(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) VVorld Intellectual Property Organization
`International Bureau
`
`(43) International Publication Date
`23 September 2010 (23.09.2010)
`
`International Patent Classification:
`C09K 11/06 (2006.01)
`
`(10) International Publication Number
`
`WO 2010/107244 A2
`
`ung S00 [KR/KR]; #405—1409, Samik Apt, Suseo—dong,
`Gangnam-gu, Seoul 135-884 (KR).
`
`International Application Number:
`PCT/KR2010/001647
`
`Agents: KWON, Oh-Sig et aI.; 4F, Jooeunleaderstel,
`921, Dunsan—dong, Seo—gu, Daejeon 302-120 (KR).
`
`International Filing Date:
`
`Filing Language:
`
`Publication Language:
`
`17 March 2010 (17.03.2010)
`
`English
`
`English
`
`KR
`
`Designated States (unless otherwise indicated, for every
`kind ofnational protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW', BY, BZ,
`CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO,
`DZ, EC, EE, EG, ES, FI, GB, GD, GE, GII, GM, GT,
`HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP,
`KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
`MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO,
`NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE,
`SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT,
`TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`Priority Data:
`10-2009-0023944 20 March 2009 (20.03.2009)
`
`Applicant (for all designated States except US): DOW
`ADVANCED
`DISPLAY MATERIALS,
`LTD.
`[KR/KR]; 735-2, Baekseok-dong, Seobuk-gu, Cheonan-
`si, Chungcheongnam-do 331-980 (KR).
`
`Inventors; a11d
`Inventors/Applicants (for US only): KIM, Chi Sik [KR/
`KR]; F3,
`14-60, Seongsul-ga, Seongdong-gu, Seoul
`133-111 (KR). CHO, Young Ju11 [KR/KR]; #101-1111,
`Samsung Apt., 15-1, Donam-dong, Seongbuk-g11, Seoul
`136-060
`(KR). KVVON, Hyuck
`J00
`[KR/KR];
`#224-2001, Sarnsung Raemian 2 Cha,
`Jangan-dong,
`Dongdaemun-gu, Seoul 130-100 (KR). KIM, Bong Ok
`[KR/KR]; #101—1108, Hansol Apt., 4, Samseong—dong, published;
`.
`.
`1
`.
`Gangnam-gu, Seoul 135-090 (KR). KIM, Sung Min
`.
`[KR/KR]; #109902) Mokdong Paragon, 917) Mok 1_ — without international search report and to be republished
`dong, Yangcheon—gu, Seoul 158-761 (KR). YOON, Se-
`“P0” rem?‘ ‘’f”“" ’“P”’"’ (R1419 48-213))
`
`Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ,
`TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE,
`ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
`MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM,
`TR), OAPI (BF, BJ, CI", CG, CI, CM, GA, GN, GQ, GW,
`ML, MR, NE, SN, TD, TG).
`
`N <<
`
`1-
`<1-
`
`Nl
`
`\aV
`
`-1E
`
`(54) Title: NOVEL ORGANIC IJLECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DE-
`VICE USING THE SAME
`
`(57) Abstract: Disclosed are a novel organic electroluminescent compound and an organic electroluminescent device comprising
`the same. When used as host material of organic electroluminescent material of an OLl£l) device, the disclosed organic electrolu-
`minescent compound exhibits high luminous efficiency and excellent life property of the material as compared to conventional
`host material. Therefore, it can be used to manufacture OLEDS having Very good ope1'ation life.
`
`aV
`
`-1
`
`eN g
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000001
`
`

`
`W0 2010/107244
`
`PCT/KR20l0/001647
`
`Description
`
`Title of Invention: NOVEL ORGANIC ELECTROLUMINESCENT
`
`COMPOUNDS AND ORGANIC ELECTROLUMINESCENT
`
`DEVICE USING THE SAME
`
`Technical Field
`
`The present invention relates to novel organic electroluminescent compounds and
`
`organic electroluminescent devices comprising the same. Specifically, it relates to
`
`novel organic electroluminescent compounds employed as electroluminescent material,
`
`and organic electroluminescent devices using them as a host.
`
`Background Art
`
`The most important factor to determine luminous efficiency of an OLED (organic
`
`light—emitting diode) is the type of electroluminescent material. Though fluorescent
`
`materials has been widely used as an electroluminescent material up to the present, de-
`
`velopment of phosphorescent materials is one of the best methods to improve the
`
`luminous efficiency theoretically up to four(4) times, in view of electroluminescent
`mechanism.
`
`Up to now, iridium (III) complexes are widely known as phosphorescent material,
`
`including (acac)Ir(btp)2, Ir(ppy)g, and Firpic, as the red, green and blue one, re-
`
`spectively. In particular, a lot of phosphorescent materials have been recently in-
`
`vestigated in Japan, Europe and America.
`
`Me
`
`O.
`
`,
`
`yr
`
`/
`-0'
`Me
`
`I \
`'N /
`
`/ 3
`
`2
`
`\
`I
`.N /
`
`‘
`
`Ir’
`
`(acac)lr(btp)2
`
`”lPPVl3
`
`Firpic
`
`As a host material for phosphorescent light emitting material,
`
`4,4'—N,N'—dicarbazole—biphenyl (CBP) has been most widely known up to the present,
`
`and OLED's having high efficiency to which a hole blocking layer (such as BCP and
`
`BAlq) had been applied have been known. Pioneer (Japan) or the like reported OLED's
`
`of high performances which employs
`
`bis(2—methyl—8—quinolinato)(p—phenylphenolato)aluminum (III) (BAlq) derivatives as
`the host.
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000002
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`BA|q
`
`BA|q derivative
`
`Though the materials in prior art are advantageous in View of light emitting property,
`
`they have low glass transition temperature and very poor thermal stability, so that the
`
`materials tend to be changed during the process vapor—deposition in vacuo at high tem-
`
`perature. In an OLED, it is defined that power efficiency 2 (rt/voltage) X cun‘ent ef-
`
`ficiency. Thus, the power efficiency is inversely proportional to the voltage, and the
`
`power efficiency should be higher in order to obtain lower power consumption of an
`
`OLED. In practice, a11 OLED employing phosphorescent electroluminescent material
`
`shows significantly higher current efficiency (cd/A) than an OLED employing flu-
`
`orescent EL material. However, in case that a conventional material such as BAlq and
`
`CBP as host material of the phosphorescent material is employed, no significant
`
`advantage can be obtained in terms of power efficiency (lm/w) because of higher
`
`operating voltage as compared to an OLED employing a fluorescent material.
`
`Moreover, such an OLED cannot result in satisfactory device life.
`
`Thus, development of host material having more improved stability and per-
`
`formances is required.
`
`Disclosure of Invention
`
`Technical Problem
`
`The present inventors endeavored to overcome the problems of conventional
`
`techniques, and consequently invented novel electroluminescent compounds to realize
`
`organic electroluminescent devices having excellent luminous efficiency and re-
`
`markably lengthened device life.
`
`Thus, the object of the invention is to overcome those problems and to provide
`
`organic electroluminescent compounds comprising a backbone to result in better
`
`luminous efficiency, improved device life, and appropriate color coordinate, as
`
`compared to conventional host materials.
`
`Another object of the invention is to provide organic electroluminescent devices
`
`having high efficiency and long life, which employ such organic electroluminescent
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000003
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`compounds as electroluminescent material.
`
`Solution to Problem
`
`Specifically, the present invention relates to organic electroluminescent compounds
`
`represented by one of Chemical Formulas (1) to (5), and organic electroluminescent
`
`devices compiising the same. Since the organic electroluminescent compounds
`
`according to the present invention provide better luminous efficiency and excellent life
`
`property as compared to conventional host material, OLED's having excellent
`
`operation life can be obtained therefrom.
`
`[Chemical Formula 1]
`
`[Chemical Formula 4]
`
`Z2'Z3
`Z?
`.-
`
`[Chemical Formula 5]
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000004
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`22]
`
`z
`
`,’z5
`5‘.
`z,-zs
`
`wherein,
`
`X and Y are independently selected from N(Ar1), O and S, wherein Ari may be
`
`different from one another, and Arl may be represented as Arl or Arg where there are
`
`two or more Ar, groups;
`
`Z1 through Z3 are independently selected from C(Ar3) and N, wherein Ar3 may be
`
`different from one another, and adjacent AI3 groups may be linked together to form a
`
`ring;
`
`Ari and Ar; are independently selected from (Cl—C60)all<yl, (C3—C60)cycloall<yl, 5-
`
`or 6—membered heterocycloalkyl containing one or more heteroatom(s) selected from
`
`N, O, S, Si a11d P, (C7—C60)bicycloall<yl, adamantyl, (C2—C60)all<enyl,
`
`(C2—C60)alkynyl, (C6—C60)aryl and (C3—C60)heteroaryl;
`
`AI3 are independently selected from hydrogen, (_Cl—C60)alkyl, halogen, cyano,
`
`(C3—C60)cycloalkyl, 5- or 6—membered heterocycloalkyl containing one or more
`
`heteroatom( s) selected from N, O, S, Si and P, (C7—C60)bicycloalkyl, adamantyl,
`
`(C2—C60)alkenyl, (C2—C60)alkynyl, (C6—C60)aryl, (Cl—C60)alkoXy, (_C6—C60)aryloXy,
`
`(C3—C60)heteroaryl, (_C6—C60)arylthio, (_Cl—C60)alkylthio, mono— or
`
`di(Cl—C30)alkylamino, mono— or di(C6—C30)arylamino, tri(Cl—C30)all<ylsilyl,
`
`di(Cl—C30)alkyl(C6—C30)arylsilyl, tri(C6—C30)arylsilyl, 1nono— or
`
`di(C6—C30)arylboranyl, mono— or di(Cl—C60)alkylboranyl, nitro and hydroxyl; and
`
`the alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, adamantyl, alkenyl, alkynyl,
`
`aiyl, alkoxy, aryloxy, heteroaiyl, arylthio, alkylthio, alkylamino, aiylamino,
`
`tri-
`
`alkylsilyl, dialkylarylsilyl, triarylsilyl, arylboranyl or alkylboranyl of Arl through AF3
`
`may be further substituted by one or more substituent(s) selected from a group
`
`consisting of (Cl—C60)alkyl, halogen, cyano, (C3—C60)cycloalkyl, 5- or 6—membered
`
`heterocycloalkyl containing one or more heteroatom(s) selected from N, O, S, Si and
`
`P, (C7—C60)bicycloalkyl, adamantyl, (C2—C60)alkenyl, (C2—C60)all<ynyl,
`
`(C6—C60)aryl, (Cl—C60)alkoXy, (C6—C60)aryloXy, (C6—C60)aryl substituted by P(=O)R
`
`,Rb [Ra and Rb independently represent (Cl—C60)al1<yl or (C6—C60)aryl],
`
`(C3—C60)heteroa1yl, (C3—C60)heteroaryl subsitituted by (C6—C60)aryl,
`
`(C3—C60)heteroaryl substituted by (Cl—C60)alkyl, (C6—C60)ar(Cl—C60)alkyl,
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000005
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`(C6—C60)arylthio, (Cl—C60)alkylthio, mono— or di(Cl—C30)a]kylamino, mono— or
`
`di(_C6—C30)arylamino, tri(C l —C30)alkylsilyl, di(C l —C30)alkyl(C6—C30)arylsilyl,
`
`tri(C6—C30)arylsilyl, mono— or di(C6—C30)arylboranyl, mono— or
`
`di(C 1 —C60) alkylboranyl, nitro and hydroxyl,
`
`excluding the case where both X and Y are N(Ar1) and all of Z1 through Z3 are C(Ar;.
`
`).
`
`The substituents, as described here, which comprises "(Cl—C60)alkyl" moiety may
`
`contain from 1 to 60 carbon atoms, from 1 to 20 carbon atoms, or from 1 to 10 carbon
`
`atoms. The substituents comprising "(_C6—C60)aryl" moiety may contain from 6 to 60
`
`carbon atoms, from 6 to 20 carbon atoms, or from 6 to 12 carbon atoms. Those
`
`comprising "(C3—C60)heteroaryl" moiety may contain from 3 to 60 carbon atoms, from
`
`4 to 20 carbon atoms, or from 4 to 12 carbon atoms. Those comprising
`
`"(C3—C60)cycloa1kyl" moiety may contain from 3 to 60 carbon atoms, from 3 to 20
`
`carbon atoms, or from 3 to 7 carbon atoms. The substituents comprising
`
`"(C2—C60)alkenyl or alkynyl" moiety may contain from 2 to 60 carbo11 atoms, from 2
`
`to 20 carbon atoms, or from 2 to 10 carbon atoms.
`
`The term 'alkyl' of the present invention include linear or branched saturated
`
`monovalent hydrocarbon radicals or combinations thereof, which are composed only
`
`of carbon atoms and hydrogen atoms. The term 'alkoxy' means —O—a]kyl group, in
`
`which alkyl is defined as above.
`
`The term "aryl" described herein represents an organic radical derived from aromatic
`
`hydrocarbon by deleting one hydrogen atom therefrom. Aryl groups include
`
`monocyclic and fused ring system, each ring of which suitably contains from 4 to 7,
`
`preferably from 5 or 6 cyclic atoms. Structures wherein two or more aryl groups are
`
`combined through chemical bond(s) are also included. Specific examples include
`
`phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, tiiphenylenyl,
`
`pyrenyl, perylenyl, chrysenyl, naphtacenyl, fluoranthenyl and the like, but are not re-
`stricted thereto.
`
`The term "heteroaryl" described herein means an aryl group containing from 1 to 4
`
`heteroatom( s) selected from N, O and S for the aromatic cyclic backbone atoms, and
`
`carbon atom(s) for remaining aromatic cyclic backbone atoms. The heteroaryl may be
`
`a 5- or 6—membered monocyclic heteroaryl or a polycyclic heteroaryl which is fused
`
`with one or more benzene 1ing(s), and may be partially saturated. The structures
`
`having one or more heteroaryl groups bonded through chemical bond(s) are also
`
`included. The heteroaryl groups may include divalent aryl groups of which the het-
`
`eroatoms are oxidized or quartemized to f0I‘l’1’1 N—oxides, quaternary salts, or the like.
`
`Specific examples include mo11ocyclic heteroaryl groups such as furyl, thienyl,
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000006
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl,
`
`oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl,
`
`pyrazinyl, pyrimidinyl, pyridazinyl; polycyclic heteroaryl groups such as benzofuryl,
`
`benzothienyl, isobenzofuryl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, ben-
`
`zisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl,
`
`isoquinolyl, cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenan—
`
`thridinyl and benzodioxolylg and corresponding N—oXides (for example, pyridyl N-
`
`oxide, qui11olyl N—oXide) and quaternary salts thereof; but they are not restricted
`thereto.
`
`The organic electroluminescent compounds according to the invention can be ex-
`
`emplified by the compounds represented by one of the following chemical formulas:
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000007
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000008
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`wherein, A11 and Ar; are defined as in Chemical Formulas (1) to (5).
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000009
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`[55]
`
`Furthermore, the organic electroluminescent compounds according to the present
`
`invention can be exemplified by the compounds represented by one of the following
`chemical formulas:
`
`A’I~N
`
`O
`
`Ar1~N
`
`O
`
`ArI~N
`
`O
`
`O
`
`O
`
`O
`
`Ar1~N
`
`O
`
`”’ I
`Ar‘. \
`‘Arz
`
`Ar,
`
`ArI~N
`Ar1~N
`Ar1~N
`_Ar,
`_Ar2
`’Arz
`_Ar,
`_Ar;
`,A "2
`Q I‘ Q N Q N Q I‘ Q N Q I Q N
`‘N
`\
`\
`I \
`‘N
`I ‘N
`I \
`I
`I
`I
`I J
`/
`/N
`Na
`N /
`Mr
`N /
`N\¢N
`
`TB1
`
`TB2
`
`TB3
`
`TB4
`
`TB5
`
`TB6
`
`TBT
`
`‘N
`/
`
`I
`
`TB8
`
`TB5Z
`
`wherein, A11 and Ar; are defined as in Chemical Formulas (l) to (5).
`
`The organic electroluminescent compounds according to the present invention can be
`
`specifically exemplified by the compounds represented by one of the following
`chemical formulas:
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000010
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`[65]
`
`0 Q
`Q J
`
`Q
`O
`
`TC3
`
`Q Q Q
`:1 0
`
`T
`
`0 00 Q s
`s O O Q Q
`0
`550V
`0
`TC1 0
`TC12
`
`TC11
`
`wherein, Ar. is defined as in Chemical Formulas (1) to (5).
`
`More specifically, Arl and Arg independently represent phenyl, l—naphthyl or
`
`2—naphthyl, or a substituent represented by one of the following chemical formulas, but
`
`they are not restricted thereto.
`
`_,N
`
`H2
`
`,
`
`_
`
`H3 D H4 Q
`
`9 ‘N
`
`H6
`
`H7
`
`-
`
`H8
`
`0 ‘F
`as \
`H10
`
`«NI
`M=\N ‘
`N=N/
`N—/
`»N.N ‘(Q ’ N»
`\ I
`:1
`\N I
`:1
`I : at \ : : = \N /
`H11 H H13
`H19
`
`H14
`
`H15
`
`H16
`
`H17
`
`H18
`
`,
`
`/
`
`N-
`
`=N@
`
`H9
`
`WJQ
`*«-&’N
`H20
`
`N-
`I‘
`N,
`1 N9 ffl
`___
`‘
`__ N‘ Q
`* *’Q *’K\—N N *
`‘N * "(£13 *‘<l|\:g fl
`H:
`H24
`H35
`H27
`\
`H28
`
`H21
`
`"22
`
`3
`
`H25
`
`as
`
`'‘
`
`H30
`
`H29
`
`«:1 «:1: «:1 Q 6
`
`Q ?
`
`H38
`
`N
`*.4\N]
`H37
`
`H34
`
`H35
`
`H36
`
`«:1 «:1:
`
`H32
`
`H31
`
`H33
`
`N
`
`*
`
`H42
`
`g r
`
`N
`
`\
`/ [N
`
`x
`
`43
`
`N
`
`H44
`
`/1 ‘UN 1
`\ N
`H45 ‘N
`
`QNQ
`C25
`0 «:20
`t.@;‘3:h1,®*,@-N©t.©"©*.® ,,©:;“
`
`H50
`
`H51
`
`H52
`
`H53
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000011
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`[80]
`
`The present invention also provides an organic electroluminescent device which is
`
`comprised of a first electrode; a second electrode; and at least one organic layer(s) in-
`
`terposed between the first electrode and the second electrode; wherein the organic
`
`layer comprises one or more organic electroluminescent compound(_s) represented by
`
`one of Chemical Formulas (1) to (5).
`
`The organic electroluminescent device according to the present invention is char-
`
`acterized in that the organic layer comprises an electroluminescent layer, which
`
`comprises one or more compound(s) represented by one of Chemical Formulas (1) to
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000012
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`(5) as electroluminescent host, and one or more phosphorescent dopant(s). The dopant
`
`is not particularly restricted.
`
`The organic electroluminescent device according to the invention may further
`
`comprise one or more compound(s) selected from a group consisting of arylamine
`
`compounds and styrylaiylamine compounds, as well as one or more organic electrolu-
`
`minescent compound(s) represented by one of Chemical Formulas (l) to (5).
`
`In an organic electroluminescent device according to the present invention, the
`
`organic layer may further comprise one or more 1netal(s) selected from a group
`
`consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition
`
`metals, lanthanide metals and d—transition elements, or complex(es) thereof, as well as
`
`one or more organic electroluminescent compound(s) represented by one of Chemical
`
`Formulas (1) to (5). The organic layer may comprise an electroluminescent layer and a
`
`charge generating layer.
`
`The organic electroluminescent device may also comprise one or more organic elec-
`
`troluminescent layer(s) emitting blue, green or red light, in addition to the organic elec-
`
`troluminescent compou11d(s) as described above, to form a11 organic electroluminescent
`
`device emitting white light.
`
`Advantageous Effects of Invention
`
`The organic electroluminescent compounds according to the invention exhibit
`
`excellent luminous efficiency and very good life property of material when they are
`
`employed as host material of organic electroluminescent material of an OLED, so that
`
`OLED's having very good operation life can be manufactured therefrom.
`
`Mode for the Invention
`
`The present invention is further described by refeiring to Preparation Examples and
`
`Examples in order to illustrate representative organic electroluminescent compounds,
`
`preparation thereof and luminescent properties of the electroluminescent devices
`
`according to the present invention, but those examples are provided for better under-
`
`standing of the embodiments of the present invention only but are not intended to limit
`
`the scope of the invention by any means.
`
`[Preparation Examples]
`
`[Preparation Example l] Pneparation of Compound (A)
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000013
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`Preparation of Compound (A-l )
`
`A mixture of bromo-2-nitrobenzene (30 g, 148.5 mmol), 1-naphtaleneboronic acid
`
`(30.6 g, 178.2 mmol), Pd(PPh3)4 (5.14 g, 4.45 mmol), aqueous 2M KZCO3 solution
`
`(297.01 mmol), toluene (500 mL) and ethanol (200 1nL) was stirred under reflux for 4
`
`hours. After cooling the mixture to ambient temperature, distilled water was added
`
`thereto. The resultant mixture was extracted with ethyl acetate, and the extract was
`
`dried over magnesium sulfate, and distilled under reduced pressure. Purification
`
`through a column gave Compound (A-1) (31 g, 124.3 mmol, 84.03%).
`
`Preparation of Compound (A-2)
`
`A mixture of Compound (A-1) (31 g, 124.3 mmol) and triethylphosphite (300 mL)
`
`was stirred under reflux for 10 hours. After cooling the mixture to ambient tem-
`
`perature, organic solvent was distilled off under reduced pressure. Distilled water was
`
`added thereto, and the mixture was extracted with ethyl acetate. The extract was dried
`
`over magnesium sulfate and distilled under reduced pressure. Purification through a
`
`column gave Compound (A-2) (18 g, 82.84 mmol, 66.81%).
`
`Preparation of Compound (A-32
`
`A mixture of Compound (A-2) (18 g, 82.84 mmol), 1,5 -diphenyl-3-chloropyridine
`
`(26.4 g, 99.41 mmol), Pd(OAc)2 (1.85 g, 8.28 mmol), P(t-bu)3 (8.17 ml, 16.5 mmol,
`
`50% in xylene), NaOt-bu (23.8 g, 248.5 mmol) and toluene (500 mL) was stirred under
`
`reflux for 12 hours. After cooling the mixture to ambient temperature, distilled Water
`
`was added thereto, and the mixture was extracted with ethyl acetate. The extract was
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000014
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`dried over magnesium sulfate and distilled under reduced pressure. Purification
`
`through a column gave Compound (A-3) (19 g, 42.54 mmol, 51.36%).
`
`Preparation of Compound (A-4)
`
`To a solution of Compound (A-3) (19 g, 42.54 mmol) dissolved in DMF (200 mL),
`
`added was NBS (8.33 g, 46.80 mmol). After 10 hours at ambient temperature, organic
`
`solvent was distilled off under reduced pressure. Distilled water was added thereto, and
`
`the mixture was extracted with ethyl acetate. The extract was dried over magnesium
`
`sulfate, and distilled under reduced pressure. Purification through a column gave
`
`Compound (A-4) (20 g, 38.06 mmol, 89.47%).
`
`Preparation of Compound (A-5 Q
`
`To a solution of Compound (A-4) (20 g, 38.06 mmol) dissolved in THF 200 mL,
`
`slowly added was n-buLi (15.22 mL, 38.06 mmol, 2.5 M in hexane) at -78°C. After
`
`stirring for an hour, trimethylborate (5.51 mL, 49.48 mmol) was added thereto. The
`
`mixture was slowly warmed to ambient temperature, and stirred for 12 hours. Distilled
`
`was added, and the mixture was extracted with ethyl acetate. The extract was dried
`
`over magnesium sulfate, a11d distilled under reduced pressure. Purification through a
`
`column gave Compound (A-5) (8 g, 16.31 mmol, 42.86%).
`
`Preparation of Compound (A-6)
`
`A mixture of Compound (A-5) (8 g, 16.31 mmol), bromo-2-nitrobenzene (3.95 g,
`
`19.57 mmol), Pd(PPh3)4 (0.56 g, 0.48 mmol), aqueous 2M KZCO3 solution (16 mL,
`
`32.62 mmol), toluene (70 mL) and ethanol (20 mL) was stirred under reflux.
`
`According to the same procedure as synthesis of Compound (A-1), obtained was
`
`Compound (A-6) (7 g, 12.33 mmol, 75.62%).
`
`Preparation of Compound (A-7)
`
`Compound (A-6) (7 g, 12.33 mmol) was mixed with triethylphosphite ( 100 mL), and
`
`the same procedure as for synthesis of Compound (A-2) was carried out to give
`
`Compound (A-7) (4 g, 7.46 mmol, 58.33%).
`
`Preparation of Compound (A)
`
`A mixture of Compound (A-7) (4 g, 7.46 mmol), iodobenzene (1.25 mL, 11.2
`
`mmol), copper powder (0.71 g, 11.20 mmol), KZCO3 (3.09 g), 18-Crown-6 (0.15 g,
`
`0.59 mmol) and 1,2-dichlorobenzene (100 mL) was stirred under reflux for 15 hours.
`
`After cooling the reaction mixture to ambient temperature, organic solvent was
`
`distilled off under reduced pressure. Distilled water was added thereto, and the mixture
`
`was extracted with ethyl acetate. The extract was purified through a column to obtain
`
`Compound (A) (3.6 g, 5.88 mmol, 78.88%).
`
`[Preparation Example 2] Preparation of Compound (B)
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000015
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`[110]
`
`[111]
`
`Preparation of Compound (B-1 )
`
`A mixture of 1,4-dibromo-2,3-dinitrobenzene (20 g, 61.36 mmol),
`
`1-naphthaleneboronic acid (26 g, 153.42 mmol), Pd(PPh3)4 (3.54 g, 3.06 mmol),
`
`aqueous 2 M KZCO3 solution (90 mL), toluene (200 mL) and ethanol (100 1nL) was
`
`stirred under reflux for 10 hours. After cooling the reaction mixture to ambient tem-
`
`perature, distilled water was added thereto, and the resultant mixture was extracted
`
`with ethyl acetate. The extract was dried over magnesium sulfate, a11d distilled under
`
`reduced pressure. Purification through a column gave Compound (B-1) ( 22 g, 52.32
`
`mmol, 85.28%).
`
`Preparation of Compound (B-2)
`
`Compound (B-1) (22 g, 52.32 mmol) and triethylphosphite (200 mL) were mixed and
`
`stirred at 180°C. According to the same procedure as for synthesis of Compound (A-2),
`
`obtained was Compound (B-2) (10 g, 28.05 mmol, 53.95%).
`
`Preparation of Compound (B-3)
`
`A mixture of Compound (B-2) (10 g, 28.05 mmol), 2—iodonaphthalene (7.1 g, 28.05
`
`mmol), copper powder (2.67 g, 42.08 mmol), K3CO3 (11.63 g, 84.17 mmol),
`
`l8—Crown—6 (0.59 g, 2.24 mmol) and 1,2-dichlorobenzene (100 mL) was stirred at
`
`190°C for 20 hours. After cooling to ambient temperature, the organic solvent was
`
`distilled off under reduced pressure. Distilled water was added thereto, and the mixture
`
`was extracted with ethyl acetate. The extract was dried over magnesium sulfate and
`
`distilled under reduced pressure. Purification through a column gave Compound (B-3)
`
`(4 g, 8.28 mmol, 29.60%).
`
`Preparation of Compound (B)
`
`To a reaction vessel containing a solution of NaH (0.49 g, 12.43 mmol, 60%
`
`dispersion in mineral oil) dissolved in DMF (20 mL), added was a solution of
`
`Compound (B-3) (4 g, 8.28 mmol) dissolved in DMF (20 1nL). After one hour, a
`
`solution of 2—chloro—4,6—diphenylt1iazine (2.66 g, 9.94 mmol) dissolved in DMF (20
`
`mL) was added thereto. After stirring for 12 hours, distilled water was added, and the
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000016
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`solid produced was filtered under reduced pressure. Recrystallization from ethyl
`
`acetate and DMF gave Compound (B) (3.5 g, 4.90 mmol, 59.21%).
`
`[Preparation Example 3] Preparation of Compound (C)
`
`o
`
`0
`
`H15
`
`C-1
`
`
`
`Q0—""N"mo
`
`0
`
`C-2
`
`/
`
`8* *
`
`c4
`
`C-5
`
`Pre aration of Com ound C—l
`
`To a solution of 1,2-cyclohexyldione (42.52 g, 379.26 mmol) dissolved in ethanol
`
`(1000 mL), slowly added was 2-naphthyl hydrazine (20 g, 126.42 mmol). Acetic acid
`
`(0.28 mL, 5.05 mmol) was added thereto, and the mixture was heated to 40°C. After 2
`
`hours, the mixture was cooled and distilled water was added thereto. The solid
`
`produced was filtered under reduced pressure to obtain Compound (C-1) (17 g, 67.37
`
`mmol, 53.47%).
`
`Preparation of Compound (C-2)
`
`To a solution of Compound (C-1) (17 g, 67.37 mmol) dissolved in acetic acid (100
`
`mL), added was trifluoroacetic acid (10 mL). After stirring at ambient temperature for
`
`2 hours, distilled water was added thereto. The mixture was neutralized by means of
`
`aqueous NaOH solution, and extracted with ethyl acetate. The extract was dried over
`
`magnesium sulfate, and distilled under reduced pressure. Purification through a column
`
`gave Compound (C-2) (ll g, 46.75 mmol, 69.39%).
`
`Preparation of Compound (C-31
`
`According to the same procedure for synthesis of Compound (B-3), obtained was
`
`Compound (C-3) (10 g, 32.11 mmol, 68.69%).
`
`Preparation of Compound (C-4)
`
`According to the same procedure for synthesis of Compound (C-1), obtained was
`
`Compound (C-4) (12 g, 29.88 mmol, 93.07%).
`
`Preparation of Compound (C-5 1
`
`According to the same procedure for synthesis of Compound (C-2), obtained was
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000017
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`Compound (C-5) (6 g, 15.68 mmol, 52.50%).
`
`Preparation of Compound (C)
`
`According to the same procedure for synthesis of Compound (B), obtained was
`
`Compound (C) (5 g, 8.14 mmol, 51.95%).
`
`[Preparation Example 4] Preparation of Compound (D)
`
`(HO)2B
`o
`O 0
`O o
`,\
`-9» O -1 ~ 9
`1
`0-2
`“'3
`
`D.
`
`D
`
`Preparation of Q ;ompound (D-2)
`
`According to the same procedure for synthesis of Compound (A-1) but using
`
`Compound (D-1). obtained was Compound (D-2) (11 g, 38.02 mmol, 89.22%).
`
`Preparation of Compound §D—3)
`
`According to the same procedure for synthesis of Compound (A-2), obtained was
`
`Compound (D-3) (8 g, 31.09 mmol, 81.78%).
`
`Preparation of Compound (D)
`
`According to the same procedure for synthesis of Compound (B), obtained Was
`
`Compound (D) (6 g, 12.30 mmol, 38.70%).
`
`[Preparation Example 5] Preparation of Compound E and F
`
`(Holza —"° —”
`
`—>
`
`1 o
`
`4"1"
`
`o —» O0
`
`o
`
`0
`
`F 0
`
`Preparation of Compound (E-21
`
`According to the same procedure for synthesis of Compound (A-1) but using
`
`Compound (E-1), obtained Was Compound (E-2) (15 g, 51.85 mmol, 86.51%).
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000018
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`[147]
`
`[148]
`
`[149]
`
`[150]
`
`[151]
`
`[152]
`
`[153]
`
`[154]
`
`[155]
`
`[156]
`
`[157]
`
`[158]
`
`[159]
`
`Preparation of Compound gE—3]
`
`According to the same procedure for synthesis of Compound (A-2), obtained was
`
`Compound (E-3) (6 g, 23.31 mmol, 44.97%).
`
`Preparation of Compound [E]
`
`According to the same procedure for synthesis of Compound (B), obtained was
`
`Compound (E) (5 g, 10.25 mmol, 43.99%).
`
`Preparation of Compound gF—1[
`
`According to the same procedure for synthesis of Compound (A-2), obtained was
`
`Compound (F—1) (3 g, 1 1.65 mmol, 22.48%).
`
`Preparation of Compound (F1
`
`According to the same procedure for synthesis of Compound (B), obtained was
`
`Compound (F) (3 g, 6.15 mmol, 52.81%).
`
`[Preparation Example 6] Preparation of Compound (G) and (H)
`
`HN/|:|*§
`
`H-1
`
`Preparation of Compound (G—l )
`
`A mixture of carbazole (20 g, 119.6 mmol), iodobenzene (20 mL, 179.41 mmol),
`
`copper (11.4 g, 179.41 mmol), KZCO3 (49 g, 358.8 mmol), 18—Crown—6 (2.5 g, 9.56
`
`mmol) and l,2—dichlorobenzene was stirred at 190°C for 12 hours. After cooling to
`
`ambient temperature, the reaction mixture was distilled under reduced pressure.
`
`Distilled water was added thereto, and the resultant mixture was extracted with ethyl
`
`acetate. The extract was dried over magnesium sulfate, and distilled under reduced
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000019
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`pressure. Purification through a column gave Compound (G-1) (22 g, 90.42 mmol,
`
`75.60%).
`
`Preparation of Compound (G-2)
`
`According to the same procedure for synthesis of Compound (A-4), obtained was
`
`Compound (G-2) (25 g, 77.59 mmol, 85.81%).
`
`Preparation of Compound gG-32
`
`According to the same procedure for synthesis of Compound (A-5), obtained was
`
`Compound (G-3) (11 g, 38.31 mmol, 49.37%).
`
`Preparation of Compound (G-4)
`
`According to the same procedure for synthesis of Compound (A-1), obtained was
`
`Compound (G-4) (12 g, 32.84 mmol, 85.72%).
`
`Preparation of Compound §G—5 2
`
`According to the same procedure for synthesis of Compound (A-2), reaction was
`
`carried out for 4 hours to obtain Compound (G—5) (6 g, 17.99 mmol, 54.80%).
`
`Preparation of Compound (G:
`
`According to the same procedure for synthesis of Compound (B), obtained was
`
`Compound (G) (7 g, 12.39 mmol, 68.91%).
`
`Preparation of Compound (H-1 1
`
`According to the same procedure for synthesis of Compound (A-2), the reaction was
`
`carried out for 4 hours to obtain Compound (H-1) (2 g, 5.99 mmol, 18.26%).
`
`Preparation of Compound (Hg
`
`According to the same procedure for synthesis of Compound (B), obtained was
`
`Compound (H) (1.7 g, 3.01 mmol, 50.26%).
`
`Organic electroluminescent compounds (TA, TB and TC) were prepared according to
`
`the procedures of Preparation Examples (1)-(6). The substituents (Ari, Ar2) of those
`
`organic electroluminescent compounds thus prepared, and ‘H NMR and MS/FAB data
`
`of the compounds are listed in Tables 1 and 2.
`
`[Table 1]
`
`DUK SAN NEOLUX
`EXHIBIT 1008
`PAGE 000020
`
`

`
`WO 2010/107244
`
`PCT/KR2010/001647
`
`MS! FAB
`found calculated
`
`‘H NMFKCDCI3’ 200 MHL)
`7.05(2H. m). 7,2-9(1H.
`"n). 7,45~7.57(I5H.
`5 =
`7,94~7.95<'4H, m).
`a412~E..16(2H_
`m).611‘.73
`m).
`8.3(4H. m). 8.54(1H.
`rm)
`7./|1~7.5‘(10H. m).
`5
`=
`?.29(1H. m).
`7.58~7.e7(5H. m). 7J9(4H. m). 7,94~7.96(4H. 512.72
`rn), 8.12~8.15(2H.
`rn). 8.54(1H, 5), 8.63(1H.
`s3
`5
`=
`7.29(1H. m).
`7.41~.7.5‘(1DH.
`7.58~-7.67(5H.
`m).
`7.E}4~7.95[4H_.
`8.‘2~8.16(2H, m). 8.28(4H.
`rn). 8.54(IH. m)
`rn),
`5
`=
`7‘29(1H.
`m).
`?',45~7.5(4H,
`T.58~7.67’(5H,
`rn), 7.8(1H, m), 7.94~7_96(4 ,
`,
`8.05~8.16E_5H_. m). 8.54(1H. m), 9.74(1
`,
`
`.
`.
`
`'
`
`43-—‘rs:
`
`pheny
`
`pheny
`
`phony
`
`“H
`
`rn,
`T.45~7.67(11H.
`rn).
`7.29(1H.
`7.94~8.o1(5H. m). 8.12~8.18(3H. m). 8.5/|(1
`.
`m)
`
`L/‘I
`
`.
`
`,
`.
`
`7.45~7.
`7.25~7.33(4H_ m).
`:
`7’.58~7.67’(1OH.
`m).
`?.94~7.9E(
`8.'2~8.16(3F, m). 8.54~8.55(2H. m)
`rn),
`5
`—
`7’.29~7.32(2H.
`rn).
`7.45~?’.5(4H.
`T.58~7.72(7|-. m). 7,86(1H. m).
`7,94~7.96(4 .
`In), 8.12“-8,16(2H. HI), 8.54(1H, HI), 8.760 ,
`m), 8.98{1H, m),
`9.75(1H. m)
`2
`7.99m , m), 7,45~7.5r:(17||, m), 7.790 .
`m),
`7‘94~7.96(4H. m).
`5.12-«3.2:j4H,
`m),
`.
`‘ a.54(IH.
`rn)
`rn),
`'
`. m),
`I.88(2H. mil. 2.72(1H.
`rn),
`rn)_. 7‘29(1H.
`rn).
`7,4w~7_5m0H,
`3.5404.
`T_58~7_71(6k, m). 7.a4~7.95(2H, m),
`8_O5(1
`,
`.
`ra(?H_ rn). BPBMH. m). 8_54(1
`.
`
`.
`
`Qmapmhyl
`
`‘_"a‘”‘”‘y'
`
`H94
`
`l‘43(4H. mil. 1‘65(4H, m).
`. m).
`:
`2‘O9(1H.
`s).
`?.29(1H,
`In).
`m).
`1.8(2H.
`m),
`7,58-«7‘71(6H.
`rn),
`7.41~7.51(1oH,
`rn)‘ 8_O5(1H,
`rn).
`8.12-~8_16(2 ,
`7.94-~7_95(2+,
`m). 8.2a:j4H. m), 8.54{1H, ml
`5
`=
`?.29(IH,
`rn),
`7.35~7,41(3H,
`
`m),
`
`,
`rn), 7.59~7.6?(5H. m). 7_83(|
`T.5~7.5l(5H,
`m). 7.94~8(7H. m). 8.12~8.w3(2H. m). 8.28(4 .
`rn), 8.54{1H, m)
`= 7.29(TH, m), 7:41(2H. m). 7_45(1H. m).
`
`;:£914{1:;:;;57gr|Ej||,—Lm]. 8.n:1?3‘~s.1a(5i4r,B(rf1|:,' 8.54%:
`m)
`?,36~7.41(3H. m).
`7,25~7‘29(3H, m),
`:
`5
`7.5~7.51(5H,
`m).
`.7.59~7.68(7H,
`rn),
`7_79~7_85(5H‘
`m).
`7_94~8(7H.
`m).
`8.'2~8.16(2H. m). 8.28(4H. m). S.54(l