WO2018054877A1 - Procédé pour préparer des bistolanes substitués - Google Patents

Procédé pour préparer des bistolanes substitués Download PDF

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Publication number
WO2018054877A1
WO2018054877A1 PCT/EP2017/073578 EP2017073578W WO2018054877A1 WO 2018054877 A1 WO2018054877 A1 WO 2018054877A1 EP 2017073578 W EP2017073578 W EP 2017073578W WO 2018054877 A1 WO2018054877 A1 WO 2018054877A1
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formula
atoms
independently
compound
rest rest
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PCT/EP2017/073578
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German (de)
English (en)
Inventor
Andreas Lohr
Juergen Schemel
Mansoor D'lavari
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Merck Patent Gmbh
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Priority to CN201780057752.3A priority Critical patent/CN109715590B/zh
Priority to DE112017004727.7T priority patent/DE112017004727A5/de
Publication of WO2018054877A1 publication Critical patent/WO2018054877A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • 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
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a process for the preparation of
  • Bistolanes which are substituted in the 1, 1 'position with halogen and products of these compounds.
  • the C-C triple bonds of the bistolanes are generated by elimination reactions.
  • BistolanENSen are among others as performance chemicals such.
  • 1, 1 'dihalo-bis-olane derivatives are important as useful intermediates for the construction of highly conjugated aromatic compounds, e.g. B. oligo- (p-phenyleneethynylene) s.
  • bisiodebistolane is prepared from 1,4-diiodobenzene and 1,4-bisethynylbenzene.
  • the present invention therefore has for its object to provide a process for the preparation of halogenated bistolanes, which gives the desired product in high yield and purity and is safe and inexpensive to carry out on an industrial scale. Surprisingly, it has been found that these as well as other tasks not explicitly mentioned, however, are based on the introductory ones
  • Terephthalaldehyd or their derivatives can be produced.
  • the subject of the present invention is accordingly a
  • Each R ° is independently H or alkyl of 1 to 12 C atoms
  • r1, r2 are each independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2,
  • Ar represents an optionally substituted phenyl radical, to the carbonyl functions of a bis-aldehyde of the formula
  • Ar, X, L, r1 and r2 are independently as defined above, by means of an acid chloride R- (CO) Cl or an equivalent reagent, wherein Cyclohexyl or straight-chain or branched alkyl having 2 to 15 carbon atoms, wherein the alkyl radical is preferably a
  • L is alkyl having 1 to 4 C atoms
  • X is iodine or bromine, preferably iodine,
  • Ar is phenyl or p-tolyl.
  • a further process according to the invention therefore comprises the preparation of bistolan derivatives of the formula (VI)
  • a compound of formula (I) is prepared according to the process of the invention described above, and then reacted in one or more subsequent steps to give a compound of formula (VI), wherein in one of said subsequent steps a compound of the formula (I) is reacted with a substituted ethyne.
  • the compound of formula (I) is reacted by metal-catalyzed coupling at the position of the substituent X in the presence of a palladium complex (Sonogashira coupling).
  • a 1 "4 are each independently a radical selected from the following groups a) the group consisting of trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene and 4,4 '-Bicyclohexylen, in which one or more non-adjacent CH 2 groups may be replaced by -O- and / or -S- and in which also one or more H atoms may be replaced by a group L,
  • Y 1 ' 2 are each independently H, F, Cl, CN or R °,
  • R °, R 00 are each independently H or alkyl of 1 to 12 C atoms, m and n are independently 0, 1, 2, 3 or 4, o and p are independently 0, 1, 2, 3 or 4,
  • Alkynyl radicals at least two and the branched radicals at least three Having C atoms
  • one or more non-adjacent CH 2 groups are each independently selected from -O-, -S-, -Si (R 00 R 000 ) -, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N (R 00 ) -CO-O-,
  • Represents -O-CO-CH CH- or a single bond, preferably -CO-O- or -O-CO-,
  • R 00 is independently alkyl having 1 to 12 C atoms
  • Each R 000 is independently H or alkyl of 1 to 12 carbon atoms
  • Y 2 and Y 3 are each independently H, F, Cl or CN.
  • the required alkyne is a compound of the formula
  • the alkyne may already be substituted as the end compound of the formula (I), or it may correspond to an intermediate compound which is converted into a compound of the formula (VI) in a further reaction step (cf., Example 2.2)
  • the compound of the formula (VI) is in particular a compound selected from the compounds of the formulas (VI-1), (VI-2) and (VI-3):
  • R 1 and R 2 are as defined in formula (VI), and
  • q is 1, 2, 3, 4, 5 or 6, preferably 4.
  • the bistolane compounds obtainable by the process according to the invention are obtained in high purities and high yields of pure product. Furthermore, the products can be obtained overall cost-effective and without serious threat to humans and the environment.
  • the use of very toxic chlorophosphates as in conventional alkyne syntheses can likewise be dispensed with by the process according to the invention.
  • reaction is also suitable for additionally substituted dihalo-bistolanes of the formula (I) which are accessible by appropriately substituted starting materials of the formulas (II) and (III).
  • substituing derivatives are generally known or obtainable by conventional methods in analogy.
  • the ring system Ar contained in the intermediates of the formula (II) and (IV) is optionally substituted by one or more radicals, preferably radicals L 2 , which are independently defined when occurring repeatedly.
  • the radical L 2 mentioned as substituent of the ring system Ar preferably denotes, in each case independently of one another, F, Cl, Br, I, -CN, -NO 2, straight-chain or branched alkyl, alkenyl, alkynyl, alkoxy,
  • alkyl means a straight-chain or branched, saturated or
  • unsaturated, preferably saturated, aliphatic hydrocarbon radical of 1 to 15 i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15
  • alkoxy is meant an O-alkyl radical in which the oxygen atom is bonded directly to the group or substituted ring substituted by the alkoxy radical and alkyl is as defined above;
  • alkyl is then alkanyl or alkenyl.
  • Preferred alkoxy radicals are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy and octoxy, where any of these radicals can also be substituted, preferably with one or more fluorine atoms. Particular preference is given to alkoxy -OCH 3 , -OC 2 H 5, -OnC 3 H 7 , -OnC 4 H 9 , -OtC 4 H 9 , -OCF 3 ,
  • An alkenyl radical may contain from 2 to 15 (ie 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms and is branched chain or preferably straight chain. The rest is unsubstituted or monosubstituted or polysubstituted or differently substituted in particular with F, Cl, Br, I and / or CN.
  • CH CH group on both carbon atoms another When R Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest
  • Pentenyl 1E-hexenyl, 1E-heptenyl, 2-propenyl, 2E-butenyl, 2E-pentenyl, 2E-hexenyl, 2E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4- Pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl and 6-heptenyl.
  • Particularly preferred alkenyl radicals are vinyl, 1E-propenyl and 3E-butenyl.
  • an alkynyl radical is present.
  • the replacement of one or more CH 2 groups by -CO-O- or -O-CO- is possible.
  • the following of these radicals are preferred: acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl,
  • Butyryloxymethyl pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl or 4- (methoxycarbonyl) butyl.
  • cycloalkyl means a cyclic aliphatic (alicyclic) radical having 3 to 16 carbon atoms which is saturated or partially unsaturated and unsubstituted or mono- or polysubstituted by halogen, carboxy, nitro, alkanyl, alkoxy, -NH 2 and / or is substituted with -N (alkanyl) 2 , wherein the multiple substitution with the same or different
  • cycloalkyl radical is unsubstituted and has 5, 6 or 7 carbon atoms.
  • cycloalkyl is a cyclohexyl radical.
  • alkylene means a divalent aliphatic hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms in the chain, optionally also mono- or polysubstituted by halogen, CN, carboxy, nitro , Alkanyl, alkoxy, -NH 2 or substituted with -N (alkanyl) 2 , which multiple substitution can be made with the same or different substituents.
  • alkylene is a straight-chain, unsubstituted or mono- or disubstituted by methyl, saturated aliphatic radical having 1, 2, 3, 4, 5 or 6 carbon atoms, in particular -CH 2 CH 2 CH 2 - and -CH 2 C. (CH 3 ) 2 CH 2 -.
  • the radical X in the formulas (I), (II) and (IV) is preferably iodine or bromine, more preferably iodine.
  • the iodine compounds of the formula (I) can advantageously be easily derivatized.
  • For the reaction of terminal alkynes by Sonogashira coupling are iodaryl compounds
  • aldehydes of the formula (III) are preferably selected from the following sub-formulas:
  • alkyl means a linear or branched alkyl radical having 2 to 15 carbon atoms.
  • the inventive method is characterized by the fact that the compound of formula (IV) in reaction step b) from a
  • reaction step a) is preferably a
  • carboxylic acid chloride of the formula R- (CO) CI.
  • Other activated carboxylic acid derivatives e.g., anhydrides
  • the preferred carboxylic acid derivatives have a radical R selected from cyclohexane and alkyl having 3 to 15 C atoms.
  • Preferred radicals are cyclohexane and alkyl radicals having 3 to 15 carbon atoms, wherein the alkyl radical is preferably a secondary or tertiary alkyl radical, that is, the ⁇ -C atom is a secondary or tertiary carbon atom for steric shielding. Particular preference is given to cyclohexane, radicals having 3-5 C atoms, such as isopropyl, tert-butyl, isobutyl, tert-pentyl and sec-pentyl.
  • the reaction in step b) is preferably carried out between -70 ° C and 25 ° C.
  • the reaction time should be chosen so that the reaction has progressed sufficiently, but side reactions do not or only to a small extent occur.
  • the reaction time is typically less than 120 minutes, preferably less than 80 minutes.
  • step c) on the compounds of formula (IV) towards the bistolanes of formula (I) is carried out in the presence of an alkali metal base.
  • Alkali in this context means Li, Na, K, etc.
  • the base is preferably not nucleophilic. Strong bases are also preferred.
  • the alkali metal bases are preferably bases of alcohols, N-H compounds (eg, amines, silazanes) and CH compounds.
  • Suitable bases are KOtBu, LiHMDS, NaHMDS, KHMDS, LiTMP (lithium 2,2,6,6-tetramethylpiperidine), NaOtBu, Na-amylate (sodium tert-pentoxide), K-amylate (Potassium tert-pentoxide), LDA (lithium diisopropylamide), sec-butyl lithium and other organometallic reagents.
  • bases of the HMDS (1,1,1,3,3,3-hexamethyldisilazane).
  • the less expensive base KOtBu potassium tert-butylate
  • the preferred reaction temperature is between -30 ° C and 5 ° C.
  • the process according to the invention is preferably carried out using a solvent.
  • a solvent This means that the starting materials are preferably dissolved in a homogeneous phase or present as a suspension and react.
  • the solvents to be used include polar and hydrophobic solvents.
  • the sulfone of the formula (II) used is relatively sparingly soluble, especially in cold solvent. It is preferably initially charged in tetrahydrofuran (THF). The sulfone goes in a preferred
  • Embodiment slowly in solution and is immediately quantitatively deprotonated while the temperature of the reaction mixture of sulfone and base (eg KOtBu) is continuously increased.
  • This implementation prevents the formation of stilbene derivatives.
  • the base used is an alkali metal base (preferably soluble, for example KOtBu) instead of NaH.
  • the dosage is much easier compared to solid NaH on an industrial scale.
  • the compounds of the formula (I) prepared according to the invention can be excellently further derivatized, in particular by the known transition metal-catalyzed couplings of aryl halides.
  • Catalysts for carrying out Sonogashira, Heck or Suzuki coupling on the products of formula (I) are well known, preferably containing palladium compounds.
  • the preferred catalysts to be used can be made from common palladium (II) salts such as palladium chloride, bromide, iodide, acetate, acetylacetonate optionally substituted by further ligands, such as.
  • B. alkylnitriles may be stabilized, or from Pd (0) species such as palladium on activated carbon or tris (dibenzylideneacetone) dipalladium and phosphine ligands are generated in situ.
  • the base to be used in the Sonogashira coupling is preferably a nitrogen base, e.g. As pyridine or secondary amine, which can also serve as a solvent.
  • the Suzuki coupling base to be used is preferably selected from bases such as sodium hydroxide, sodium methoxide, sodium acetate, potassium fluoride, potassium phosphate or potassium carbonate (see Zysman-Colman, E., Science of Synthesis (2010) 45, 175, Chapter 45.4.2.1. 4 Method 4: Alkylation of Arenes via Suzuki Reaction of Alkylboranes and Related Alkylboron Reagents with Aryl Halides, DOI: 10.1055 / sos-SD-045-00123).
  • the process according to the invention and the subsequent work-up of the reaction mixture and / or the further reaction can in principle be carried out as a batch reaction or in a continuous reaction mode.
  • the continuous reaction includes z.
  • a stirred tank cascade As the reaction in a continuous stirred tank reactor, a stirred tank cascade, a loop or cross-flow reactor, a flow tube or in a microreactor.
  • the work-up of the reaction mixtures is optionally carried out, as required, by filtration over solid phases,
  • Solvents and / or azeotropic mixtures selective distillation, sublimation, crystallization, cocrystallization or by nanofiltration on membranes.
  • Iodobenzyl bromide (45.0 kg, 152 mol), sodium benzenesulfinate (26.2 kg, 160 mol) and ethanol (270 kg) are refluxed for 3 h. After cooling to 20 ° C., water (270 kg) is metered in over the course of 15 minutes, and the mixture is stirred further for 1 h. The product is isolated by filtration and the filter cake washed with water (180 kg) and ethanol (120 kg). The product is dried at 80 ° C in a vacuum.
  • Example 1.2 1, 1 'diiodobistolane 4-iodobenzylphenylsulfone (18.0 kg, 50.3 mol) is dissolved in tetrahydrofuran
  • Tetrahydrofuran 60 kg is added. The mixture is warmed to -25 ° C and stirred at this temperature for a further 90 min. The solution is cooled to -70 ° C and a solution of terephthalaldehyde (3.15 kg, 23.5 mol) in tetrahydrofuran (75 kg) is metered in so that the temperature is maintained in the range of -65 ° C ⁇ 5K. The mixture is stirred for a further 30 min. Cyclohexanecarboxylic acid chloride (9.3 kg, 63.4 mol) is metered in over the course of 15 minutes and the metering line is rinsed with 20 kg of tetrahydrofuran.
  • the mixture is heated at a rate of 3K / min to 20 ° C and stirred at this temperature for 1 h.
  • the mixture is again cooled to -20 ° C and LiHMDS in THF (20%, 157 kg, 188 mol) added so that the temperature remains below 0 ° C.
  • the mixture is stirred for a further 40 min at 0 ° C and then heated for 40 min at reflux.
  • hydrochloric acid (2 mol / L, 130 kg, 250 mol
  • the solid is isolated by filtration and washed with water (180 kg) and tetrahydrofuran (160 kg).
  • the product is dried at 50 ° C in a vacuum. Yield: 1 1, 4 kg (21, 5 mol, 91%). Purity: 99.6% (HPLC).
  • 1, 1 'Diiodobistolan, copper iodide and bis (triphenylphosphine) - palladium dichloride are suspended in a mixture of THF and diisopropylam and the mixture is heated to 60 ° C. Subsequently, a solution of the alkyne in tetrahydrofuran is added slowly.
  • Reaction mixture is cooled to room temperature and stirred overnight. After work-up, crystallization, filtration of the solid and drying, the product is obtained in 80% yield.
  • Diiodobistolan (Example 1 .2) is suspended at 20 ° C in toluene.
  • the corresponding cyclohexylcarboxylic acid acrylate compound, DMAP and stabilizer are added.
  • a solution of DCC in toluene is metered in and the mixture stirred for a further 5 h at 20 ° C.
  • the resulting N.N'-dicyclohexylurea is filtered off and the filtrate is worked up further. After crystallization, filtration of the solid and drying, the product is obtained in 75% yield.
  • the exemplary compound and the compounds of formula (VI) generally have a negative optical dispersion and impart special retardation properties to optical films (see WO 2016/020035 A1).

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

Abstract

La présente invention concerne un procédé de préparation de bistolanes qui sont substitués en position 1,1' avec halogène et des produits de ces composés. Les triples liaisons C-C des bistolanes sont produites par des réactions d'élimination.
PCT/EP2017/073578 2016-09-21 2017-09-19 Procédé pour préparer des bistolanes substitués WO2018054877A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780057752.3A CN109715590B (zh) 2016-09-21 2017-09-19 制备取代的双二苯乙炔的方法
DE112017004727.7T DE112017004727A5 (de) 2016-09-21 2017-09-19 Verfahren zur herstellung von substituierten bistolanen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16189875 2016-09-21
EP16189875.4 2016-09-21

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016020035A1 (fr) 2014-08-04 2016-02-11 Merck Patent Gmbh Matière polymérisable à cristaux liquides et film de polymère présentant une dispersion optique négative
EP3053909A1 (fr) 2013-09-30 2016-08-10 LG Chem, Ltd. Composé dispersible en longueur d'onde inverse, et composition dispersible en longueur d'onde inverse et corps optiquement anisotrope la comprenant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE46426E1 (en) * 2007-03-30 2017-06-06 Merck Patent Gmbh Birefringent polymer film with negative optical dispersion

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3053909A1 (fr) 2013-09-30 2016-08-10 LG Chem, Ltd. Composé dispersible en longueur d'onde inverse, et composition dispersible en longueur d'onde inverse et corps optiquement anisotrope la comprenant
WO2016020035A1 (fr) 2014-08-04 2016-02-11 Merck Patent Gmbh Matière polymérisable à cristaux liquides et film de polymère présentant une dispersion optique négative

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
TADAKATSU MANDAI ET AL: "Novel synthesis of acetylenes and polyenes via a desulfonylation reaction", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 106, no. 12, 1 June 1984 (1984-06-01), US, pages 3670 - 3672, XP055434800, ISSN: 0002-7863, DOI: 10.1021/ja00324a044 *
XUE CUIHUA ET AL: "Rapid syntheses of oligo(p-phenyleneethynylene)s via iterative convergent approach", TETRAHEDRON, vol. 60, no. 30, 19 June 2004 (2004-06-19), pages 6285 - 6294, XP085039563, ISSN: 0040-4020, DOI: 10.1016/J.TET.2004.05.085 *
XUE ET AL., TETRAHEDRON, vol. 60, 2004, pages 6285 - 6249
ZYSMAN-COLMAN, E., SCIENCE OF SYNTHESIS, vol. 45, 2010, pages 175

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TW201819346A (zh) 2018-06-01
CN109715590A (zh) 2019-05-03
DE112017004727A5 (de) 2019-06-19
CN109715590B (zh) 2022-07-22

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