WO2006011880A1 - Amines aromatiques a faible solvatation - Google Patents

Amines aromatiques a faible solvatation Download PDF

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Publication number
WO2006011880A1
WO2006011880A1 PCT/US2004/021140 US2004021140W WO2006011880A1 WO 2006011880 A1 WO2006011880 A1 WO 2006011880A1 US 2004021140 W US2004021140 W US 2004021140W WO 2006011880 A1 WO2006011880 A1 WO 2006011880A1
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process according
solvation
solvent
independently selected
alcohol
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PCT/US2004/021140
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English (en)
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Jason Hirsch
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Eastman Kodak Company
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Priority to PCT/US2004/021140 priority Critical patent/WO2006011880A1/fr
Publication of WO2006011880A1 publication Critical patent/WO2006011880A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification

Definitions

  • This invention relates to the field of organic syntheses and to a process for forming an aromatic amine compound with low solvation.
  • Aromatic amine compounds are very useful materials and consequently there is a continuing need for improved synthetic methods that allow their preparation in an economical manner and in high purity, hi particular, tertiary amine compounds have found use in electroluminescent (EL) devices such as organic light-emitting diodes (OLEDs).
  • EL electroluminescent
  • OLEDs organic light-emitting diodes
  • an organic EL device is comprised of an anode for hole injection, a cathode for electron injection, and an organic medium sandwiched between these electrodes to support charge recombination that yields emission of light. These devices are also commonly referred to as organic light- emitting diodes, or OLEDs. Representative of earlier organic EL devices are Gurnee et al. US 3,172,862, issued Mar. 9, 1965; Gurnee US 3,173,050, issued Mar.
  • organic EL devices include an organic EL element consisting of extremely thin layers (e.g., less than 1.0 ⁇ m) between the anode and the cathode.
  • organic EL element encompasses the layers between the anode and cathode. Reducing the thickness lowered the resistance of the organic layer and has enabled devices that operate at much lower voltage.
  • one organic layer of the EL element adjacent to the anode is specifically chosen to transport holes, and therefore, it is referred to as the hole-transporting layer, and the other organic layer is specifically chosen to transport electrons, and is referred to as the electron-transporting layer. Recombination of the injected holes and electrons within the organic EL element results in efficient electroluminescence.
  • the hole-transporting layer of the organic EL device contains at least one hole-transporting compound such as an aromatic tertiary amine, where the latter is understood to be a compound containing at least one trivalent nitrogen atom that is bonded only to carbon atoms, at least one of which is a member of an aromatic ring.
  • the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine. Exemplary monomelic triarylamines are illustrated by Klupfel et al. US 3,180,730.
  • triarylamines substituted with one or more vinyl radicals and/or comprising at least one active hydrogen containing group are disclosed by Brantley et al US 3,567,450 and US 3,658,520.
  • a more desirable class of aromatic tertiary amines include at least two aromatic tertiary amine moieties as described in US 4,720,432 and US 5,061,569.
  • Suitable tertiary amine derivatives can be synthesized by various methods including the Ullmann condensation which involves the coupling of aryl halides with copper, for example see J. March, Advanced Organic Chemistry, 3 rd Ed., John Wiley and Sons, NY, 1985, page 597.
  • S. Turner and coworkers in US 4,764,625 describe a process of preparing a tertiary amine by the condensation of an amine compound and an iodoaryl compound. The reaction is carried out in the presence of potassium hydroxide, and a copper catalyst at a temperature between 120 0 C to about 190 0 C, however these are harsh conditions and can cause substantial decomposition of sensitive compounds.
  • the organic materials in an OLED device are often conveniently deposited through sublimation.
  • the material to be deposited by sublimation can be vaporized from a sublimator "boat" often comprised of a tantalum material, e.g., as described in US 6,237,529, or can be first coated onto a donor sheet and then sublimed in closer proximity to the substrate. Layers with a mixture of materials can utilize separate sublimator boats or the materials can be pre-mixed and coated from a single boat or donor sheet.
  • the material to be deposited be substantially free of volatile solvents. If the material contains solvents that are released during the sublimation process the vacuum will be disrupted and the equipment may be contaminated and this will interrupt the manufacturing process.
  • solvent is incorporated into the crystal lattice of the material.
  • the solvent cannot be removed by normal drying methods, that is, by subjecting the material to low vacuum and moderate heating.
  • Solvent can be removed from solvated materials by subliming the material, however, this requires the use of expensive equipment and a time-consuming procedure. Consequently there remains a need for a process to prepare materials such as aromatic amines with low solvation to be used in EL devices.
  • the invention provides a process for preparing a polymorph of a N 5 N 5 TV ,/V -tetraaryldiamine having low solvation comprising: a) crystallizing the diamine from a solvent comprising a hydrocarbon to form a solvated polymorph; b) mixing the amine with an alcohol; c) distilling the mixture to remove a portion of the solvent; and d) repeating steps b and c until the desired level of low solvation is achieved.
  • the invention provides aromatic amines with low solvation as needed for organic electroluminescent devices.
  • FIG. 1 shows a XRD spectrum of a solvated crystal form of 4,4'- Bis[iV-(l-naphthyl)-N-(2-na ⁇ hthyl)amino]biphenyl (AA-I).
  • FIG. 2 shows a XRD spectrum of a crystal form of 4,4'-Bis[N-(l- naphthyl)-iV-(2-naphthyl)amino]bi ⁇ henyl that is not solvated.
  • the invention process is summarized above.
  • the process is useful to provide a polymorph comprising a iV, ⁇ jV,iV-tetraaryldiamine compound having low solvation.
  • polymorphism The ability of a substance to crystallize with more than one type of lattice structure is known as polymorphism, and a particular form is known as a polymorph.
  • Some polymorphs incorporate solvent in the crystal lattice during crystallization to form a solvate, such polymorphs are also referred to as solvates or psuedopolymorphs.
  • Solvated polymorphs are not desirable, as already mentioned, for applications wherein the material will be subjected to vapor phase deposition, such as in an OLED device, because volatile solvent will be released during sublimation process.
  • the first step of the process, step (a) includes crystallizing the amine from a solvent comprising a hydrocarbon.
  • a hydrocarbon solvent comprises a saturated aliphatic hydrocarbon of 5 to 12 carbons, for example cyclohexane, heptane, and octane are such solvents.
  • cyclohexane, heptane, and octane are such solvents.
  • the solvated polymorph is converted to one that is not solvated.
  • the amine compound is mixed with an alcohol.
  • the alcohol comprises an aliphatic alcohol of 1 to 12 carbons, for example, ethanol or isopropanol. It is often the case that the amine compound is not very soluble in the alcohol but desirably it partially dissolves. When even a small amount does dissolve it can release some of the trapped hydrocarbon solvent from the crystal lattice.
  • step (c) a portion of the solvent is removed by distillation. This distillation removes both some alcohol solvent and some of the hydrocarbon solvent that has been released from the crystal lattice.
  • Steps (b) and (c) were then repeated. Each time the steps were repeated more of the trapped hydrocarbon solvent is released and removed from the reaction mixture. The steps were repeated as often as necessary until the desired level of low solvation is achieved.
  • a representative sample of the amine compound can be isolated and dried to remove any solvent external to the crystal lattice.
  • the solvation level can then be determined by H 1 NMR analysis. In the NMR spectrum the peaks due to the solvent molecules that were trapped in the crystal lattice can be compared to those due to the amine compound to determine the amount of solvent present relative to the amine.
  • the level of solvation of a representative sample can be determined by GC headspace analysis. For example see, B. V. Ioffe, A. G. Vitenberg, and I. A. Mamantov, Head-Space Analysis And Related Methods In Gas Chromatography, New York, John Wiley & Sons (1984). Li this method a sample of known weight is volatilized to release solvent molecules, which are then analyzed by gas chromatography. Another method to determine solvation is to measure the X-ray diffraction (XRD) pattern of a sample and compare it to a reference sample that is known to have low solvation, for example a sample that has been sublimed. If the sample affords the same XRD pattern as the reference sample, then it has low solvation. In one embodiment the level of solvent in the amine compound is suitably less than 0.50 % by weight, commonly less than 0.10 % and desirably less than 0.05 % by weight.
  • N'-tetraaryldiamine compounds are substituted with at least two independently selected diarylamine substituents which can be represented by Formula (A).
  • Ar 1 and Ar 2 represent independently selected aryl groups.
  • at least one of Ar 1 and Ar 2 contains a polycyclic fused ring structure, such as a naphthalene group.
  • Useful N !l ⁇ iV',iV'-tetxaaryldiamine compounds include those represented by structural Formula (1).
  • Q 1 and Q 2 are independently selected aromatic tertiary amine moieties and G is a linking group such as an arylene, cycloalkylene, or alkylene group of a carbon to carbon bond.
  • G is a linking group such as an arylene, cycloalkylene, or alkylene group of a carbon to carbon bond.
  • at least one of Q 1 or Q 2 contains a polycyclic fused ring structure, for example, a naphthalene group.
  • G is an aryl group, it is conveniently a phenylene, biphenylene, or a naphthalene moiety.
  • a useful class of NJVJV, iV- tetraaryldiamine compounds include those represented by structural Formula (2).
  • R 1 and R 2 each independently represents a hydrogen atom, an aryl group, or an alkyl group or R 1 and R 2 together represent the atoms completing a cycloalkyl group; and R 3 and R 4 each independently represents an aryl group, which is in turn substituted with a diaryl substituted amino group,
  • N 5 N 5 N 5 , ⁇ -tetraaryldiamine compounds include those represented by Formula (3).
  • each Ar represents an independently selected arylene group, such as a phenylene or anthracene moiety
  • each Ar 1 -Ar 4 represents an independently selected aryl group, such as a phenyl or naphthyl group
  • n is an integer of from 1 to 4.
  • at least one of Ar ⁇ Ar 4 is a polycyclic fused ring structure, e.g., a naphthalene moiety.
  • the compound is represented by Formula (4) wherein, as described previously, Ar 1 - Ar 4 are independently selected aryl groups.
  • Ar 1 and Ar 3 represent independently selected naphthyl groups and in one desirable embodiment Ar 1 -Ar 4 each represent independently selected naphthyl groups.
  • the various alkyl, alkylene, aryl, and arylene moieties of the foregoing structural Formulae A and (l)-(4), can each in turn be substituted.
  • Typical substituents include alkyl groups, alkoxy groups, aryl groups, and aryloxy groups.
  • the various alkyl and alkylene moieties typically contain from about 1 to 6 carbon atoms.
  • the cycloalkyl moieties can contain from 3 to about 10 carbon atoms, but typically contain five, six, or seven ring carbon atoms ⁇ e.g., cyclopentyl, cyclohexyl, and cycloheptyl ring structures.
  • the aryl and arylene moieties are usually phenyl and phenylene moieties.
  • Illustrative of useful aromatic tertiary amines are the following.
  • AA-7 Bis(4-dimethylamino-2-methylphenyl)phenylmethane AA-8 1 ,4-Bis[2-[4-[N,iV-di(/?-toly)amino]phenyl]vinyl]benzene AA-9 j y;iy; j V,JV-Tetta- j p-tolyl-4,4 l -diaminobi ⁇ henyl AA-10 NNN, N -Tetraphenyl-4,4'-diaminobiphenyl
  • substituted or “substituent” means any group or atom other than hydrogen.
  • group when the term “group” is used, it means that when a substituent group contains a substitutable hydrogen, it is also intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any substituent group or groups as herein mentioned, so long as the substituent does not destroy properties necessary for device utility.
  • a substituent group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, sulfur, selenium, or boron.
  • the substituent may be, for example, halogen, such as chloro, bromo or fluoro; nitro; hydroxyl; cyano; carboxyl; or groups which maybe further substituted, such as alkyl, including straight or branched chain or cyclic alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-£-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl,
  • the substituents may themselves be further substituted one or more times with the described substituent groups.
  • the particular substituents used may be selected by those skilled in the art to attain the desired desirable properties for a specific application and can include, for example, electron-withdrawing groups, electron-donating groups, and steric groups.
  • the substituents may be joined together to form a ring such as a fused ring unless otherwise provided.
  • the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
  • Example 1 Preparation of a polymorph of 4,4'-bis [N-(I -naphthyl)-N-(2- naphthyl)amino]biphenyl (AA-I) having low solvation.
  • N-l-Naphthyl-N-2-naphthylamine (12.7 kg, 47.14 mol)
  • 4,4'- diiodobiphenyl (9.8 Kg, 24.2 mol)
  • palladium (II) acetate (0.150 Kg, 0.663 mol)
  • toluene 140 Kg
  • Nitrogen was bubbled through the mixture for 30 min to remove oxygen.
  • the catalyst, tri-t-butylphosphine (0.6 Kg, 3.0 mol) was added as a 20 wt% solution in toluene with stirring and the mixture was heated to 75 0 C over a 1 h period.
  • the filtrate was distilled to 1/10 volume and methanol was added. After cooling to 10 °C, the product was allowed to crystallize for 12 hours and collected.
  • the crude product was dissolved in hot cyclohexane, treated with silica gel, and stirred for 16 h at 70 0 C and then filtered.
  • the filtrate was distilled to 1/10 volume and methanol was added. After cooling to 10 0 C, the product was allowed to crystallize again for 12 hours and collected.
  • the product was then slurried in isopropyl alcohol.
  • the isopropyl alcohol was distilled and replenished with fresh isopropyl alcohol. This procedure was repeated seven times for a total of eight times.
  • methanol was added, and the methanol was removed by distillation and replenished with fresh methanol. This was more two times.
  • the product mixture was cooled to 5O 0 C and the product was collected and dried at 75 °C in a vacuum oven to afford 4,4'- Bis[N-(l-naphthyl)-JV-(2-naphthyl)amino]biphenyl (7.0 Kg, 43.5 % yield).
  • Example 2 Steps b, c, and d of the process, preparation of a polymorph of AA-I having low solvation.
  • Example 2-1B was treated in the same manner as Sample 2-1 A to afford Sample 2-2B.
  • Samples 2-2A and 2-2B were combined and dried for 13 h at 75 0 C under vacuum and with nitrogen flow to afford 758 g of product with no detectible solvents present by NMR analysis.
  • Example 3 Determination of low solvation by XRD analysis.
  • Figure 1 shows a XRD spectrum of a sample of AA-I that was synthesized and not subjected to the inventive process.
  • This sample was known to contain solvent in the crystal lattice as confirmed by NMR.
  • Samples that afford the XRD pattern shown in Fig. 1 are known to have high solvation and do have solvent incorporated in the crystal lattice.
  • the sample was then treated by the process according to the invention.
  • a second XRD spectrum was then measured and is shown in Fig. 2. One can see that there are substantial differences in the spectra. Samples that afford the XRD pattern shown in Fig. 2 are known to have low solvation and do not have solvent incorporated in the crystal lattice.
  • Embodiment of this invention may provide amines of high purity and yield and low solvation.
  • the aromatic amine compounds having low solvation prepared according to this invention may be incorporated in an EL device.
  • the aromatic amine materials are included in a hole- transporting layer of an EL device.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'un polymorphe d'une N,N,N',N'-tétraaryldiamine présentant une faible solvatation. Ce procédé consiste : a) à cristalliser la diamine à partir d'un solvant contenant une hydrocarbure afin d'obtenir un polymorphe solvaté ; b) à mélanger l'amine avec un alcool ; c) à distiller le mélange afin d'éliminer une partie du solvant ; et d) à répéter les étapes b et c jusqu'à obtenir le niveau de faible solvatation désiré. Le procédé selon l'invention permet de réduire les niveaux de solvatation du polymorphe.
PCT/US2004/021140 2004-06-30 2004-06-30 Amines aromatiques a faible solvatation WO2006011880A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120223296A1 (en) * 2011-03-01 2012-09-06 Sensient Imaging Technologies Gmbh Organic Semiconducting Materials and Organic Component
US20140353617A1 (en) * 2013-06-04 2014-12-04 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting diode including the same
US10263191B2 (en) 2009-04-24 2019-04-16 Idemitsu Kosan Co., Ltd. Aromatic amine derivative, and organic electroluminescent element comprising the same
US10297765B2 (en) 2007-12-28 2019-05-21 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescent device using the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5576460A (en) * 1994-07-27 1996-11-19 Massachusetts Institute Of Technology Preparation of arylamines
US20030031893A1 (en) * 2000-12-15 2003-02-13 Shuang Xie Electroluminescent compositions and devices

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5576460A (en) * 1994-07-27 1996-11-19 Massachusetts Institute Of Technology Preparation of arylamines
US20030031893A1 (en) * 2000-12-15 2003-02-13 Shuang Xie Electroluminescent compositions and devices

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10297765B2 (en) 2007-12-28 2019-05-21 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescent device using the same
US11133478B2 (en) 2007-12-28 2021-09-28 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescent device using the same
US10263191B2 (en) 2009-04-24 2019-04-16 Idemitsu Kosan Co., Ltd. Aromatic amine derivative, and organic electroluminescent element comprising the same
US10686137B2 (en) 2009-04-24 2020-06-16 Idemitsu Kosan Co., Ltd. Aromatic amine derivative, and organic electroluminescent element comprising the same
US11024806B2 (en) 2009-04-24 2021-06-01 Idemitsu Kosan Co., Ltd. Aromatic amine derivative, and organic electroluminescent element comprising the same
US20120223296A1 (en) * 2011-03-01 2012-09-06 Sensient Imaging Technologies Gmbh Organic Semiconducting Materials and Organic Component
US9048435B2 (en) * 2011-03-01 2015-06-02 Novaled Ag Organic semiconducting materials and organic component
US20140353617A1 (en) * 2013-06-04 2014-12-04 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting diode including the same
KR20140142628A (ko) * 2013-06-04 2014-12-12 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함하는 유기 전계 발광 소자
US9876176B2 (en) * 2013-06-04 2018-01-23 Samsung Display Co., Ltd. Aryl amine condensed cyclic compound comprising pyrene moieties and organic light-emitting diode (OLED) including the same
KR102105076B1 (ko) * 2013-06-04 2020-04-28 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함하는 유기 전계 발광 소자

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