WO2007147775A1 - Procédé de synthèse de composés aromatiques - Google Patents

Procédé de synthèse de composés aromatiques Download PDF

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Publication number
WO2007147775A1
WO2007147775A1 PCT/EP2007/055923 EP2007055923W WO2007147775A1 WO 2007147775 A1 WO2007147775 A1 WO 2007147775A1 EP 2007055923 W EP2007055923 W EP 2007055923W WO 2007147775 A1 WO2007147775 A1 WO 2007147775A1
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formula
compound
process according
independently
chlorine
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Michael Gordon Hutchings
Peter Quayle
James Alan Bull
Cristina Lujan Barroso
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Dystar Textilfarben GmbH and Co Deutschland KG
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Dystar Textilfarben GmbH and Co Deutschland KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
    • 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
    • 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
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • 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
    • 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
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
    • 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
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • 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
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • C07C2603/48—Chrysenes; Hydrogenated chrysenes

Definitions

  • the present invention provides a new process for the conversion of readily available organic chemical starting materials to aromatic species, of potential use in many organic chemistry-based industries.
  • the present invention claims a process for preparing a compound of the formula (I)
  • R denotes an organic radical which, together with the two carbon atoms to which it is bonded, forms a carbocyclic or heterocyclic ring;
  • R 1 , R 2 , R 3 and X independently, denote hydrogen, halogen, nitro, cyano or an organic radical; or R 1 and R 2 or R 2 and R 3 , together with the carbon atoms to which they are bonded, form a ring; which comprises exposing a compound of the formula (II)
  • R 1 , R 2 , R 3 and X are defined as given above and Y and Z, independently, have one of the meanings of X; to an energy source in the presence of a catalyst system.
  • the carbocylic or heterocyclic ring formed by R and the two carbon atoms to which it is bonded is preferably a benzene ring, a benzene ring which is substituted by 1 , 2, 3 or 4 substituents, a benzene ring which is further condensed with other aromatic rings or other heterocyclic rings, a cyclohexene ring, a cyclohexene ring which is substituted by up to eight substituents, a 5- or 6-membered heterocyclic ring, a 5- or 6-membered heterocyclic ring which is substituted by 1 , 2, 3 or 4 substituents, a 5- or 6-membered heterocyclic ring which is further condensed with aromatic rings or a 5- or 6-membered heterocylic ring which is substituted by up to eight substituents.
  • 5- or 6-membered heterocylic rings can be aromatic or not. Examples are pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, thiophene, 2-pyrone and coumarin.
  • Examples of an organic radical standing for R 1 , R 2 , R 3 , X, Y or Z are members of the following groups:
  • W denotes alkyl, cycloalkyl, alkenyl or cycloalkenyl, all of which may be further optionally substituted and in the case of cycloalkyl or cycloalkenyl one or more of the carbocyclic ring carbons can be replaced by one or more heteroatoms such as O, N or S;
  • Ar denotes aryl or heteroaryl which can be optionally substituted
  • CONHAr, -CONWAr and -CONW 2 where W and Ar are as defined above and the two radicals W in -CONW 2 are identical or different; -OH, -OW, -OAr, -SH, -SW and -SAr where W and Ar are as defined above;
  • Rings formed by R 1 and R 2 or R 2 and R 3 , together with the carbon atoms to which they are bonded, are preferabyl 5- or 6-membered and are especially preferably cycloalkyl rings, which may optionally be substituted.
  • Alkyl groups standing for W are preferably (CrC 4 )-alkyl groups which can be straight- chain or branched and are for example methyl, ethyl, n-propyl, i-propyl and n-butyl.
  • Alkenyl groups standing for W are preferably (C 2 -C 6 )-alkenyl groups and are for example vinyl and allyl and their methylated derivatives (methallyl, crotyl).
  • Cycloalkyl groups standing for W are preferably (C 3 -C 8 )-cycloalkyl groups and are for example cyclopentyl, cyclohexyl and cyclooctyl.
  • Examples of cycloalkyl groups wherein one or more of the carbocyclic rings atoms are replaced by heteroatoms are pyrrolidinyl, tetrahydrofurfuryl, piperidinyl and morpholinyl.
  • Aryl groups standing for Ar are preferably phenyl and naphthyl.
  • Halogen is preferably fluorine, chlorine, bromine and iodine and more especially fluorine, chlorine and bromine.
  • R 1 , R 2 and R 3 independently, denote hydrogen, fluorine, chlorine, bromine; (CrC 4 )-alkyl; (CrC 4 )-alkyl, which is substituted by -OW, especially methoxy, -OAr, especially phenoxy, or by halogen, especially fluorine and chlorine; phenyl; phenyl, which is substituted by -OW, especially methoxy, -OAr, especially phenoxy, or by halogen, especially fluorine, chlorine and bromine, nitro, cyano, - CO 2 H and -CO 2 W, especially -CO 2 CH 3 ; (C r C 4 )-alkoxy; (Ci-C 4 )-alkoxy, which is substituted by -OW, especially methoxy, -OAr, especially phenoxy, or by halogen, especially fluorine and chlorine; phenoxy; or phenoxy, which is substituted by -OW, especially methoxy,
  • X, Y, and Z independently, denote hydrogen, fluorine, chlorine, bromine, iodine, W, Ar, -CO 2 H, -CO 2 W, -CO 2 Ar, -CONH 2 , -CONHW, -CONHAr, -CONWAr, -CONW 2 , -OH, -OW, -OAr, -SH, -SW, -SAr, -NH 2 , -NHW, -NW 2 , -NHAr, -NWAr, -OCOW or -OCOAr, where W and Ar are as defined above and the two radicals W in -CONW 2 and -NW 2 are identical or different.
  • Y and Z independently denote chlorine, bromine or iodine and even more preferably, Y and Z are both chlorine or bromine and most preferably, Y and Z are both chlorine.
  • X denotes chlorine, bromine or iodine and even more preferably is identical to Y and Z.
  • Said system preferably comprises a transition metal, optionally one or more ligand for that metal and optionally a Lewis acid.
  • Said system especially preferably comprises a transition metal, one or more ligand for that metal and optionally a Lewis acid.
  • the transition metal may be present as the free metal or a salt of the metal.
  • Preferred metals are copper, iron, nickel, palladium, platinum and ruthenium, especially copper, iron and ruthenium.
  • a metal which is particularly favoured is copper, used as fine metallic particles, or as copper (I) salts, or as copper (II) salts. Particularly effective are salts of copper (I), such as CuCI and CuBr.
  • Other favoured metals salts are those of iron (II), such as FeCI 2 and salts of Ru(III).
  • Metal salts are preferably free of water.
  • Another component of the catalyst system is one or more organic compounds which act as ligands for the metal.
  • organic compounds which act as ligands for the metal.
  • Particularly effective are amines, more especially di- or triamines, and aromatic bases such as optionally substituted pyridine, or dipyridyl compounds such as 2,2'-bipyridyl or the imidazolium salt species of the formula (III)
  • R 10 has a meaning of R 1 defined above and A " is an anion which is preferably chloride.
  • NHC ⁇ /-heterocyclic carbenes
  • the catalyst system is either formed in situ by reaction between the compound of formula (MIb) and a metal salt, or is an isolable complex of the formula (MIc) which can be prepared, stored, and used according to the present invention as required.
  • M is any transition metal, preferably copper, nickel, iron, ruthenium, palladium or platinum, optionally bound to additional ligands, such as halogen.
  • a preferred embodiment of (MIc) is the compound of formula (MId), where R 11 is 2,6-di-iso- propylphenyl and M is CuCI.
  • a further optional component of the catalyst system is a Lewis acid, for example a compound of boron, such as BF 3 especially as its etherate or aluminium, such as AICI 3 or ethylAICI 2 or zinc, such as ZnCI 2 or a transition metal, such as TiCI 4 or FeCI 3 or a rare earth metal, such as the rare earths triflate salts.
  • a Lewis acid for example a compound of boron, such as BF 3 especially as its etherate or aluminium, such as AICI 3 or ethylAICI 2 or zinc, such as ZnCI 2 or a transition metal, such as TiCI 4 or FeCI 3 or a rare earth metal, such as the rare earths triflate salts.
  • the energy source can be conventional external heating, for example by a heated oil bath or can be microwave irradiation, for example in a commercial microwave apparatus specially designed for chemical reactions or in a domestic microwave cooker.
  • the preferred temperature for the inventive process is between room temperature and 250 0 C, more especially between 80 and 200 0 C.
  • the reaction is maintained at the selected temperature for between 10 minutes and 10 days, more especially between 2 hours and 7 days.
  • the preferred reaction time is 5-7 days.
  • the preferred conditions are 2 hours at 200 0 C.
  • the progress of the reaction may be followed by chromatographic techniques, for example by tic or hplc or by spectroscopic techniques, for example 1 H nmr spectroscopy. By means of such analysis, the progress of the reaction can be monitored, and the optimum temperature and time of the reaction can be determined.
  • the reaction may be carried out in a normal air atmosphere or in an inert atmosphere, as provided for example by nitrogen or argon.
  • the reaction may be carried out in a vented or a closed system, so that in the latter case on heating or microwave irradiation the reaction becomes pressurised, and allows use of solvents above their normal boiling points.
  • the inventive process is carried out in the presence of a solvent.
  • Solvents which can be used include all common organic solvents, especially aromatic hydrocarbons, more especially toluene; or especially halogenated aliphatic hydrocarbons, more especially 1 ,2-dichloroethane.
  • the ligand used with the transition metal catalyst is pyridine or another liquid aromatic base, that ligand, especially pyridine, can also be used as the solvent.
  • Less traditional solvents such as ionic liquids may also be used, in which case reaction times are shorter.
  • Solvents are preferably dry, thus excluding water.
  • the compound of the formula (I) can be separated and purified free from catalyst, solvent, any remaining starting material, and any by-products, by standard organic chemical techniques, familiar to those skilled in the art.
  • R together with the two carbon atoms to which it is bonded, forms a benzene ring or a substituted benzene ring.
  • R 4 to R 7 independently, have one of the meanings defined for R 1 to R 3 above, or R 4 and R 5 or R 5 and R 6 or R 6 and R 7 , together with the carbon atoms to which they are bonded, form a ring; is treated according to the invention to form a compound of the formula (Ia)
  • n denotes 1 , 2, 3 or 4 and the substituents R 8 , independently, have one of the meanings defined for R 1 to R 3 above.
  • one of R 4 to R 7 in the compound of formula (Ma) denotes a group of the formula (IV)
  • R 1 to R 3 are defined as given above, while the two remaining groups of R 4 to R 7 are defined as given above.
  • R 5 denotes a group of the formula (IV)
  • R 6 denotes a group of the formula (V)
  • R 1 to R 4 , R 7 and X are defined as given above.
  • the compounds of the formula (If) to (Ik) are available by exposing different isomers of the compound of formula (Mb) to treatment according to the present invention.
  • two of R 4 to R 7 in the compound of formula (Ma) denote a group of the formula (IV) and two other of R 4 to R 7 denote a group of the formula (V), wherein the groups of the formulae (IV) and (V) are pairwise ortho-related to one another. Accordingly, a compound of formula (lie)
  • R 1 to R 4 , R 7 and X are defined as given above.
  • R together with the two carbon atoms to which it is bonded, forms a heterocyclic ring or a substituted heterocyclic ring.
  • R 1 to R 3 , R 8 , X and het are defined as given above, is formed.
  • Example meanings of het are pyridine, quinoline, isoquinoline, 2-pyrone and coumarin.
  • R together with the two carbon atoms to which it is bonded, forms a ring which is substitued by a group which contains a further pair or further pairs of groups of formulae (IV) and (V). Accordingly, if a compound of formula (Me)
  • each P independently is a carbocyclic aromatic or heterocyclic ring and L represents one or more direct linking bonds, or one or more linking atom or groups of atoms, or a combination of direct bonds and linking atom or atoms, wherein L can also be part of P, is treated according to the present invention a compound of the formula (Ip)
  • R 1 to R 3 , X, P and L are defined as given above, is formed.
  • the present invention further refers to a process for preparing a compound of the formula (I)
  • R denotes an organic radical which, together with the two carbon atoms to which it is bonded, forms a carbocyclic or heterocyclic ring
  • R 1 , R 2 , R 3 and X independently, denote hydrogen, halogen, nitro, cyano or an organic radical
  • R 1 and R 2 or R 2 and R 3 together with the carbon atoms to which they are bonded, form a ring; which comprises exposing a compound of the formula (Vl)
  • R 1 , R 2 , R 3 and X are defined as given above and Y and Z, independently, have one of the meanings of X; to an energy source in the presence of a catalyst system.
  • the compounds of the formula (II) can be prepared by methods which are known to those skilled in the art.
  • the compounds of the formula (II) are ortho-allyl-substituted phenyl esters which for example can be prepared by standard methods from ortho-allyl-phenol precursors. These in turn may be derived by rearrangement (e.g. the ortho-Claisen rearrangement) of the corresponding phenyl allyl ethers, themselves derived from phenols.
  • Aromatic compounds are used in many diverse areas of the chemical industry, for example, pharmaceuticals, agrochemicals, dyes and pigments, cosmetics, oil chemicals, electronics chemicals, auxiliaries, flavours and fragrances and as components of polymers and other materials, including components of catalysts.
  • the process defined in the current invention provides new ways to synthesise compounds used directly in any of the above or other industries, or to synthesise compounds used as intermediates for further chemical modification in the manufacture of ultimate products of interest in any of the above or other industries.
  • reaction vessel was cooled, and 1-chloronaphthalene was found to be the sole product by 1 H nmr spectroscopy. It was isolated in 81 % yield, and found to be identical to authentic material by chromatographic (hplc and tic) and spectroscopic comparison.
  • Example 21 is an example of a multiply-substituted precursor.
  • the allyl-substituted coumarin ester (25a) was exposed to the same conditions as Example 1 , using pro rata the same amounts of starting material, solvent and catalyst, the chloro-substituted benz-fused coumarin product (25b) was isolated, characterised by mass spectrometry and 1 H nmr and IR spectroscopy.
  • Example 26 The Examples in the following Table exemplify alternative conditions to those described in Example 1 that also lead to efficient conversion of o-allyphenyl trichloroacetate to 1-chloronaphthalene.
  • DCE 1 ,2-dichloroethane
  • MW microwave
  • IL ionic liquid (1-butyl-3-methylimidazolium chloride).
  • Catalyst (MId) is especially active in the transformations of the current invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé pour la préparation d'un composé représenté par la formule (I) dans laquelle R désigne un radical organique lequel, conjointement avec les deux atomes de carbone auxquels il est lié, forme un noyau carbocyclique ou hétérocyclique ; R1, R2, R3 et X, indépendamment, désignent hydrogène, halogène, nitro, cyano ou un radical organique ; ou R1 et R2 ou R2 et R3, conjointement aux atomes de carbone auxquels ils sont liés, forment un cycle, ledit procédé comprenant l'exposition d'un composé représenté par la formule (II) dans laquelle R1, R2, R3 et X sont définis comme indiqué ci-dessus et Y et Z, indépendamment, ont l'une des significations de X, à une source d'énergie en présence d'un système catalytique.
PCT/EP2007/055923 2006-06-20 2007-06-14 Procédé de synthèse de composés aromatiques Ceased WO2007147775A1 (fr)

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GB0612219.6 2006-06-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015512A1 (fr) 2020-12-16 2022-06-22 AMO Ireland Dispositifs optiquement actifs

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DURAND-DRAN: "Etude de la fixation de dérivés halogénés sur les allyl benzènes en présence de peroxides et cyclisation des composés polyhalogénés obtenus en dérivés naphtaléniques polysubstitués", ANNALES DE CHIMIE, vol. 13, 1959, Paris, pages 43 - 53, XP009089430 *
FRANK O H PIRRUNG, HENK HIEMSTRA, W NICO SPECKAMP: "Synthesis of medium-sized lactones by the copper(I)chloride/2,2'-bipyridine-catalyzed cyclization of di- and trichloroacetates", TETRAHEDRON, vol. 50, no. 43, 1994, pages 12415 - 12442, XP002450576 *
JUNHUA WANG, CHAOZHONG LI: "Investigation of bis(tributyltin)-initiated free radical cyclization reactions of 4-pentenyl iodoacetates", JOURNAL OF ORGANIC CHEMISTRY, vol. 67, 2002, pages 1271 - 1276, XP002450575 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015512A1 (fr) 2020-12-16 2022-06-22 AMO Ireland Dispositifs optiquement actifs
WO2022128832A1 (fr) 2020-12-16 2022-06-23 Merck Patent Gmbh Dispositifs optiquement actifs

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