In the late 1890′s and early 1900′s George Merrick and William Brickell were the main pioneers that brought the first developments to Miami. Known for its large urban neighborhood and the business district's constant growth, Downtown Miami houses over 71,000 residences and a population density of 27,438 per square mile. Downtown Miami is considered the US's hub to South America and the Caribbean Islands. Miami is home to major businesses, parks, restaurants, shops, government centers, theaters, and schools, which all connect with a 22-station Metrorail system.Downtown Miami's diverse community and warm weather are not the only things that make it a spectacular place to call home. Downtown Miami is nestled on Biscayne Bay directly west from Miami Beach.Its location is key. Any ocean view high rise has a direct view of a sleepless South Beach. Downtown Miami is full of constant excitement and cultural activities. It's home to the Americas largest music conference (Ultra), the Miami Heat's American Airlines Arena, and Americas largest art exhibits (Art Basel). It is not surprising that Miami is the home of many of the World's most famous actors and athletes.


It's intriguing to map the influences that informed British soul-pop singer John Newman on his full-length debut—but what's most interesting is the way he transmutes his inspirations into a new musical paradigm. The opening title track starts with a speaking voice reeling off a long list of classic R&B artists to whom he's offering "tribute." The singer's previous life as a house music DJ can be discerned in the insistent, pumping keyboard riffs powering some of the tracks. Yet Tribute is neither neo-soul nor house-gone-pop. "Love Me Again" (already a huge hit before the album was released) exemplifies Tribute's brand of larger-than-life pop propelled by rhythms that blend R&B with club music, adorned with arrangements that operate on an orchestral scale. At the core of it all is Newman's gritty but unfailingly flexible voice, imbuing each tune with an unquestionable level of emotional commitment.


text:
Q: Filling in time gaps I need some help with a query that will fill in some missing time (in minutes) gaps, and also persist the current status.  I work in a hospital setting and we are trying to understand the bottlenecks in a hospital Emergency department, at any given minute.
The data in my table looks like this:
Patient_Id      event_time             Event_Status_Name
98676249    2018-09-24 18:39:00.000    Expected
98676249    2018-09-24 19:17:00.000    Waiting for Triage
98676249    2018-09-24 19:28:00.000    In Triage
98676249    2018-09-24 19:29:00.000    Waiting for Room
98676249    2018-09-24 19:45:00.000    Waiting for Provider
98676249    2018-09-24 19:48:00.000    In Process
98676249    2018-09-24 21:02:00.000    Await IP Orders
98676249    2018-09-24 22:59:00.000    Await IP Bed
98676249    2018-09-25 21:44:00.000    Ready for Admit

This basically tells me at what time the patient entered a specific status.  What I need to do, however, is fill in the missing minutes, and persist the status that they are in.  As an example, from 2018-09-24 18:39:00.000 until 2018-09-24 19:16:00.000 the patient was in the "expected" status.  Just using the first status as an example, my desired query output would need to look like this:
Patient_Id  event_time             Event_Status_Name
98676249    2018-09-24 18:39:00.000    Expected
98676249    2018-09-24 18:40:00.000    Expected
98676249    2018-09-24 18:41:00.000    Expected
98676249    2018-09-24 18:42:00.000    Expected
98676249    2018-09-24 18:43:00.000    Expected
98676249    2018-09-24 18:44:00.000    Expected
98676249    2018-09-24 18:45:00.000    Expected
98676249    2018-09-24 18:46:00.000    Expected
98676249    2018-09-24 18:47:00.000    Expected
98676249    2018-09-24 18:48:00.000    Expected

etc, etc, until I hit the next status of "waiting for Triage"
...and then I'd need to do the same, for each minute of that status, until the next one...etc. etc.
How can I write query that does this, without using a loop?  There are millions of records (and minutes) to account for, so I need an inexpensive query for this.
Thanks for your help!

A: You can use a recursive CTE here. As anchor get all the existing rows along with their row number ordered by the timestamp per patient. Then select the row from the anchor applying the next event to them -- via the row number and the patient -- and check, that the next minute is less than the succeeding event's timestamp.
WITH cte
AS
(
SELECT x.patient_id,
       x.event_time,
       x.event_status_name,
       x.rn
       FROM (SELECT t.patient_id,
                    t.event_time,
                    t.event_status_name,
                    row_number() OVER (PARTITION BY t.patient_id
                                       ORDER BY t.event_time) rn
                    FROM elbat t) x
UNION ALL
SELECT c.patient_id,
       dateadd(minute, 1, c.event_time),
       c.event_status_name,
       c.rn
       FROM cte c
            CROSS APPLY (SELECT y.patient_id,
                                y.event_time
                                FROM (SELECT t.patient_id,
                                             t.event_time,
                                             row_number() OVER (PARTITION BY t.patient_id
                                                                ORDER BY t.event_time) rn
                                             FROM elbat t) y
                                     WHERE y.rn = c.rn + 1) x
        WHERE x.patient_id = c.patient_id
              AND x.event_time > dateadd(minute, 1, c.event_time)
)
SELECT *
       FROM cte c
       ORDER BY c.patient_id,
                c.event_time
OPTION (MAXRECURSION 1364);

There is one problem though. Your gaps are so large, that the maximum recursion level of 100 is exceeded. You can enlarge it by using OPTION (MAXRECURSION n). To find a suitable n, you can query the data to find the maximum difference of subsequent events in minutes. Again this uses row_number() to map succeeding events. Take that maximum minus one for the maximum recursion level.
WITH cte
AS
(
SELECT t.patient_id,
       t.event_time,
       row_number() OVER (PARTITION BY t.patient_id
                          ORDER BY event_time) rn
       FROM elbat t
)
SELECT max(datediff(minute, c2.event_time, c1.event_time)) - 1
       FROM cte c1
            INNER JOIN cte c2
                       ON c2.patient_id = c1.patient_id
                          AND c2.rn = c1.rn - 1;

db<>fiddle

A: Don't you think inserting those minutes would make your millions of rows much more millions of rows with a lot of redundant data in it? What could be the purpose? (Maybe some kind of display related work?).
Anyway, if you think you have to, then you could do that with some cross apply. ie:
WITH tally
AS (SELECT TOP (1440 * 10)
           ROW_NUMBER() OVER (ORDER BY t1.object_id) AS N
    FROM master.sys.all_columns t1
        CROSS JOIN master.sys.all_columns t2),
     missedMinutes
AS (SELECT *
    FROM dbo.Patients t1
        CROSS APPLY
    (
        SELECT DATEDIFF(MINUTE, t1.event_time, MIN(t2.event_time))
        FROM Patients t2
        WHERE t1.Patient_Id = t2.Patient_Id
              AND t2.event_time > t1.event_time
    ) t(missed)
        CROSS APPLY
    (
        SELECT TOP (ISNULL(missed, 1) - 1)
               DATEADD(MINUTE, N, t1.event_time)
        FROM dbo.Patients t2
            CROSS JOIN tally
        WHERE t2.Patient_Id = t1.Patient_Id
              AND t1.event_time = t2.event_time
        ORDER BY tally.N
    ) tt(missing) )
SELECT Patient_Id,
       missing AS event_time,
       Event_Status_Name
INTO #missInsert
FROM missedMinutes
ORDER BY event_time;

SELECT *
FROM #missInsert;

DROP TABLE #missInsert;

DBFiddle Demo here

A: Declare @calc1 as table (Paitent_event_sno int,Patient_Id int, event_time DateTime,Event_Status_Name varchar(100))
insert into @calc1 Select Paitent_event_sno = ROW_NUMBER() Over(partition by Patient_Id order by event_time Asc), *  from @Hospital
Declare @final as table (Patient_Id int, event_time DateTime,Event_Status_Name varchar(100))

Declare @Pno int, @Sno int
declare cur CURSOR LOCAL for
Select Distinct Patient_id from @calc1
open cur
fetch next from cur into @Pno
while @@FETCH_STATUS = 0
BEGIN

declare cur2 CURSOR LOCAL for
Select Distinct Paitent_event_sno from @calc1  where  Patient_Id =  @Pno
open cur2
fetch next from cur2 into @Sno
while @@FETCH_STATUS = 0
BEGIN

        declare @starttime datetime , @endtime datetime, @eventtime datetime
        insert into @final
        Select Patient_Id, event_time , Event_Status_Name from @calc1
        where Patient_Id =   @Pno and   Paitent_event_sno = @Sno

        Select @starttime = event_time , @eventtime = event_time from  @calc1 where Patient_Id =   @Pno and   Paitent_event_sno = @Sno

        Select @endtime = event_time from @calc1 where Patient_Id =   @Pno and   Paitent_event_sno = @Sno+1

        set @eventtime = dateadd(mi,1,@eventtime )

        while @eventtime < @Endtime
        begin
        insert into @final
        Select Patient_Id,  @eventtime,Event_Status_Name
        from @calc1 where Patient_Id =   @Pno and
        Paitent_event_sno = @Sno

        set @eventtime = dateadd(mi,1,@eventtime )
        end

        fetch next from cur2 into @Sno
        END
        close cur2
        deallocate cur2

        fetch next from cur into @pno
        END
        close cur
        deallocate cur

        Select * from @final

redpajama_set_name: RedPajamaStackExchange


text:
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Patent application title: COMPOUND CONTAINING 5-MEMBERED HETEROCYCLES, ORGANIC ELECTRONIC DEVICE USING SAME, AND TERMINAL COMPRISING THE LATTER
Inventors: Junghwan Park (Seoul, KR) Junghwan Park (Seoul, KR) Daesung Kim (Yongin-Si, KR) Jungcheol Park (Jinhae-Si, KR) Yongwook Park (Anyang-Si, KR) Hwasoon Jung (Chuncheon-Si, KR) Soungyun Mun (Yongin-Si, KR) Soungyun Mun (Yongin-Si, KR) Daehyuk Choi (Suwon-Si, KR) Dongha Kim (Seongnam-Si, KR) Bumsung Lee (Cheonan-Si, KR)
Assignees: DUK SAN NEOLUX CO., LTD.
IPC8 Class: AC07D49514FI
USPC Class: 544212
Class name: Substituent nitrogen bonded directly to carbon of the triazine ring additional ring containing hetero ring
Patent application number: 20150307514
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Disclosed is a compound represented by Formula 1 or Formula 2, and an organic electric element comprising a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, wherein the organic material layer comprises the compound of Formula 1 or 2 to improve luminous efficiency, stability, and life span.
1. A compound represented by Formula 1 below: ##STR00051## wherein X is O, S, C(Ra) (Rb), N(Rc), P(Rd), Si (Re) (Rf) or Ge(Rg) (Rh), wherein Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are each independently selected from the group consisting of a C6-C60 aryl group, a fluorenyl group, a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C1-C50 alkyl group, a C2-C20 alkenyl group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, and -L-N(R')(R''), R1 to R14 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a C6-C60 aryl group, a fluorenyl group, a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, and -L-N (R') (R''), and at least one of, but not all of R1 to R14 is linked to an adjacent group to form a monocyclic or polycyclic ring, L is selected from the group consisting of a single bond; a C6-C60 arylene group; a fluorenyl group; a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; and a bivalent aliphatic hydrocarbon group, wherein the arylene group, the fluorenyl group, the heterocyclic group, and the bivalent aliphatic hydrocarbon group are optionally substituted by one or more substituents selected from the group consisting of a nitro group, a cyano group, a halogen group, a C1-C2o alkyl group, a C6-C20 aryl group, a C2-C20 heterocyclic group, a C1-C20 alkoxy group, and an amino group;and R' and R'' are each independently a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C6-C20 aryl group, or a fluorenyl group; with the proviso that when R1 to R14, Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are an aryl group, a fluorenyl group, a fused ring group, a heterocyclic group, a alkyl group, a alkenyl group, a alkoxy group, or a aryloxy group, R1 to R14, Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are optionally substituted by one or more substituents selected from the group consisting of deuterium, halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, a C1-C20 alkylthio group, a C1-C20 alkoxy group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C6-C20 aryl group substituted by deuterium, a C2-C20 heterocyclic group, a C3-C20 cycloalkyl group, a C7-C20 arylalkyl group, and a C8-C20 arylalkenyl group.
2. The compound as claimed in claim 1, wherein at least one group of R1 and R2, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9, R9 and R10, and R11 and R12 forms a monocyclic or polycyclic ring.
3. The compound as claimed in claim 1, wherein at least one group of R2 and R13, R3 and R13, R10 and R14, and R11 and R14 forms a monocyclic or polycyclic ring.
4. A compound represented by Formula 2 below: ##STR00052## in Formula 2, X is O, S, C(Ra) (Rb), N(Rc), P(Rd) , Si(Re) (Rf) or Ge (Rg) (Rh), wherein Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are each independently selected from the group consisting of a C6-C60 aryl group, a fluorenyl group, a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C1-C50 alkyl group, a C2-C20 alkenyl group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, and -L-N(R')(R''), R1, R2, and R11 to R18 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a C6-C60 aryl group, a fluorenyl group, a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C1-C50 alkyl group, a C2-C20 alkenyl group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, and -L-N(R')(R''), R21 and R22 are each independently selected from the group consisting of deuterium, halogen, a cyano group, a C6-C60 aryl group, a fluorenyl group, a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C1-C50 alkyl group, a C2-C20 alkenyl group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, and -L-N(R')(R''), m and n are each an integer of 0 to 3, wherein at least one of R1, R2, R11 to R14, R21 and R22, but not all of them, is optionally linked to an adjacent group to form a monocyclic or polycyclic ring,L is selected from the group consisting of a single bond; a C6-C60 arylene group; a fluorenyl group; a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; and a bivalent aliphatic hydrocarbon group, Wherein, the arylene group, the fluorenyl group, the heterocyclic group, and the bivalent aliphatic hydrocarbon group are optionally substituted by one or more substituents selected from the group consisting of a nitro group, a cyano group, a halogen group, a C1-C20 alkyl group, a C6-C20 aryl group, a C2-C20 heterocyclic group, a C1-C20 alkoxy group, and an amino group; R' and R'' are each independently a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C6-C20 aryl group, or a fluorenyl group; with the proviso that when R1, R2, and R11 to R18 are an aryl group, a fluorenyl group, a fused ring group, a heterocyclic group, a alkyl group, a alkenyl group, a alkoxy group, or a aryloxy group, R1 to R14, Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are optionally substituted by one or more substituents selected from the group consisting of deuterium, halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, a C1-C20 alkylthio group, a C1-C20 alkoxy group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C6-C20 aryl group substituted by deuterium, a C2-C20 heterocyclic group, a C3-C20 cycloalkyl group, a C7-C20 arylalkyl group, and a C8-C20 arylalkenyl group.
5. The compound as claimed in claim 4, at least one group of R1 and R2, R11 and R12, two adjacent R21, and two adjacent R22 forms a monocyclic or polycyclic ring.
6. The compound as claimed in claim 4, wherein at least one group of R2 and R13, and R11 and R14 are linked together to form a monocyclic or polycyclic ring.
7. A compound selected from the group consisting of Compounds 1 to 96: ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##
8. An organic electronic device comprising one or more organic material layers comprising the compound as claimed in claim 1.
10. An organic electronic device comprising one or more organic material layers comprising the compound as claimed in claim 7.
11. The organic electronic device as claimed in claim 8, wherein the organic material layers comprise a light emitting layer comprising the compound.
13. The organic electronic device as claimed in claim 10, wherein the organic material layers comprise a light emitting layer comprising the compound.
14. The organic electronic device as claimed in claim 12, wherein the compound is used as a host material of the light emitting layer.
15. A terminal comprising a display device and a control part for driving the display device, the display device comprising the organic electronic device as claimed in claim 7.
18. The terminal as claimed in claim 15, wherein the organic electronic device is any one of an organic light-emitting diode, an organic solar cell, an organic photo conductor drum, an organic transistor, a photodiode, an organic laser, and a laser diode.
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation in part of U.S. patent application Ser. No. 13/390,043 filed on Feb. 10, 2012, which was a National Phase Application filed under 35 U.S.C. §371 of PCT/KR2010/005206 filed on Aug. 9, 2010, which claims priority to Korean Patent Application No. 10-2009-0073915 filed on Aug. 11, 2009, which are incorporated herein by reference in their entirety.
[0002] 1. Field of the invention
[0003] The present invention relates to a compound containing 5-membered heterocycles, an organic electronic device using the same, and a terminal including the latter.
[0004] 2. Description of the Prior Art
[0005] In general, an organic light emitting phenomenon indicates conversion of electric energy into light energy by means of an organic material. An organic electronic device using the organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer interposed therebetween. In many cases, the organic material layer has a multi-layered structure having respectively different materials in order to improve efficiency and stability of an organic electronic device. For example, it may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like.
[0006] Materials used as an organic material layer in an organic electronic device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their functions. Then, the light emitting material may be divided into a high molecular weight type and a low molecular weight type according to their molecular weight, and may be divided into a fluorescent material from electronic singlet excited states and a phosphorescent material from electronic triplet excited states according to their light emitting mechanism. Further, the light emitting material can be classified into a blue, green or red light emitting material and a yellow or orange light emitting material required for giving a more natural color, according to a light emitting color.
[0007] Meanwhile, when only one material is used as a light emitting material, an efficiency of a device is lowered owing to a maximum luminescence wavelength being moved to a longer wavelength due to the interaction between the molecules, the deterioration of color purity and the reduction in light emitting efficiency. Therefore, a host/dopant system can be used as the light emitting material for the purpose of enhancing the color purity and the light emitting efficiency through energy transfer. It is based on the principle that if a small amount of a dopant having a smaller energy band gap than a host forming a light emitting layer is mixed with the light emitting layer, excitons which are generated in the light emitting layer are transported to the dopant, thus emitting a light having a high efficiency. Here, since the wavelength of the host is moved according to the wavelength of the dopant, a light having a desired wavelength can be obtained according the kind of the dopant.
[0008] In order to allow the organic electronic device to fully exhibit the above-mentioned excellent characteristics, a material constituting the organic material layer in the device, for example, a hole injection material, a hole transport material, a light emitting material, an electron transport material and an electron injection material should be essentially composed of a stable and efficient material. However, the development of a stable and efficient organic material layer material for the organic electronic device has not yet been fully realized. Accordingly, the development of new materials is continuously desired.
[0009] In order to solve the above-mentioned problems in prior art, the inventors of the present invention found that when a novel-structural compound including three or more 5-membered heterocycles is employed in an organic electronic device, it is possible to significantly improve luminous efficiency, stability, and a life span of the device.
[0010] Accordingly, an object of the present invention is to provide a novel compound containing 5-membered heterocycles, an organic electronic device using the same, and a terminal including the latter.
[0011] In accordance with an aspect of the present invention, a compound represented by the following formula is provided:
##STR00001##
[0012] In accordance with another aspect of the present invention, another compound represented by the following formula is provided:
[0013] The inventive novel-structural compound of the formula above having three or more 5-membered heterocycles in the structure, may be used as a hole injection material, a hole transport material, a light emitting material, and/or an electron transport material appropriate for a fluorescent or phosphorescent device of all colors (such as red, green, blue, white, etc.), and is useful as a host material for various colors of a phosphorescent dopant.
[0014] Further, in accordance with an aspect of the present invention, an organic electronic device comprising either of the compounds represented by the formula above, and a terminal comprising the organic electronic device are provided.
[0015] According to an embodiment of the present invention, the compound having three or more 5-membered heterocycles in the structure can perform various roles in an organic electronic device and a terminal thereof. In particular, it is useful as a hole injection material, a hole transport material, a light emitting material, and/or an electron transport material appropriate for a fluorescent or phosphorescent device of all colors (such as red, green, blue, white, etc.), and preferably useful as a host material for various colors of a phosphorescent dopant.
[0016] The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which:
[0017] FIGS. 1 to 6 each show an example of an organic electro-luminescence device which can employ a compound according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, the same elements will be designated by the same reference numerals although they are shown in different drawings. Further, in the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
[0019] In addition, terms, such as first, second, A, B, (a), (b) or the like may be used herein when describing components of the present invention. Each of these terminologies is not used to define an essence, order or sequence of a corresponding component but used merely to distinguish the corresponding component from other component(s). It should be noted that if it is described in the specification that one component is "connected," "coupled" or "joined" to another component, a third component may be "connected," "coupled," and "joined" between the first and second components, although the first component may be directly connected, coupled or joined to the second component.
[0020] The present invention provides a compound represented by Formula 1 below:
[0021] In Formula 1,
[0022] (1) R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 each are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted C1˜C50 alkyl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), a substituted or unsubstituted C5˜C60 heteroaryl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), and a substituted or unsubstituted C5˜C60 heteroaryloxy group having at least one of sulfur, nitrogen, oxygen, phosphorous and silicon.
[0023] (2) R13 and R14 each are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted C1˜C50 alkyl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), a substituted or unsubstituted C5˜C60 heteroaryl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), and a substituted or unsubstituted C5˜C60 heteroaryloxy group having at least one of sulfur, nitrogen, oxygen, phosphorous and silicon.
[0024] (3) X may include carbon (CRaRb), nitrogen (NRc), oxygen (O), phosphorous (PRd), sulfur (S), silicon (SiReRf) or germanium (GeRgRh), wherein Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh each are independently selected from the group including an alkyl group having 1 to 50 carbon atoms, and an aryl group having 6 to 60 carbon atoms.
[0025] (4) At least one of R1 and R2, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9, R9 and R10, and R11 and R12, but not all of them, may form a saturated or unsaturated cyclic ring together with an adjacent group.
[0026] (5) R2 and R13, and/or R11 and R14 may form a saturated or unsaturated cyclic ring together with an adjacent group.
[0027] (6) The compound represented by Formula 1 may have a symmetric or asymmetric structure with respect to X.
[0028] (7) The compound having the structural formula represented by Formula 1 may be used in a soluble process.
[0029] Also, in another aspect, the present invention provides a compound represented by Formula 2:
[0030] wherein,
[0031] (1) R1, R2, R11 and R12 each are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted C1˜C50 alkyl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), a substituted or unsubstituted C5˜C60 heteroaryl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), and a substituted or unsubstituted C5˜C60 heteroaryloxy group having at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorous (P) and silicon (Si).
[0032] (2) R13 and R14 each are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted C1˜C50 alkyl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), a substituted or unsubstituted C5˜C60 heteroaryl group having at least one of sulfur (S), nitrogen (N), oxygen(O), phosphorous (P) and silicon (Si), and a substituted or unsubstituted C5˜C60 heteroaryloxy group having at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorous (P) and silicon (Si).
[0033] (3) R15, R16, R17 and R18 each are independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted C1˜C50 alkyl group having at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorous (P) and silicon (Si), a substituted or unsubstituted C5˜C60 heteroaryl group having at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorous (P) and silicon (Si), and a substituted or unsubstituted C5˜C60 heteroaryloxy group having at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorous (P) and silicon (Si).
[0034] (4) R21 and R22 are each independently selected from the group consisting of deuterium, halogen, a cyano group, a C6-C60 aryl group, a fluorenyl group, a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, a C2-C60 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, a C1-C50 alkyl group, a C2-C20 alkenyl group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, and -L-N(R')(R'').
[0036] (6) R1 and R2, or R11 and R12 may form a saturated or unsaturated cyclic ring together with an adjacent group.
[0038] According to one embodiment of the present invention, the compound of Formula 1 or 2 includes, but not limited to, the following specific compounds of Compound 1 to Compound 81, which is represented herein by Formula 3.
##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##
[0039] There exist various organic electronic devices which employ compounds including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3, as an organic material layer. The organic electronic devices in which compounds including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3 can be employed, may include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photo conductor (OPC) drum, an organic transistor (organic TFT), a photodiode, an organic laser, a laser diode, and the like.
[0040] As one example of the organic electronic devices in which compounds including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3, can be used, an organic light emitting diode (OLED) will be described below, but the present invention is not limited thereto. The above described compounds including three or more 5-membered heterocycles may be applied to various organic electronic devices.
[0041] In another embodiment of the present invention, there is provided an organic electronic device (organic electro-luminescence device) including a first electrode, a second electrode, and an organic material layer interposed between these electrodes, in which at least one of organic material layers includes the compounds represented by Formulas 1 to 3.
[0042] FIGS. 1 to 6 show examples of an organic electro-luminescence device which can employ a compound according to the present invention.
[0043] The organic electro-luminescence device according to another embodiment of the present invention may be manufactured by means of a manufacturing method and materials conventionally known in the art in such a manner that it can have a conventionally known structure, except that at least one of organic material layers including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed in such a manner that it can include the compounds represented by Formulas 1 to 3.
[0044] The structures of the organic electro-luminescence device according to another embodiment of the present invention are shown in FIGS. 1 to 6, but the present invention is not limited to the structures. Herein, the reference numeral 101 indicates a substrate, 102 indicates an anode, 103 indicates a hole injection layer (HIL), 104 indicates a hole transport layer (HTL), 105 indicates a light emitting layer (EML), 106 indicates an electron injection layer (EIL), 107 indicates an electron transport layer (ETL), and 108 indicates a cathode. Although not shown, such an organic electro-luminescence device may further include a hole blocking layer (HBL) for blocking movement of holes, an electron blocking layer (EBL) for blocking movement of electrons, and a protective layer. The protective layer may be formed in such a manner that it, as an uppermost layer, can protect an organic material layer or a cathode.
[0045] Herein, the compound including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3, may be included in at least one of organic material layers including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the compound including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3, may be substituted for at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, and a protective layer, or may be used in combination with these layers. Of course, the compound may be used for not only one layer of the organic material layers but also two or more layers.
[0046] Especially, the compound including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3, may be used as a hole injection material, a hole transport material, a light emitting material, and/or an electron transport material appropriate for a fluorescent or phosphorescent device of all colors (such as red, green, blue, white, etc.), and especially is useful as a green phosphorescent host material.
[0047] For example, in manufacturing of the organic electro-luminescence device according to another embodiment of the present invention, a metal, a conductive metal oxide, or an alloy thereof is deposited on a substrate by means of PVD (physical vapor deposition) such as sputtering or e-beam evaporation so as to form an anode, and then an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and a material used as a cathode is deposited thereon.
[0048] Besides, on a substrate, a cathode material, an organic material layer, and an anode material may be sequentially deposited so as to provide an organic electronic device. The organic material layer may be formed in a multi-layered structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but the present invention is not limited thereto. It may be formed in a single layer structure. Further, the organic material layer may be manufactured with a smaller number of layers by using various polymer materials by means of a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer) instead of deposition.
[0049] In the organic electro-luminescence device according to another embodiment of the present invention, the organic material layer (e.g., a light emitting layer) may be formed by a soluble process of the above described compound including three or more 5-membered heterocycles.
[0050] The substrate is a support for the organic electro-luminescence device, and may employ a silicon wafer, a quartz or glass plate, a metallic plate, a plastic film or sheet.
[0051] On the substrate, an anode is positioned. Such an anode allows holes to be injected into a hole injection layer positioned thereon. As an anode material, a material having a high work function is preferably used so that injection of holes into an organic material layer can be smoothly carried out. Specific examples of an anode material used for the present invention may include: metals (such as vanadium, chromium, copper, zinc, gold) or alloys thereof; metallic oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); a metal-oxide combination such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole and polyaniline, but the present invention is not limited thereto.
[0052] On the anode, a hole injection layer is positioned. A material for such a hole injection layer is required to have a high efficiency for injecting holes from an anode, and to be able to efficiently transport the injected holes. For this, the material has a low ionization potential, a high transparency against visible light, and a high stability for holes.
[0053] As a hole injection material, a material into which holes can be well injected from an anode at a low voltage is used. Preferably, HOMO (highest occupied molecular orbital) of the hole injection material ranges from a work function of an anode material to HOMO of adjacent organic material layers. Specific examples of the hole injection material may include metal porphyrine-, oligothiophene-, and arylamine-based organic materials, hexanitrile hexaazatriphenylene- and quinacridone-based organic materials, perylene-based organic materials, and anthraquinone-, polyaniline-, and polythiophene-based conductive polymers, but the present invention is not limited thereto.
[0054] On the hole injection layer, a hole transport layer is positioned. Such a hole transport layer receives holes transferred from the hole injection layer and transfers them to an organic light emitting layer positioned thereon. Further, the hole transport layer has a high hole mobility and a high hole stability and performs a role of blocking electrons. Besides these general requirements, it requires heat-resistance against a device when applied to an automobile display, and thus is preferably made of a material having a glass transition temperature (Tg) of 70° C. or more. The examples of a material satisfying these conditions may include NPD (or NPB), spiro-arylamine-based compound, perylene-arylamine-based compound, azacycloheptatriene compound, bis(diphenylvinylphenyl)anthracene, silicongermaniumoxide compound, silicon-based arylamine compound, and the like.
[0055] On the hole transport layer, an organic light emitting layer is positioned. Such an organic light emitting layer is made of a material having a high quantum efficiency, in which holes and electrons which are injected from an anode and a cathode, respectively, are recombined so as to emit light. As a light emitting material, a material allowing holes and electrons transferred from a hole transport layer and an electron transport layer, respectively, to be combined so as to emit visible light is used. Preferably, a material having a high quantum efficiency against fluorescence or phosphorescence is used.
[0056] As a material or a compound satisfying these conditions, for a green color, Alq3 may be used, and for a blue color, Balq(8-hydroxyquinoline beryllium salt), DPVBi(4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl) based material, Spiro material, spiro-DPVBi(Spiro-4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl), LiPBO (2-(2-benzoxazoyl)-phenol lithium salt), bis(diphenylvinylphenylvinyl)benzene, aluminum-quinoline metal complex, imidazole, thiazol and oxazole-metal complex, or the like may be used. In order to improve the luminous efficiency of a blue color, perylene, and BczVBi(3,3'[(1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl]bis(9-ethyl)-9H-ca- rbazole; DSA(distrylamine)) may be doped in a small amount. For a red color, a green light emitting material may be doped with DCJTB([2-(1,1-dimethylethyl)-6-[2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- -1H,5H-benzo(ij)quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene]-propanedinitr- ile) in a small amount. When a process such as inkjet printing, roll coating, spin coating, is used to form a light emitting layer, polyphenylenevinylene (PPV)-based polymer or poly fluorene may be used for an organic light emitting layer.
[0057] On the organic light emitting layer, an electron transport layer is positioned. Such an electron transport layer requires a material which has a high efficiency for electrons injected from a cathode positioned thereon, and can efficiently transport the injected electrons. For this, a material having a high electron affinity, a high electron mobility, and a high electron stability is required. The examples of an electron transport material satisfying these conditions may include Al complex of 8-hydroxyquinoline; complex including Alq3; organic radical compound; and hydroxyflavone-metal complex, but the present invention is not limited thereto.
[0058] On the electron transport layer, an electron injection layer is layered. The electron injection layer may be manufactured by using a metal complex compound (such as Balq, Alq3, Be(bq)2, Zn(BTZ)2, Zn(phq)2, PBD, spiro-PBD, TPBI, and Tf-6P) or a low molecular material including an aromatic compound having an imidazole ring or a boron compound. Herein, the electron injection layer may be formed in a thickness range of 100 Å to 300Å.
[0059] On the electron injection layer, a cathode is positioned. Such a cathode performs a role of injecting electrons into the electron injection layer. As a material for the cathode, the same material as that used for an anode may be used. In order to achieve efficient electron injection, a metal having a low work function is more preferable. Especially, metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or alloys thereof may be used. Further, a double-layered electrode (e.g., lithiumfluoride and aluminum, lithium oxide and aluminum, and strontium oxide and aluminum) with a thickness of 100 μm or less may be used.
[0060] As described above, the compound including three or more 5-membered heterocycles, as described with reference to Formulas 1 to 3, may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material and/or an electron injection material appropriate for a fluorescent or phosphorescent device of all colors (such as red, green, blue, white, etc.), and may be used as a host material for various colors of a phosphorescent dopant.
[0061] The organic electro-luminescence device according to the present invention may be manufactured in a front luminescent type, a rear luminescent type, or a both-side luminescent type according to its materials.
[0062] Meanwhile, the present invention provides a terminal which includes a display device and a control part for driving the display device, the display device including the above described organic electronic device. The terminal means a wired/wireless communication terminal which is currently used or will be used in the future. The above described terminal according to the present invention may be a mobile communication terminal such as a cellular phone, and may include all kinds of terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation unit, a game player, various kinds of TVs, and various kinds of computers.
[0063] Hereinafter, the present invention will be described more specifically with reference to Preparation Examples and Experimental Examples. However, the following examples are only for illustrative purposes and are not intended to limit the scope of the invention.
PREPARATION EXAMPLE
[0064] Hereinafter, Preparation Examples or Synthesis Examples of the compounds including three or more 5-membered heterocycles, represented by Formula 3, will be described. However, since there are many compounds including three or more 5-membered heterocycles, represented by Formula 3, one compound or two compounds from among the compounds will be exemplified. A person skilled in the art of the invention should realize that other compounds including three or more 5-membered heterocycles can be prepared through Preparation Examples as described below although they are not exemplified.
[0065] step 1) Synthesis of intermediate A
[0066] In a 250 mL round-bottom flask, N,N,N',N'-Tetramethylenediamine (TMEDA) was dissolved in anhydrous Hexane. At 0° C., n-BuLi (1.6 M in hexane) was slowly added thereto for 30 minutes, and the mixture was stirred for 30 minutes at room temperature. Dibenzothiophene diluted with Hexane was added thereto, and the resultant product was stirred at 60° C. for 2 hours. Then, the temperature of the product was lowered to -70° C., and chlorotrimethylsilane was added thereto, followed by stirring for 1 hour. After the completion of the reaction, the resultant product was extracted with Hexane, and washed with water.
[0067] From the extract, a small amount of water was removed by MgSO4 (anhydrous), followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography (solvent: Pentane) to give a required intermediate A (yield: 30%).
[0068] step 2) Synthesis of Intermediate B
[0069] The intermediate A obtained from the step 1) was dissolved in Carbon tetrachloride. The temperature of the resultant product was lowered to -15° C., and Bromine was slowly added thereto. Then, the resultant product was stirred at 0° C. for 1 hour, and water was added thereto to quench the reaction. The organic layer was washed with
[0070] Brine. Anhydrous MgSO4 was used to remove water within the resultant product. After vacuum-filtration, the product obtained by concentration of an organic solvent was purified by column chromatography to give a required intermediate B (yield: 89%).
[0071] step 3) Synthesis of Intermediate C
[0072] The intermediate B obtained from the step 2) was dissolved in anhydrous THF. The temperature of the resultant product was lowered to -78° C., and n-BuLi (1.6 M in Hexane) was slowly added thereto. Then, the resultant product was stirred at 0° C. for 1 hour. Then, the temperature of the resultant product was lowered to -78° C., and
[0073] Trimethyl borate was added thereto, followed by stirring at room temperature for 12 hours. After the completion of the reaction, the resultant product was added with 2N HCl aqueous solution, stirred for minutes, and extracted with Ether. From the extract, a small amount of water was removed by anhydrous MgSO4, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required intermediate C (yield: 70%).
[0074] step 4) Synthesis of Intermediate D
[0075] The intermediate C obtained from the step 3), Pd(PPh3)4, and K2CO3 were dissolved in anhydrous THF and a small amount of water, followed by reflux for 24 hours. After the completion of the reaction, the resultant product was cooled to room temperature, extracted with CH2Cl2, and washed with water. From the extract, a small amount of water was removed by anhydrous MgSO4, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required intermediate D (yield: 77%).
[0076] Step 5) Synthesis of Intermediate E
[0077] The intermediate D obtained from the step 4) and triphenylphosphine were dissolved in o-dichlorobenzene, followed by reflux for 24 hours. After the completion of the reaction, the solvent was removed by vacuum distillation. Then, the concentrated product was purified by column chromatography to give a required intermediate E (yield: 57%).
Synthesis Example 1
Synthesis of Compound 1
[0079] The intermediate E synthesized from the step 5), Iodobenzene, Pd2(dba)3, P(tBu)3 and NaOtBu were dissolved in Toluene solvent, followed by stirring at 110° C. for 6 hours. After the completion of the reaction, the resultant product was cooled to room temperature, extracted with CH2Cl2, and washed with water. From the extract, a small amount of water was removed by anhydrous MgSO4, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required compound 1 (yield: 65%).
Synthesis of Compound 10
[0081] The intermediate E synthesized from the step 5) was dissolved in anhydrous THF. The temperature of the resultant product was lowered to -78° C., and n-BuLi (1.6 M in Hexane) was slowly added thereto. Then, the resultant product was stirred at 0° C. for 1 hour. Then, the temperature of the resultant product was lowered to -78° C., and 2-Chloro-4,6-diphenylpyrimidine dissolved in anhydrous THF was slowly added thereto, followed by stirring at 60° C. for 12 hours. After the completion of the reaction, the resultant product was cooled to room temperature, extracted with CH2Cl2, and washed with water. From the extract, a small amount of water was removed by anhydrous MgSO4, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required compound 10 (yield: 48%).
[0082] Step 6) Synthesis of Intermediate F
[0083] The compound 1 obtained from Synthesis Example 1, NBS (N-bromosuccinimide), and BPO (benzoyl peroxide) were dissolved in CH2Cl2, followed by stirring at room temperature for 6 hours. After the completion of the reaction, the resultant product was added with a sodium bicarbonate aqueous solution, stirred for 30 minutes, and extracted with CH2Cl2. Anhydrous MgSO4 was used to remove water within the resultant product. After vacuum-filtration, the product obtained by concentration of an organic solvent was purified by column chromatography to give a required intermediate F (yield: 77%).
[0085] The intermediate F obtained from the step 6), 4-(1-Phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid, Pd(PPh3)4, and K2CO3 were dissolved in anhydrous THF and a small amount of water, followed by reflux for 24 hours. After the completion of the reaction, the resultant product was cooled to room temperature, extracted with CH2Cl2, and washed with water. From the extract, a small amount of water was removed by anhydrous MgSO4, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required compound 27 (yield: 57%).
[0087] The intermediate F obtained from the step 6), diphenylamine, Pd2(dba)3, P(tBu)3 and NaOtBu were dissolved in Toluene solvent, followed by stirring at 110° C. for 9 hours. After the completion of the reaction, the resultant product was cooled to room temperature, extracted with CH2Cl2, and washed with water. From the extract, a small amount of water was removed by anhydrous MgSO4, followed by vacuum-filtration. Then, the product obtained after concentration of an organic solvent was purified by column chromatography to give a required compound 58 (yield: 60%).
##STR00040## ##STR00041##
[0089] (1) Synthesis Method of Sub 1-II
[0090] In a round-bottom flask, Sub 1-I (308 g, 701.42 mmol), (2-nitrophenyl)boronic acid (117.1 g, 701.42 mmol), Pd(PPh3)4 (24.32 g, 21.04 mmol), NaOH (84.17 g, 2104 mmol), THF (3086 ml), and water (1543 ml) were placed and heated to reflux at 80˜90° C. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 219.3 g of product (yield: 72).
[0091] (2) Synthesis Method of Sub 1-III
[0092] The obtained Sub 1-II (219 g, 504.25 mmol) was dissolved in o-dichlorobenzene (2017 ml) in a round bottom flask, and triphenylphosphine (396.8 g, 1512 mmol) was added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 87.2g of product (yield: 43%).
[0093] (3) Synthesis Method of Sub 1-IV
[0094] The obtained Sub 1-III (79 g, 196.36 mmol) was dissolved in nitrobenzene (981 ml) in a round bottom flask, and 4-iodo-1,1'-biphenyl (60.5 g, 216 mmol), Na2SO4 (27.9 g, 196.36 mmol), K2CO3 (27.1 g, 196.36 mmol), and Cu (3.7 g, 58.9 mmol) were added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, nitrobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 48.9g of product (yield: 45%).
[0095] (4) Synthesis Method of Sub 1-V
[0096] In a round-bottom flask, Sub 1-IV (48 g, 86.6 mmol), (2-nitrophenyl)boronic acid (14.45 g, 86.6 mmol), Pd(PPh3)4 (3.0 g, 2.6 mmol), NaOH (10.39g, 259.7 mmol), THF (380 ml), and water (190 ml) were placed and heated to reflux at 80˜90° C. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 35.12g of product (yield: 68%)
[0097] (5) Synthesis Method of Intermediate G
[0098] The obtained Sub 1-V (31 g, 51.95 mmol) was dissolved in o-dichlorobenzene (208 ml) in a round bottom flask, and triphenylphosphine (40.9 g, 155.86 mmol) was added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 13.2g of product (yield: 45%).
[0099] (6) Synthesis Method of Compound 83
[0100] The obtained Intermediate G (13.2 g, 23.38 mmol) was dissolved in nitrobenzene (117 ml) in a round bottom flask, and iodo-phenyl (5.2 g, 25.71 mmol), Na2SO4 (3.3 g, 23.38 mmol), K2CO3 (3.2 g, 23.38 mmol), and Cu (0.4 g, 7.013 mmol) were added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, nitrobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 7.19g of product (yield: 48%).
[0103] Using Sub 2-I (260 g, 668.3 mmol), (3-nitro-[1,1'-biphenyl]-4-yl)boronic acid (162.41 g, 668.3 mol), Pd(PPh3)4 (23.17 g, 20.05 mmol), NaOH (80.2 g, 2004.9 mmol), THF (2940 ml), and water (1470 ml), the same procedure as described in the synthesis method of Sub 1-II was carried out to obtain 215.35g of product (yield: 70%).
[0105] Using Sub 2-II (190 g, 412.7 mmol), o-dichlorobenzene (1651 ml), and triphenylphosphine (324.8 g, 1238.2 mmol), the same procedure as described in the synthesis method of Sub 1-III was carried out to obtain 83.09g of product (yield: 47%).
[0107] Using Sub 1-III (83 g, 193.77 mmol), nitrobenzene (969 ml), 5'-iodo-1,1':3',1''-terphenyl (75.9 g, 213.15 mmol), Na2SO4 (27.5 g, 193.77 mmol), K2CO3 (26.8 g, 193.78 mmol), and Cu (3.7 g, 58.13 mmol), the same procedure as described in the synthesis method of Sub 1-IV was carried out to obtain 62.35g of product (yield: 49%).
[0109] Using Sub 2-IV (62 g, 94.42 mmol), (1-nitronaphthalen-2-yl)boronic acid (20.49 g, 94.42 mmol), Pd(PPh3)4 (3.27 g, 2.83 mmol), NaOH (11.33 g, 283.27 mmol), THF (415 ml), and water (208 ml), the same procedure as described in the synthesis method of Sub 2-V was carried out to obtain 36.06g of product (yield: 51%).
[0110] (5) Synthesis Method of Intermediate H
[0111] Using the obtained Sub 2-V (36 g, 48.07 mmol), o-dichlorobenzene (192 ml), and triphenylphosphine (37.8 g, 144 mmol), the same procedure as described in the synthesis method of Intermediate G was carried out to obtain 16.89g of product (yield: 49%).
[0113] The obtained Intermediate H (16.8 g, 23.44 mmol) was dissolved in nitrobenzene (117 ml) in a round bottom flask, and iodo-phenyl (5.3 g, 25.78 mmol), Na2SO4 (3.3 g, 23.44 mmol), K2CO3 (3.2 g, 23.44 mmol), and Cu (0.4 g, 7.03 mmol) were added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, nitrobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 8.18g of product (yield: 44%).
[0115] (1) Synthesis Method of Intermediate I
[0116] In a round-bottom flask, compound 82 (30 g, 54.68 mmol), NBS (20.4 g, 114.83 mmol) and BPO (1.3g, 5.47 mmol) were placed and CH2Cl2(164 ml) as a solvent were added to the reaction solution, followed by stirring at room temperature for 5 hrs. Upon completion of the reaction, the reaction product was diluted with dichrolomethane as a solvent and then extracted. The extracted solution was dried with MgSO4 and vacuum-dried, and then crude product was obtained. The obtained crude product was recrystallized with diethylether and n-hexane and then separated by a silica gel column to obtain 28.2 g of intermediate I (yield: 73%).
[0118] In a round-bottom flask, intermaeiate I (2.4 g, 14.01 mmol), diphenylamine (9 g, 12.74 mmol), Pd2(dba)3 (1.2 g, 1.27 mmol), P(t-Bu)3 (0.5 g, 2.55 mmol), NaO(t-Bu) (6.1 g, 63.7 mmol), and Toluene (134 mL) were placed and heated to reflux at 110° C. for 3 hrs. Upon completion of the reaction, the reaction product was diluted with dichrolomethane as a solvent and then extracted. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with methylene chloride and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was dissolved in toluene and separated by a silica filter. Upon completion of the filter, the solution was concentrated, and recrystallized with toluene and acetone to obtain 7.43g of product (yield: 66%).
[0121] In a round-bottom flask, Sub 3-I (150.08g, 457.7 mmol), 1-bromo-3-iodo-2-nitrobenzene (180 g, 457.7 mmol), Pd(PPh3)4 (15.87 g, 13.73 mmol), K2CO3 (189.78 g, 1373 mmol), THF (2014 ml), and water (1006 ml) were placed and heated to reflux at 80˜90° C. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 243.36 of product (yield: 71%).
[0123] The obtained Sub 3-II (243.35 g, 442.91 mmol) was dissolved in o-dichlorobenzene (1771 ml) in a round bottom flask, and triphenylphosphine (348.5 g, 1328.72 mmol) was added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 93.96 g of product (yield: 41%).
[0125] In a round-bottom flask, Sub 3-III (93.9 g, 181.47 mmol), (3-nitro-[1,1'-biphenyl]-4-yl)boronic acid (44.1 g, 181.47 mmol), Pd(PPh3)4 (6.29 g, 5.44 mmol), K2O03 (75.24 g, 544.41 mmol), THF (798 ml), and water (399 ml) were placed and heated to reflux at 80˜90° C. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 75.6 g of product (yield: 69%).
[0127] The obtained Sub 4-IV (75.6 g, 118.92 mmol) was dissolved in o-dichlorobenzene (476 ml) in a round bottom flask, and triphenylphosphine (93.6 g, 356.76 mmol) was added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 30.87 g of product (yield: 43%).
[0129] In a round-bottom flask, Sub 3-V (30.8 g, 51.02 mmol), bromobenzene (24.8 g, 158.15 mmol), Pd2(dba)3 (2.8 g, 3.06 mmol), P(t-Bu)3 (3.1 g, 15.31 mmol), NaO(t-Bu) (34.3 g, 357.11 mmol), and Toluene (536 mL) were placed and heated to reflux at 110° C. for 3 hrs. Upon completion of the reaction, the reaction product was diluted with dichrolomethane as a solvent and then extracted. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with methylene chloride and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was dissolved in toluene and separated by a silica filter. Upon completion of the filter, the solution was concentrated, and recrystallized with toluene and acetone to obtain 28.44 g of product (yield: 67%).
[0132] In a round-bottom flask, Sub 4-I (180 g, 689.44 mmol), 3-bromo-1-iodo-2-nitronaphthalene (260.6 g, 689.44 mmol), Pd(PPh3)4 (23.9 g, 20.68 mmol), K2CO3 (285.9 g, 2068.33 mmol), THF (3034 ml), and water (1517 ml) were placed and heated to reflux at 80˜90° C. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 238.42 of product (yield: 74%).
[0134] The obtained Sub 4-II (238 g, 509.3 mmol) was dissolved in o-dichlorobenzene (2037 ml) in a round bottom flask, and triphenylphosphine (400.8 g, 1527.89 mmol) was added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 88.68g of product (yield: 40%).
[0136] In a round-bottom flask, Sub 4-III (88.3 g, 233.65 mmol), (2-nitrophenyl)boronic acid (61 g, 233.65 mmol), Pd(PPh3)4 (8.1 g, 7.01 mmol), K2CO3 (96.9 g, 700.94 mmol), THF (1028 ml), and water (514 ml) were placed and heated to reflux at 80˜90° C. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 82.98g of product (yield: 76%).
[0138] The obtained Sub 4-IV (82 g, 171.72 mmol) was dissolved in o-dichlorobenzene (687 ml) in a round bottom flask, and triphenylphosphine (135.1 g, 515.17 mmol) was added to the reaction solution, followed by stirring at 200° C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 33.66g of product (yield: 44%).
[0140] In a round-bottom flask, Sub 4-V (33.5 g, 75.2 mmol), bromobenzene (36.6 g, 233.104 mmol), Pd2(dba)3 (4.1 g, 4.51 mmol), P(t-Bu)3 (4.6 g, 22.56 mmol), NaO(t-Bu) (50.6 g, 526.36 mmol), and Toluene (789 mL) were placed and heated to reflux at 110° C. for 3 hrs. Upon completion of the reaction, the reaction product was diluted with dichrolomethane as a solvent and then extracted. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with methylene chloride and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was dissolved in toluene and separated by a silica filter. Upon completion of the filter, the solution was concentrated, and recrystallized with toluene and acetone to obtain 31.41 g of product (yield: 62%).
Synthesis Example 10
[0142] (1) Synthesis Method of Intermediate J
[0143] In a round-bottom flask, compound 91 (30 g, 36.19 mmol), NBS (13.5 g, 76 mmol) and BPO (0.9 g, 3.62 mmol) were placed and CH2Cl2(109 ml) as a solvent were added to the reaction solution, followed by stirring at room temperature for 5 hrs. Upon completion of the reaction, the reaction product was diluted with dichrolomethane as a solvent and then extracted. The extracted solution was dried with MgSO4 and vacuum-dried, and then crude product was obtained. The obtained crude product was recrystallized with diethylether and n-hexane and then separated by a silica gel column to obtain 24.64 g of intermediate J (yield: 69%)
[0145] In a round-bottom flask, intermaeiate J (15 g, 15.2 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-3-amine (9.1 g, 31.92 mmol), Pd2(dba)3 (0.6 g, 0.608 mmol), P(t-Bu)3 (0.6 g, 3.04 mmol), NaO(t-Bu) (8.8 g, 91.21 mmol), and Toluene (160 mL) were placed and heated to reflux at 110quadrature for 3 hrs. Upon completion of the reaction, the reaction product was diluted with dichrolomethane as a solvent and then extracted. Upon completion of the reaction, the reaction product was diluted with distilled water at room temperature and then extracted with methylene chloride and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was dissolved in toluene and separated by a silica filter. Upon completion of the filter, the solution was concentrated, and recrystallized with toluene and acetone to obtain 13.37 g of product (yield: 63%).
[0146] Fabrication Test of Organic Electro-Luminescence Device
[0147] An organic electro-luminescence device was manufactured according to a conventional method by using each of compounds 1, 10, 27, and 58 obtained by synthesis as a light emitting host material for a light emitting layer. First, on an ITO layer (anode) formed on a glass substrate, a copper phthalocyanine (hereinafter, referred to as CuPc) film as a hole injection layer was vacuum-deposited with a thickness of 10 nm.
[0148] Then, on this film, 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter, referred to as a-NPD) as a hole transport compound was vacuum-deposited with a thickness of 30nm so as to form a hole transport layer. After the hole transport layer was formed, each of the compounds 1, 10, 27 and 58 as a phosphorescence host material was deposited on the hole transport layer so as to form a light emitting layer.
[0149] At the same time, as a phosphorescent Ir metal complex dopant, tris(2-phenylpyridine)iridium (hereinafter, referred to as Ir(ppy)3) was added. Herein, in the light emitting layer, the concentration of Ir(ppy)3 was 5 wt %. As a hole blocking layer, (1,1-bisphenyl)-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter, referred to as BAlq) was vacuum-deposited with a thickness of 10 nm, and then as an electron injection layer, tris(8-quinolinol)aluminum (hereinafter, referred to as Alga) was film-formed with a thickness of 40 nm. Then,
[0150] LiF (alkali-metal halide) was deposited with a thickness of 0.2 nm, and Al was deposited with a thickness of 150 nm. The Al/LiF was used as a cathode while the organic electro-luminescence device was fabricated.
Comparison Example 1
[0151] For comparison, instead of the inventive compound, a compound (hereinafter, referred to as CBP) represented by Formula 4 was used as a light emitting host material so as to fabricate an organic electro-luminescence device with the same structure as that of Test Example.
TABLE-US-00001 TABLE 1 Host lu- chro- material minous maticity of light current lu- ef- co- emitting Voltage density minance ficiency ordinates layer (V) (mA/cm2) (cd/m2) (cd/A) (x, y) Example 1 compound 5.8 0.31 107 45.3 (0.30, 1 0.60) Example 2 compound 5.6 0.33 105 52.2 (0.32, 10 0.61) Example 3 compound 5.6 0.31 107 50.3 (0.30, 27 0.60) Example 4 compound 5.0 0.31 107 38.3 (0.30, 58 0.60) Com- CBP 6.1 0.31 101 32.6 (0.33, parative 0.61) Example 1
[0152] From the results noted in Table 1, it can be seen that in an organic electro-luminescence device using the inventive material for the organic electro-luminescence device, it is possible to obtain long-life green light with a high efficiency, and an improved color purity. Thus, the inventive material as a green phosphorescence host material for an organic electro-luminescence device can significantly improve the luminous efficiency and life span.
[0153] It is natural that even though the inventive compounds are applied to other organic material layers of an organic electro-luminescence device, e.g., an electron injection layer, an electron transport layer, a hole injection layer and a hole transport layer as well as a light emitting layer, it is possible to achieve the same effects.
[0154] Although a preferred embodiment of the present invention has been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Therefore, the embodiments disclosed in the present invention are intended to illustrate the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiment.
[0155] The scope of the present invention shall be construed on the basis of the accompanying claims in such a manner that all of the technical ideas included within the scope equivalent to the claims belong to the present invention.
Patent applications by Bumsung Lee, Cheonan-Si KR
Patent applications by Daehyuk Choi, Suwon-Si KR
Patent applications by Daesung Kim, Yongin-Si KR
Patent applications by Dongha Kim, Seongnam-Si KR
Patent applications by Hwasoon Jung, Chuncheon-Si KR
Patent applications by Jungcheol Park, Jinhae-Si KR
Patent applications by Junghwan Park, Seoul KR
Patent applications by Soungyun Mun, Yongin-Si KR
Patent applications by Yongwook Park, Anyang-Si KR
Patent applications by DUK SAN NEOLUX CO., LTD.
Patent applications in class Hetero ring
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redpajama_set_name: RedPajamaCommonCrawl


Gul'dan: Has received updated visual effects to make his Abilities easier to spot during battle.
The following new bundles are available for a limited time.
We've once again teamed up with Carbot Animations to add even more HeroStorm-themed portraits and sprays in their signature art style.
Try Mode: Tychus' Dash Talent now correctly grants its Movement Speed reward after using the Complete Quests button.; Uther's Silver Touch Talent now correctly grants its second Mana cost reduction reward to Holy Light after using the Complete Quests button.
Fog of War: Hitting an enemy with certain targeted, ranged Abilities, like Sylvanas' Shadow Dagger, just before the target enters Fog of War or a Line of Sight Blocker now correctly reveal that enemy.; Fixed an issue in which attempting to cast a targeted Ability through the Fog of War on a snapshot of a unit that no longer exists could cause the Hero to path into the terrain and become stuck.
Kel'Thuzad: Phylactery of Kel'Thuzad can no longer be activated before its animation completes.


text:
import { RouteRecordRaw } from 'vue-router';

export const routeLandingGameApi: RouteRecordRaw = {
	name: 'landing.game-api',
	path: '/game-api',
	component: () => import('./game-api.vue'),
};

redpajama_set_name: RedPajamaGithub


When we got our new cat tree, the weather was super nice, so I decided to spend a day enjoying it. Sawyer was in the top cup, and Cooper Murphy had claimed the bottom of the tree. But I got the very best section. Here's the original photo.
To create my art for the blog hop, Mom used LunaPic. She began with K3 Art Effect, then added the Blurred Border and Photo Spread. The last step was the addition of the HDR effect from Picasa. I hope you like it as much as I do; though, I am feeling a bit disjointed. MOL!
In addition to my foray to the catio, I have been exceptionally brave this week. I have joined Mom in bed on a couple of mornings for snuggling and loving. Of course, I made certain Misty May was already up. And just last night while Mom was typing this for me, I joined a passel of other Kitties Blue as well as Mom and Dad on the bed. Misty May was there, but she was snoozing. I still didn't go near her. I have my paws crossed that since she has lost most of her hearing and cannot hear me when she chases me and I squeal, that she will stop bullying me.
Now the I have finished my update, I am hopping over to participate in Athena Cat Goddess Wise Kitty's Caturday Art blog hop. To join in the fun or submit some art of your own, click on Athena's badge.
And finally, I have the privilege of reminding you that tomorrow is our blog hop. Spruce yourself up now and get that photo taken so you can spend your Sunday taking it easy. As usual, we have no idea who will be your host, but whichever one of us shows up, you'll be welcomed with open paws.
The art came out great, Astrid!
You look so pawsome in the cat tree Astrid. We need to either bring our old tree down or have Dad get a new one.
Astrid, that new cat tree is pawsome! We're glad you decided to climb up there and enjoy it.
Astrid, you are getting bolder!
That is a good spot in the cat tree for your Caturday Art, Astrid.
That is very pretty sweet Astrid and I'm glad to hear you had some snuggle time!
We have a spot like that on our cat tree too and we think it's the PRIMO spot!!
The Florida Furkids with smoochies and love to Mau from Allie and paw pats and headbonks to Sawyer from Noelle.
Astrid I think you got the best spot on the new cat tree………! I also think it's very nice that you can sneak up on the bed without "YOU KNOW WHO" whapping you.
Astrid, I am glad your bravery and perseverance is helping you to have good furmily snuggles!


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Consecration of the House
Opening of the 6th Vilnius Piano Festival
2019 November 23, Saturday, 19.00
Lithuanian National Philharmonic Hall, Vilnius
Soloist MŪZA RUBACKYTĖ (piano; Lithuania, France, Switzerland)
Conductor RENATO BALSADONNA (Italy)
LUDWIG VAN BEETHOVEN – Overture Die Weihe des Hauses, Op. 124
ROBERT SCHUMANN – Symphony No. 4 in D minor, Op. 120
JOHANNES BRAHMS – Concerto for piano and orchestra No. 1 in D minor, Op. 15
For the sixth time the Lithuanian National Philharmonic Society invites piano music lovers to the Vilnius Piano Festival launched by pianist Prof. Mūza Rubackytė in 2009. In the initial year the Festival joined the festivities of a millennium since the first mention of Lithuania's name in written records; two years later (2011) it celebrated the legacy of Hungarian composer Ferenc Liszt and paid tribute the Lithuanian artist and composer Mikalojus Konstantinas Čiurlionis on his 100th death anniversary; in 2013, already an event with enthusiastic following, the Festival presented Touched by the Muses concert series and marked the 80th anniversary of Polish contemporary composer Krzysztof Penderecki; in 2015, the Festival's intriguing theme Tandems offered seven stunning piano encounters; in 2017, the event focused on pianists' creative rendezvous and partnership in music, which entitles blossoming of new talents and emerging of new masterpieces.
In 2019, the Festival celebrates its 10th anniversary. Its theme – A Woman's Love and Life – was adopted as the Festival's epigraph from German romanticist Robert Schumann's namesake vocal cycle (Frauen-Liebe und Leben). This year's Festival is dedicated to Clara Schumann, one of the most illustrious 19th-century female pianists, and men composers of genius Robert Schumann and Johannes Brahms, two of her companions in life and music. Their music will be featured in every concert of the Festival.
At the opening concert the audience will meet the Lithuanian piano Maestra Mūza Rubackytė and Italian baton master Renato Balsadonna, who is back on the Festival podium. Both musicians will join the Lithuanian National Symphony Orchestra in Brahms' First Piano Concerto. The concert programme also includes two symphonic scores: monumental Fourth Symphony by Robert Schumann and Beethoven's majestic overture Consecration of the House. The latter was chosen deliberately – after a year-long renovation the National Philharmonic Hall opens the door again with a promise of memorable musical delights.
Mūza Rubackytė, the initiator of the Festival, dedicates this concert to the memory of her Mother T. Rubackienė, pianist and pedagogue. Brahms' First Piano Concerto was of importance to her Mother – accompanied by her Professor Balys Dvarionas she performed it at the graduation of the Vilnius Conservatoire.
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Walleye: Stardew Valley Fishing Guide
rapthar
Fishing is an important part of Stardew Valley, and there are many different types of fish that players can catch in different areas of the map. Walleye is one of the fish that many people want to catch. This guide will help players add Walleye to their collection by telling them where to find them, how to catch them, and what to do with them.
Where to Find Walleye
Stardew Valley players can only fish for Walleye during the fall/winter season, on rainy days. To catch one, players must cast their rod between noon and 2pm at one of the following locations:
Pelican Town River
Cindersap Forest Pond
Mountain Lake
It is important to note that the Walleye can only be found during the two seasons and the specific times listed above, and it must be raining. In addition, players must have a Rain Totem to summon rain in winter.
And those who do not like fishing and are lucky, in autumn and winter, you can find a random Walleye in the trash and on mobile. When purchased, it costs between 315 and 1,000 g.
How to Farm Walleye
The best thing you can do with these special fish is to sell them. It is quite easy to create a Walleye farm and sell them for extra gold. To start, you have to go to Robin's carpentry shop and buy a 5,000 g fish pond. It will take you two days to build the pond.
Initially, there may be three fish in the pond, but if the player completes all the fishing tasks, the capacity of the pond can reach ten. To increase the number of Walleye in the pond, take the following items and place them in the pond.
Capacity 5: Acorns x3, Bug Meat x10, Maple Seeds x3, Pine Cones x3
Capacity 7: Gold Ore x3, Maple Syrup x1, Mixed Seeds x5
Capacity 10: Crayfish x1, Honey x1, Jade x2, Periwinkle x1
It takes three days for a Walleye to spawn in the pond, so players will have to wait a few weeks to reach full production. Hatchlings can be sold for 105g, which can increase to 131g or 157g if the player is a male or female angler respectively.
Walleye | Recipes, Tailoring, and Quests
There are no recipes in Stardew Valley that specifically require a wallet. However, there are three different recipes in which it can be used:
Maki Roll
Quality Fertilizer
For those who want to improve their relationship with Linus, sashimi is one of his favorite dishes, and is a good way to win some friendly hearts. On the other hand, a roll of maki restores 100 energy and 45 health. Of course, it's also good to always have quality fertilizer on your farm to increase the likelihood of producing a quality crop.
You will also need a bag to work on the sewing machine to make a fishing vest.
As for quests, players can go to the "Help Wanted" board in the Stone Shop to receive a random quest that will require them to obtain a wallet. Upon completion of this quest, players will receive 315g and 150 friendship points.
Do Any Villagers Like Walleye?
There are six villagers who are neutral about the walleye and three who hate it. So there is no point in giving a fish to anyone in town. However, if you give a fish as a gift, be sure to give it to one of the villagers from the list below, as it won't hurt your friendship.
Giving the fish to the other villagers will damage the relationship. After all, who wants a smelly fish as a gift?
Here's everything you need to fish for Walleye in Stardew Valley! So wait for the rain, grab some bait and cast your rod. If not, you can always rummage through the trash.
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The eight in the series of CoLIS (Conceptions of Library and Information Science) conferences was held this month in Copenhagen. The splendidly efficient organization was provided by the Royal School of Librarianship and Information Science, the Danish iSchool, now being incorporated into the University of Copenhagen's Arts faculty.
As always with CoLIS, the topics covered were very varied, with an emphasis on theoretical and conceptual issues; this continues to make CoLIS a unique forum in the library/information science (LIS) area. This time there was an increased focus on cultural heritage, practice theory and humanities perspectives, although information literacy and knowledge organization were also well represented. It will be interesting to see if this move to a cultural paradigm is continued in future CoLIS meetings, though not, it is to be hoped, at the expense of other themes and perspectives.
For me, the highpoint of the conference was the panel discussion on the philosophy of information, and Luciano Floridi's contribution in particular, a wide-ranging examination of epistemological and ethical issues around information in an age of 'hyper-history'. Following pre-history, in which there were no information and communication technologies (ICTs), and the age of history in which society uses ICTs from the advent from writing to the late twentieth century, a hyper-historical society is entirely reliant on ICTs. I also very much liked Floridi's concept, appropriate to the conference location on one of the many islands of which much of Denmark is composed, of the idea of information as an archipelago, with various answers to the question "what is information' relating to the different islands. Having said that, I admit to feeling most comfortable with Birger Hjørland's reiteration that LIS is primarily concerned with information instantiated in documents, with that term understood very widely. There papers, together with a variety of other perspectives on the nature of information will appear later this year in an issue of Cybernetics and human knowing.
In a new departure for CoLIS, and indeed any other information conference I have attended, Theresa Anderson built on her studies of the value of 'pausing' and 'playing' in complex, pressurized information environments, to offer a space for, among other things, guided meditation and the composing of Zen poetry.
The full proceedings may be found here, and papers from them will appear in September in Information Research. My own paper, jointly written with Lyn Robinson, on the ways in which information can be considered physical, and why this might matter for LIS, can be found here.
Isto Huvila has written reports of aspects of CoLIS on his blog, and other thoughts and musings on the conference can be found on Twitter, with the hashtags #colis8 and #colis2013.
The next Colis conference will be held in June 2016 in Uppsalla, Sweden, organized jointly by the Departments of Archive, Library and Museum Studies at Uppsala and Lund Universities. Updates will be on Twitter, with hashtag colis2016.
Next Post As long as we don't pretend that it is science?


When it comes to the world wide web, it comes with a wide range of web hosts. If you plan to make some online noise with your own website, it is best that you choose only the best web hosting services being offered out there. If you talk about web hosting services, it is crucial to remember that there is wide array of choices out there for you. Nevertheless, you should always remember that not all web hosting services are being offered by web hosts. So, how will you know that you are eyeing on the perfect web host as well as web hosting services for your website? The best method to determine which web host you will be choosing is to first determine what kind of web hosting services each of them can provide. After knowing what these web hosting services, you should then determine if which one of them will be fitting to your requirements and needs. There are a lot of web hosting services that web hosting companies offer, and the following will be made mention and discussed below.
Co-location hosting: With this type of web hosting service, you can have your own web server and even get the services of a co-located server being offered by a third party host. The web hosting company will then make sure that your server is placed on their network. In addition, they make sure to take charge with the availability of your network as well as your administration.
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text:
{-# LANGUAGE OverloadedStrings #-}

module Unison.TypeParser where

import Unison.Prelude

import qualified Text.Megaparsec as P
import qualified Unison.Lexer as L
import           Unison.Parser
import           Unison.Type (Type)
import qualified Unison.Type as Type
import           Unison.Var (Var)
import qualified Unison.Builtin.Decls as DD
import qualified Unison.HashQualified as HQ
import qualified Unison.Name as Name
import qualified Unison.Names3 as Names
import qualified Data.Set as Set
import Control.Monad.Reader (asks)

-- A parsed type is annotated with its starting and ending position in the
-- source text.
type TypeP v = P v (Type v Ann)

-- Value types cannot have effects, unless those effects appear to
-- the right of a function arrow:
--   valueType ::= Int | Text | App valueType valueType | Arrow valueType computationType
valueType :: Var v => TypeP v
valueType = forall type1 <|> type1

-- Computation
-- computationType ::= [{effect*}] valueType
computationType :: Var v => TypeP v
computationType = effect <|> valueType

valueTypeLeaf :: Var v => TypeP v
valueTypeLeaf =
  tupleOrParenthesizedType valueType <|> typeAtom <|> sequenceTyp

-- Examples: Optional, Optional#abc, woot, #abc
typeAtom :: Var v => TypeP v
typeAtom = hqPrefixId >>= \tok -> case L.payload tok of
  HQ.NameOnly n -> pure $ Type.var (ann tok) (Name.toVar n)
  hq -> do
    names <- asks names
    let matches = Names.lookupHQType hq names
    if Set.size matches /= 1
    then P.customFailure (UnknownType tok matches)
    else pure $ Type.ref (ann tok) (Set.findMin matches)

type1 :: Var v => TypeP v
type1 = arrow type2a

type2a :: Var v => TypeP v
type2a = delayed <|> type2

delayed :: Var v => TypeP v
delayed = do
  q <- reserved "'"
  t <- effect <|> type2a
  pure $ Type.arrow (Ann (L.start q) (end $ ann t))
                    (DD.unitType (ann q))
                    t

type2 :: Var v => TypeP v
type2 = do
  hd <- valueTypeLeaf
  tl <- many (effectList <|> valueTypeLeaf)
  pure $ foldl' (\a b -> Type.app (ann a <> ann b) a b) hd tl

-- ex : {State Text, IO} (List Int)
effect :: Var v => TypeP v
effect = do
 es <- effectList
 t <- valueTypeLeaf
 pure (Type.effect1 (ann es <> ann t) es t)

effectList :: Var v => TypeP v
effectList = do
  open <- openBlockWith "{"
  es <- sepBy (reserved ",") valueType
  close <- closeBlock
  pure $ Type.effects (ann open <> ann close) es

sequenceTyp :: Var v => TypeP v
sequenceTyp = do
  open <- reserved "["
  t <- valueType
  close <- reserved "]"
  let a = ann open <> ann close
  pure $ Type.app a (Type.list a) t

tupleOrParenthesizedType :: Var v => TypeP v -> TypeP v
tupleOrParenthesizedType rec = tupleOrParenthesized rec DD.unitType pair
  where
    pair t1 t2 =
      let a = ann t1 <> ann t2
      in Type.app a (Type.app (ann t1) (DD.pairType a) t1) t2

--  valueType ::= ... | Arrow valueType computationType
arrow :: Var v => TypeP v -> TypeP v
arrow rec =
  let eff = mkArr <$> optional effectList
      mkArr Nothing a b = Type.arrow (ann a <> ann b) a b
      mkArr (Just es) a b = Type.arrow (ann a <> ann b) a (Type.effect1 (ann es <> ann b) es b)
  in chainr1 (effect <|> rec) (reserved "->" *> eff)

-- "forall a b . List a -> List b -> Maybe Text"
forall :: Var v => TypeP v -> TypeP v
forall rec = do
    kw <- reserved "forall" <|> reserved "∀"
    vars <- fmap (fmap L.payload) . some $ prefixDefinitionName
    _ <- matchToken $ L.SymbolyId "." Nothing
    t <- rec
    pure $ Type.foralls (ann kw <> ann t) vars t


Apologies! The website is in need of an update here. I'm hoping my roommate will have time to get my banner done and my new graphics before his break is over. I want this place finished before I have to renew my domain! I've also got to get those new costumes up, though I need to get them photographed.
I got a Sweetie Belle costume done to run around with the Dangerous Ladies as Rarity and Pinkie, Gina as Scootaloo and Alex as Spike. The only photo I have of it completed is here on my tumblr. I feel like such a slacker for not having more for you. The cape was made by Gina. Many thanks to her!
In other news, I got another job, so hopefully I can continue to pump out new costumes and make it to more events. After the holidays I'll probably finally quit my other job to focus on the one awesome job. So that's exciting. I love my new coworkers, and I'm finally working in a kitchen.
Happy holidays to everyone! I hope the season is awesome and New Year's is awesome. Look forward to changes in the new year! Love you all!
Previous Previous post: Halloween and More – The Recap!


text:
GOPATH=$GOPATH:`pwd`

cd src/server && fresh


text:
<?php $this->load->view('templates/message_handler') ?>

    <form method="post" target="_blank" action="<?php echo base_url();?>hrm/ReportPembayaran/print_pdf" id="dataForm" class="form-horizontal row-form">

    		Karyawan

                <select name="kary" id="kary" class="form-control select2 input-sm" style="width: 100%;">
    				<option value="0">All / Semua Karyawan</option>
					<?php foreach($kary as $row){?>
					<option value="<?php echo $row->id;?>"><?php echo $row->nik_kary." - ".$row->nama_kary;?></option>
					<?php } ?>
    			</select>

    		Periode Pembayaran

                <select name="per_pnj" id="per_pnj" class="form-control select2 input-sm" style="width: 100%;">
    				<option value="0">All / Semua Waktu</option>
    				<option value="1">Pilihan Tanggal</option>
    			</select>

    		Dari Tanggal

                <input
                    class="form-control input-sm datepicker"
                    type="text"
                    name="start_from"
                    id="start_from"
                    placeholder="Dari Tanggal"
					style="text-align:right"
                    required="true"/>

    		Sampai Dengan Tanggal

                <input
                    class="form-control input-sm datepicker"
                    type="text"
                    name="end_from"
                    id="end_from"
                    placeholder="Sampai Dengan Tanggal"
					style="text-align:right"
                    required="true"/>

                <input type="hidden" name="id" value="<?php echo (empty($contentData['id']))? '' : $contentData['id']; ?>"/>
    			<button type="button" class="btn btn-flat btn-primary color-palette btn-sm submit" dataRow="print_pdf">  Print PDF </button>

    <?php echo form_close(); ?>