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-nitrobenzaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-nitrobenzaldehyde and hexyl aldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-nitrobenzaldehyde and dodecyl aldehyde following procedure similar to the one described in Example 1.
  • This compound was prepared from 4-cyanobenzaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-cyanobenzaldehyde and hexyl aldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-cyanobenzaldehyde and dodecyl aldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-allyloxybenzaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-prop-2-yn- 1 -yloxybenzaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-(methoxybenzyloxy) benzaldehyde propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from anthracene-9-carboxaldehyde and propionaldehyde following the procedure similar to the one described in Example 1.
  • This compound was prepared from 4-fluorobenzaldehyde and heptaldehyde following the procedure similar to the one described in Example 1.
  • ADVANTAGES OF INVENTION The process of the invention yields aryl olefins of Formula- 1 that can serve as intermediates for many other compounds having biological activity.
  • the present invention does not use inert atmosphere, dry solvents, and cryogenic conditions.
  • the hazardous chemicals and strong bases are avoided and the easily available starting materials lead to aryl olefins in single step with a variety of substituent with good yield and trans selectivity. Additionally the desired aryl olefins can be easily separated from other products formed.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé en une étape pour la synthèse de composés d'aryloléfine répondant à la formule (1) par mise en réaction d'aldéhydes aryliques avec des aldéhydes alkyliques en présence de malononitrile et d'un acide ou d'une base ou d'un sel, facultativement en présence de solvant.
PCT/IN2013/000688 2012-11-09 2013-11-08 Procédé en une étape pour la préparation d'aryloléfines WO2014073003A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253207A (zh) * 2020-03-05 2020-06-09 苏州大学 可见光催化的芳香族烯烃的双氯加成产物的制备方法
CN114195610A (zh) * 2022-01-05 2022-03-18 海南大学 一种e式内部烯烃类化合物的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674884A (en) 1967-08-04 1972-07-04 Ube Industries Process for the preparation of aromatic hydrocarbons containing monoethylenic unsaturated radicals
US4965361A (en) 1989-02-27 1990-10-23 Eastman Kodak Company Preparation of 4-substituted aryl olefins
US7282618B2 (en) 2000-12-13 2007-10-16 Yeda Research And Development Co., Ltd. Method for the production of aryl alkenes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674884A (en) 1967-08-04 1972-07-04 Ube Industries Process for the preparation of aromatic hydrocarbons containing monoethylenic unsaturated radicals
US4965361A (en) 1989-02-27 1990-10-23 Eastman Kodak Company Preparation of 4-substituted aryl olefins
US7282618B2 (en) 2000-12-13 2007-10-16 Yeda Research And Development Co., Ltd. Method for the production of aryl alkenes

Non-Patent Citations (19)

* Cited by examiner, † Cited by third party
Title
ALEXANDER, CANADIAN JOURNAL OF CHEMISTRY, vol. 43, 1965, pages 3437
B. GREEN ET AL: "Unusual Knoevenagel condensations of 16a-substituted-16-methylene-17-keto-steroids", TETRAHEDRON, vol. 32, no. 24, 1 January 1976 (1976-01-01), pages 2997 - 3001, XP055104545, ISSN: 0040-4020, DOI: 10.1016/0040-4020(76)80158-5 *
DANIELA MIRK ET AL., SYNLETT, vol. 8, 2006, pages 1255 - 1259
E. PEYROUX ET AL., EUR. J ORG. CHEM., 2004, pages 1075
FELIPE GÁNDARA ET AL: "Two-Dimensional Hybrid Germanium Zeotype Formed by Selective Coordination of the trans -1,2-Diaminocyclohexane Isomer to the Ge Atom: Heterogeneous Acid-Base Bifunctional Catalyst", INORGANIC CHEMISTRY, vol. 47, no. 15, 1 August 2008 (2008-08-01), pages 6791 - 6795, XP055104207, ISSN: 0020-1669, DOI: 10.1021/ic8004097 *
H. B. BORATE ET AL., TETRAHEDRON LETT., vol. 52, 2011, pages 5491 - 5493
HANUMANT B. BORATE ET AL: "One-step method for the synthesis of aryl olefins from aryl aldehydes and aliphatic aldehydes", TETRAHEDRON LETTERS, vol. 54, no. 12, 1 March 2013 (2013-03-01), pages 1528 - 1530, XP055103874, ISSN: 0040-4039, DOI: 10.1016/j.tetlet.2013.01.008 *
J.-X. WANG ET AL., SYNTHESIS, 2003, pages 1506 - 1510
JANUSZ POPLAWSKI ET AL: "Synthesis and Hypolipidemic and Antiplatelet Activities of [alpha]-Asarone Isomers in Humans (in Vitro), Mice (in Vivo), and Rats (in Vivo)", JOURNAL OF MEDICINAL CHEMISTRY, vol. 43, no. 20, 1 October 2000 (2000-10-01), pages 3671 - 3676, XP055104555, ISSN: 0022-2623, DOI: 10.1021/jm000905n *
JANUSZ POPLAWSKI, J. MED. CHEM., vol. 43, no. 20, 2000, pages 3671 - 3676
LIU J-T ET AL: "One-pot synthesis of trans-beta-alkylstyrenes", TETRAHEDRON LETTERS, PERGAMON, GB, vol. 42, no. 35, 27 August 2001 (2001-08-27), pages 6147 - 6150, XP004298202, ISSN: 0040-4039, DOI: 10.1016/S0040-4039(01)01185-6 *
MANGOLD; HANNA, J. MED CHEM, vol. 25, 1982, pages 630
MAYER ET AL., CHEMCATCHEM, vol. 3, 2011, pages 1567
QI-XIONG CHEN, BIOLOGICAL & PHARMACEUTICAL BULLETIN, October 2012 (2012-10-01)
SANGMESHWER P SAWARGAVE ET AL: "One-step synthesis of 4-alkyl-3-aryl-2,6-dicyanoanilines and their use in the synthesis of highly functionalized 2,3,5,6,7- and 2,3,4,5,7-substituted indoles", TETRAHEDRON LETTERS, PERGAMON, GB, vol. 52, no. 42, 10 August 2011 (2011-08-10), pages 5491 - 5493, XP028293801, ISSN: 0040-4039, [retrieved on 20110818], DOI: 10.1016/J.TETLET.2011.08.064 *
SHARMA ET AL., BULL CHEM SOC JPN, vol. 77, 2004, pages 2231
TUNTIWACHWUTTIKUL ET AL., PHYTOCHEMISTRY, vol. 20, 1981, pages 1164
XIE; WANG, CHEM EUR J, vol. 17, 2011, pages 4972
ZHANG ET AL., SYNLETT, vol. 23, 2012, pages 1221 - 1224

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253207A (zh) * 2020-03-05 2020-06-09 苏州大学 可见光催化的芳香族烯烃的双氯加成产物的制备方法
CN111253207B (zh) * 2020-03-05 2022-04-01 苏州大学 可见光催化的芳香族烯烃的双氯加成产物的制备方法
CN114195610A (zh) * 2022-01-05 2022-03-18 海南大学 一种e式内部烯烃类化合物的合成方法

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