KR20210083749A - New thiazole monomer including fluorine atoms and manufacturing method thereof - Google Patents

New thiazole monomer including fluorine atoms and manufacturing method thereof Download PDF

Info

Publication number
KR20210083749A
KR20210083749A KR1020190176354A KR20190176354A KR20210083749A KR 20210083749 A KR20210083749 A KR 20210083749A KR 1020190176354 A KR1020190176354 A KR 1020190176354A KR 20190176354 A KR20190176354 A KR 20190176354A KR 20210083749 A KR20210083749 A KR 20210083749A
Authority
KR
South Korea
Prior art keywords
formula
compound
temperature
equivalents
reaction
Prior art date
Application number
KR1020190176354A
Other languages
Korean (ko)
Other versions
KR102300998B1 (en
Inventor
김인태
Original Assignee
광운대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 광운대학교 산학협력단 filed Critical 광운대학교 산학협력단
Priority to KR1020190176354A priority Critical patent/KR102300998B1/en
Publication of KR20210083749A publication Critical patent/KR20210083749A/en
Application granted granted Critical
Publication of KR102300998B1 publication Critical patent/KR102300998B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • H01L51/0069—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring

Abstract

The present invention relates to a novel thiazole monomer containing a fluorine atom and a method for preparing the same. The present invention is to provide: a novel monomer which has a donor-acceptor structure and can be used for the synthesis of a conjugated polymer having high conductivity, by preparing thiazole from thiourea, introducing fluorine to aminothiazole to prepare fluorothiazole, and preparing a novel thiazole monomer containing a fluorine atom and having a π-conjugated structure from the thiazole derivative; and a method for preparing the novel monomer. According to the present invention, the thiazole monomer containing a fluorine atom shows an increased function as an acceptor as compared to existing sulfur-containing thiazole monomers and can be used advantageously for preparing a donor-acceptor polymer, and has an advantage of showing improved properties such as increased conductivity derived from the extension of a conjugation length and absorption of a wavelength in a near IR region, and can provide increased applicability to a conductive polymer. In addition, the thiazole monomer containing a fluorine atom can be used for solar cells, transparent conductors, thin film transistors, organic light emitting diodes (OLED or organic EL), or the like through the synthesis of a conjugated polymer having a donor-acceptor structure.

Description

플루오린 원자가 포함된 신규 싸이아졸 단량체 및 그 제조 방법{New thiazole monomer including fluorine atoms and manufacturing method thereof}New thiazole monomer including fluorine atoms and manufacturing method thereof

본 발명은 플루오린 원자가 포함된 신규 싸이아졸 단량체 및 그 제조 방법에 관한 것으로, 보다 상세하게는 싸이아졸에 전자를 끄는 작용기인 플루오린 원자를 합성하는 것을 시작으로, 이 유도체로부터 π-공액 구조를 갖는 새로운 구조의 싸이아졸 단량체를 합성하는 기술에 관한 것이다.The present invention relates to a novel thiazole monomer containing a fluorine atom and a method for preparing the same, and more particularly, starting by synthesizing a fluorine atom, which is a functional group that attracts electrons to thiazole, a π-conjugated structure from this derivative It relates to a technology for synthesizing a thiazole monomer having a new structure.

칼코겐족(chalcogen group)으로 불리우는 16족 원소들은 그 족의 전자적 특징 때문에, 유기물질에 다양하게 응용되고 있다. 대표적으로 황을 이용한 단량체 합성에 관한 연구가 있다. Group 16 elements called chalcogen group are variously applied to organic materials because of the electronic characteristics of the group. A representative study is on the synthesis of monomers using sulfur.

한편, 16족 원소 중 황은 이를 도입하면 원자 크기가 크기 때문에 Pz 오비탈의 결합이 약해져 밴드 갭(band gap)을 감소시킬 수 있는 장점이 있다.On the other hand, when sulfur among the group 16 elements is introduced, since the atomic size is large, the Pz orbital bond is weakened, thereby reducing the band gap.

황을 도입하면 컨쥬게이션의 길이가 늘어나 이로 인한 전도도의 증가, 근적외선 영역의 파장 흡수같은 성질로 인해 전도성 고분자에 응용성을 높일 수 있다는 장점이 있다.When sulfur is introduced, the length of the conjugation increases, which has the advantage of increasing its applicability to conductive polymers due to properties such as increased conductivity and absorption of wavelengths in the near-infrared region.

또한, 이러한 황을 포함하는 그룹에 전자를 끄는 치환기(F)의 도입으로 이를 이용한 단량체를 만든다면, 어셉터의 효과가 커져서 도너-어셉터(D-A) 고분자를 만드는데 더욱 유용하다는 장점이 있다.In addition, if a monomer is made by introducing an electron-withdrawing substituent (F) to the group containing sulfur, the effect of the acceptor is increased, so that it is more useful for making a donor-acceptor (D-A) polymer.

하지만 아직까지 전자 끄는 치환기가 포함된 싸이아졸 단량체의 장점에도 불구하고 전자 끄는기를 포함하는 황이 들어간 단량체 합성 기술은 기본적으로 황이 들어간 단량체 합성 기술보다 연구 사례가 적은 편이다. 그 이유는 단량체에 황만을 도입하여 합성하는 것 보다 전자끄는기를 갖는 단량체를 합성하는 것 자체가 어렵기 때문이다.However, despite the advantages of thiazole monomers with electron-withdrawing substituents, there are fewer research cases for monomer synthesis techniques containing sulfur containing electron-withdrawing groups than those with sulfur-containing monomers. The reason is that it is more difficult to synthesize a monomer having an electron withdrawing group than to synthesize it by introducing only sulfur into the monomer.

따라서 이러한 전자끄는기를 포함하고 황을 도입한 새로운 단량체 합성 기술의 필요성이 대두되고 있는 실정이다.Therefore, the need for a new monomer synthesis technology including such an electron withdrawing group and introducing sulfur is emerging.

한국 등록특허공보 등록번호 10-0820935(2008.04.02)Korean Patent Publication No. 10-0820935 (2008.04.02) 한국 등록특허공보 등록번호 10-1597205(2016.02.18.)Korea Patent Publication No. 10-1597205 (2016.02.18.) 한국 등록특허공보 등록번호 10-0773650(2007.10.30.)Korea Patent Publication No. 10-0773650 (2007.10.30.) 한국 등록특허공보 등록번호 10-0679777(2007.01.31.)Korean Patent Publication No. 10-0679777 (Jan. 31, 2007)

상기와 같은 문제점을 해결하기 위한 본 발명의 목적은 도너-억셉터 구조를 가져 높은 전도도를 갖는 공액 고분자 합성에 사용될 수 있는 신규 단량체를 얻기 위해 싸이오 우레아를 이용한 싸이아졸 합성과 이후 아미노 싸이아졸에 플루오린을 도입하여 플루오로 싸이아졸을 합성한 후 싸이아졸 유도체로부터 π-공액 구조를 갖는 플루오린 원자가 포함된 신규 싸이아졸 단량체 및 그 제조방법을 제공하는데 있다.An object of the present invention to solve the above problems is to synthesize thiazole using thiourea to obtain a novel monomer that has a donor-acceptor structure and can be used for synthesizing a conjugated polymer having high conductivity, followed by amino thiazole. An object of the present invention is to provide a novel thiazole monomer containing a fluorine atom having a π-conjugated structure from a thiazole derivative after synthesizing fluorothiazole by introducing fluorine and a method for preparing the same.

상기한 바와 같은 목적을 달성하고 종래의 결점을 제거하기 위한 과제를 수행하는 본 발명은 하기 화학식 1로 표시되는 플루오린 원자가 포함된 신규 싸이아졸 단량체를 제공함으로써 달성된다.The present invention for achieving the above object and for eliminating the conventional drawbacks is achieved by providing a novel thiazole monomer containing a fluorine atom represented by the following formula (1).

<화학식 1><Formula 1>

Figure pat00001
Figure pat00001

상기 화학식 1에서 A는 H, Br, Cl, I, 중에서 선택된 어느 하나이다.In Formula 1, A is any one selected from H, Br, Cl, and I.

본 발명은 다른 실시양태로,The present invention in another embodiment,

a) Thiourea에 diethyl 2-chloro-3-oxosuccinate를 가하여 하기 화학식 2로 표현되는 화합물을 제조하는 단계;a) preparing a compound represented by the following Chemical Formula 2 by adding diethyl 2-chloro-3-oxosuccinate to Thiourea;

b) 화학식 2의 화합물에 Nitrosonium tetrafluoroborate을 이용한 할로젠화로 화학식 3으로 표현되는 화합물을 제조하는 단계;b) preparing a compound represented by Formula 3 by halogenating the compound of Formula 2 with Nitrosonium tetrafluoroborate;

c) 화학식 3의 화합물에 diisobutylaluminum hydride를 사용하여 ester 그룹을 alcohol 그룹으로 환원시켜 하기 화학식 4로 표현되는 화합물을 제조하는 단계;c) reducing the ester group to an alcohol group using diisobutylaluminum hydride in the compound of Formula 3 to prepare a compound represented by the following Formula 4;

d) 화학식 4로 표현되는 화합물을 이루는 alcohol 그룹을 치환하여 하기 화학식 5로 표현되는 화합물을 제조하는 단계;d) preparing a compound represented by the following formula (5) by substituting an alcohol group constituting the compound represented by formula (4);

e) ethly alcohol에 sodium sulfide nonahydrate를 녹여서 화학식 5의 화합물과 함께 적가하여 하기 화학식 6으로 표현되는 화합물을 제조하는 단계;e) dissolving sodium sulfide nonahydrate in ethly alcohol and adding it dropwise together with the compound of formula 5 to prepare a compound represented by the following formula (6);

f) 화학식 6의 화합물에 용매와 함께 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 첨가하여 하기 화학식 7로 표현되는 화합물을 제조하는 단계; 및f) preparing a compound represented by the following formula 7 by adding 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) to the compound of formula 6 with a solvent; and

g) 화학식 7의 화합물을 용매에 녹인 후 할로젠화 반응을 통한 단계를 거쳐 청구항 1의 화학식 1로 표시되는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법을 제공함으로서 달성된다. g) It is achieved by providing a method for preparing a novel thiazole monomer containing a fluorine atom represented by Formula 1 of claim 1 through a step through a halogenation reaction after dissolving the compound of Formula 7 in a solvent.

<화학식 2><Formula 2>

Figure pat00002
Figure pat00002

<화학식 3><Formula 3>

Figure pat00003
Figure pat00003

<화학식 4><Formula 4>

Figure pat00004
Figure pat00004

<화학식 5><Formula 5>

Figure pat00005
Figure pat00005

상기 화학식 5에서 A는 Br, Cl, I 중에서 선택된 어느 하나이다.In Formula 5, A is any one selected from Br, Cl, and I.

<화학식 6><Formula 6>

Figure pat00006
Figure pat00006

<화학식 7><Formula 7>

Figure pat00007
Figure pat00007

바람직한 실시예로, 상기 a)단계에서 diethyl 2-chloro-3-oxosuccinate는 thiourea 대비 당량 기준으로 1.1 ~ 1.2 당량 사용할 수 있다.In a preferred embodiment, in step a), 1.1 to 1.2 equivalents of diethyl 2-chloro-3-oxosuccinate may be used based on equivalents compared to thiourea.

바람직한 실시예로, 상기 a)단계는 thiourea 1 ~ 50g을 N2 가스하에서 무수물 ethylalcohol(EtOH)용매를 사용하여 상온에 용해시킨 후, 액체 상태인 diethyl 2-chloro-3-oxosuccinate 1.1 ~ 1.2 당량을 첨가해주고 상온에서 1시간 교반하고, 교반 후에 60∼７0℃에서 교반 후에 반응이 종료된 혼합물을 상온으로 내려 재결정 과정을 거친 후, ethylalcohol로 워싱 및 필터링하여 필터지 위에 있는 화합물을 상온세 1시간 건조하는 과정으로 아미노기를 갖도록 하는 단계일 수 있다.In a preferred embodiment, in step a), 1 to 50 g of thiourea is dissolved at room temperature using an anhydrous ethylalcohol (EtOH) solvent under N2 gas, and 1.1 to 1.2 equivalents of diethyl 2-chloro-3-oxosuccinate in a liquid state are added. After stirring at room temperature for 1 hour, after stirring, the reaction mixture was lowered to room temperature after stirring at 60 to 70 ° C, and recrystallized, washed with ethylalcohol and filtered to dry the compound on filter paper at room temperature for 1 hour. The process may be a step to have an amino group.

바람직한 예로 상기 b)단계는 NOBF4를 화학식 2의 화합물 대비 당량기준으로 1.2 ~ 1.5 당량을 사용할 수 있다.As a preferred example, in step b) , 1.2 to 1.5 equivalents of NOBF 4 may be used based on equivalents compared to the compound of Formula 2.

바람직한 실시예로, 상기 b)단계는 화학식 2의 화합물 1.0 ~ 10g에 48 wt% HBF4 (tetrafluoroboric acid) 용액에 넣어 녹인 후 N2 가스 하에서 반응용기의 온도를 ice와 acetone(C3H6O)을 이용하여 -10℃로 내려준 후, NOBF4를 화학식 2의 화합물 대비 당량 기준으로 1.2 ~ 1.5 당량을 적가한 다음 0℃에서 20분동안 교반한 다음 diethyl eter(C4H10O)를 첨가하여 dry ice와 acetonitrile을 이용하여 -42℃로 내려준 후 30분 동안 교반하여 생성된 고체를 diethyl ether를 이용하여 워싱 및 필터링 후에 생성된 고체를 toluene에 녹여 90℃로 1 ~ 2시간 교반 후 생성된 여액을 rotary evaporator를 이용하여 용매를 모두 제거한 후에 건조된 혼합물을 silica gel column chromato graphy(Methylene chloride : Hexane = 5 : 5(부피비))를 통해 정제하는 과정을 포함할 수 있다.In a preferred embodiment, in step b), 1.0 to 10 g of the compound of Formula 2 is dissolved in 48 wt% HBF 4 (tetrafluoroboric acid) solution, and then the temperature of the reaction vessel is adjusted to ice and acetone (C 3 H 6 O) under N 2 gas. ) using ) , 1.2 to 1.5 equivalents of NOBF 4 were added dropwise based on the equivalent weight of the compound of Formula 2, followed by stirring at 0° C. for 20 minutes, and then diethyl eter (C 4 H 10 O) was added. After addition, the solid was lowered to -42°C using dry ice and acetonitrile and stirred for 30 minutes. After washing and filtering with diethyl ether, the formed solid was dissolved in toluene and stirred at 90°C for 1 to 2 hours. After removing all the solvent from the resulting filtrate using a rotary evaporator, it may include a process of purifying the dried mixture through silica gel column chromatography (Methylene chloride: Hexane = 5: 5 (volume ratio)).

바람직한 실시예로, 상기 c)단계는 DIBAL-H(diisobutyl aluminium hudrid)를 화학식 3의 화합물 대비 당량 기준으로 4.4 ~ 4.8 당량을 사용할 수 있다.In a preferred embodiment, in step c), 4.4 to 4.8 equivalents of diisobutyl aluminum hudrid (DIBAL-H) may be used based on the equivalent weight of the compound of Formula 3.

바람직한 실시예로, 상기 c)단계는 화학식 3의 화합물 1.0 ~ 20g에 toluene을 넣어 녹인 후 N2 가스 하에서 반응용기의 온도를 dry ice와 acetone(C3H6O)을 이용하여 -78℃로 내려준 후, 액체상태의 DIBAL-H(diisobutyl aluminium hudrid)을 화학식 3의 화합물 대비 당량기준으로 4.4 ~ 4.8 당량을 적가한 다음, 천천히 온도를 올려 상온에서 12시간 동안 교반하여 반응시키고, 이후 반응이 끝난 반응용기의 온도를 다시 0 ~ -10℃로 다시 내려준 후, methanol과 potassium sodium tartrate 용액을 넣어 반응을 종결하고, Ethyl acetate(EA)를 이용하여 유기물을 추출하며, 추출된 유기층에 남아있는 소량의 물을 MgSO4를 넣어 제거한 다음, rotary evaporator를 이용하여 용매를 모두 제거하고 흰색 고체 화합물을 얻어내는 과정을 포함할 수 있다.In a preferred embodiment, in step c), toluene is dissolved in 1.0 to 20 g of the compound of Formula 3, and then the temperature of the reaction vessel is lowered to -78° C. under N 2 gas using dry ice and acetone (C 3 H 6 O). After lowering, 4.4 to 4.8 equivalents of DIBAL-H (diisobutyl aluminum hudrid) in the liquid state were added dropwise based on equivalents compared to the compound of Formula 3, and then the temperature was slowly raised to react by stirring at room temperature for 12 hours, and then the reaction was After lowering the temperature of the finished reaction vessel to 0 ~ -10℃ again, methanol and potassium sodium tartrate solution are added to terminate the reaction, and the organic material is extracted using ethyl acetate (EA), and the remaining A small amount of water is removed by adding MgSO 4 , and then using a rotary evaporator to remove all of the solvent and obtain a white solid compound.

바람직한 실시예로, 상기 d)단계는 화학식 4의 화합물 0.1 ~ 20g을 THF 10 ~ 1000 mL를 사용하여 녹인 다음, 반응용기의 온도를 얼음과 acetone(C3H6O)을 이용하여 0 ~ -10℃로 내려준 후 반응 용기 내부의 온도가 외부의 온도와 같아 질 때까지 방치한 다음, pyridine을 화합물 대비 1.0 ~ 1.5 당량기준으로 0.05 ~ 25 mL을 넣고 30 ~ 120분 동안 교반하고, 이후 반응용기 온도가 0 ~ -10℃로 유지된 상태에서 액체 상태의 phosphorous tribromide(PBr3), phosphorous trichloride(PCl3), phosphorous triiodide(PI3) 중에서 할로젠화 반응물로 선택된 어느 하나를 0.5 ~ 1.5 당량으로 천천히 적가하며, 이후 상온까지 서서히 온도를 올리면서 2 ~ 12 시간 동안 교반하여 반응시키고, 반응이 끝난 후 반응용기의 온도를 0 ~ -10 ℃로 다시 내려준 후 차가운 물을 넣어 반응을 종결하고 Metylene chloride(MC)를 이용하여 유기물을 추출하며, 추출된 유기층에 남아있는 소량의 물을 MgSO4를 넣어 제거 후 필터링 하고 유기층을 vacuum evaporator를 이용하여 용매를 모두 제거하여 화합물을 얻은 후 silica gel column chromatography( Ethyl acetate : hexane = 1 : 9(부피비))를 통해 정제하는 과정을 포함할 수 있다.In a preferred embodiment, in step d), 0.1 to 20 g of the compound of Formula 4 is dissolved using 10 to 1000 mL of THF, and then the temperature of the reaction vessel is adjusted to 0 to - using ice and acetone (C 3 H 6 O). After lowering the temperature to 10℃, let it stand until the temperature inside the reaction vessel becomes the same as the temperature outside, then add 0.05 ~ 25 mL of pyridine based on 1.0 ~ 1.5 equivalents of the compound, stir for 30 ~ 120 minutes, and then react 0.5 to 1.5 equivalents of any one selected as a halogenation reactant among liquid phosphorous tribromide (PBr 3 ), phosphorous trichloride (PCl 3 ), and phosphorous triiodide (PI 3 ) when the container temperature is maintained at 0 ~ -10℃ After the reaction is stirred for 2 to 12 hours while slowly raising the temperature to room temperature, the temperature of the reaction vessel is lowered to 0 ~ -10 ℃ again after the reaction is completed, and then cold water is added to terminate the reaction. The organic material is extracted using methylene chloride (MC), and a small amount of water remaining in the extracted organic layer is removed by adding MgSO 4 , filtered, and the organic layer is removed using a vacuum evaporator to remove all solvents to obtain the compound, followed by silica gel column It may include a process of purification through chromatography ( Ethyl acetate : hexane = 1 : 9 (volume ratio)).

바람직한 실시예로, 상기 e)단계는 화학식 5의 화합물을 sodium sulfide nonahydrate 대비 당량기준으로 1.0 ~ 1.3 당량을 사용할 수 있다.In a preferred embodiment, in step e), 1.0 to 1.3 equivalents of the compound of Formula 5 may be used on an equivalent basis relative to sodium sulfide nonahydrate.

바람직한 실시예로, 상기 e)단계는 고리 닫힘 반응을 sodium sulfide nonahydrate을 화합물 5 대비 당량 기준으로 1.0 ~ 1.3 당량을 N2 가스하에서 무수물의 ethyl alcohol을 넣어 녹인 후, 화학식 5의 화합물 1.0g ~ 4.0g을 ethyl alcohol을 넣어 녹인 후 빈 반응용기에 ethyl alcohol 70mL ~ 500mL을 넣고 N2 가스하에서 실린지 펌프를 이용하여 6 ~ 22시간 동안 적가하면서, sodium sulfide nonahydrate를 dropping funnel로 천천히 적가하고, 온도는 얼음과 acetone(C3H6O)을 이용하여 0 ~ -10 ℃ 로 낮추어 준 다음, 1 ~ 2 시간 동안 -10 ~ 5℃에서 교반한 후 상온으로 온도를 서서히 올려 2 ~ 6시간동안 교반하여 반응시키고, 반응이 종료된 후 용매를 ethyl alcohol을 vacuum evaporator를 통해 제거하여 화합물을 얻고, 이 화합물을 n-hexane으로 녹여서 안녹는 고체를 필터링을 한 후 n-hexane에 녹은 화합물을 TEA로 Neutralization 처리 된 silica gel 컬럼(Ethyl Acetate : Hexane = 1 : 9(부피비))으로 정제하는 과정을 포함할 수 있다.In a preferred embodiment, in step e), 1.0 to 1.3 equivalents of sodium sulfide nonahydrate relative to compound 5 were dissolved in anhydrous ethyl alcohol under N 2 gas for the ring closing reaction, and 1.0g to 4.0 of the compound of Formula 5 After dissolving g in ethyl alcohol, put 70mL ~ 500mL of ethyl alcohol into an empty reaction vessel and add sodium sulfide nonahydrate dropwise with a dropping funnel while using a syringe pump under N 2 gas for 6 to 22 hours. It was lowered to 0 ~ -10 ℃ using ice and acetone (C 3 H 6 O), and then stirred at -10 ~ 5℃ for 1 to 2 hours, then slowly raised to room temperature and stirred for 2 to 6 hours. After the reaction was completed, the solvent was removed by removing ethyl alcohol through a vacuum evaporator to obtain a compound, and the compound dissolved in n- hexane was dissolved in n-hexane to filter the insoluble solid, and the compound dissolved in n- hexane was treated with TEA for neutralization. It may include the process of purification with a silica gel column (Ethyl Acetate: Hexane = 1 : 9 (volume ratio)).

바람직한 실시예로, 상기 f)단계는 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 화학식 6의 화합물 대비 당량기준으로 1.0 ~ 1.3 당량을 사용할 수 있다.In a preferred embodiment, in step f), 1.0 to 1.3 equivalents of 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) may be used on the basis of equivalents compared to the compound of Formula 6.

바람직한 실시예로, 상기 f)단계는 화학식 6의 화합물 0.3 ~ 0.5 g을 N2 가스하에서 유기용매를 넣어 교반 후, 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 화학식 6의 화합물 대비 당량기준으로 1.0 ~ 1.2 당량을 넣어 60 ~ 80 ℃에서 8 ~ 36시간 동안 교반하여 반응시키고, 반응이 끝난 용액을 silica gel 칼럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))을 이용하여 fresh 컬럼하여 정제하는 과정을 포함할 수 있다.In a preferred embodiment, in step f), 0.3 to 0.5 g of the compound of Formula 6 is stirred by adding an organic solvent under N 2 gas, and then 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) was added 1.0 to 1.2 equivalents based on the equivalent of the compound of Formula 6, stirred at 60 to 80 ° C. for 8 to 36 hours, and the reaction solution was transferred to a silica gel column (Ethyl acetate : hexane = 0.5 : 9.5 (volume ratio) ) using a fresh column to purify.

바람직한 실시예로, 상기 g)단계는 할로젠화 반응물인 N-bromosuccinimide(NBS), N-chlorosuccinimide(NCS), N-iodosuccinimide(NIS)중에서 선택된 어느 하나를 화학식 8의 화합물 대비 당량기준으로 2.0 ~ 2.5 당량을 사용할 수 있다.In a preferred embodiment, in step g) , any one selected from the halogenation reactants N- bromosuccinimide (NBS), N- chlorosuccinimide (NCS), and N- iodosuccinimide (NIS) is 2.0 ~ 2.5 equivalents may be used.

바람직한 실시예로, 상기 g)단계는 화학식 7의 화합물 0.1 ~ 10g과 유기용매를 혼합하여 용해한 후 dry ice와 aceone을 이용하여 -78 ~ -40℃에서 N2 가스를 순환시키면서 교반하고, 할로젠화 반응물인 N-bromosuccinimide(NBS), N-chlorosuccinimide(NCS), N-iodosuccinimide(NIS) 중에서 선택된 어느 하나를 화학식 7의 화합물 대비 당량기준으로 2.0 ~ 2.5 당량 사용하여 고체 상태로 빠르게 첨가하고 1 ~ 2 시간 동안 온도를 서서히 상온으로 올리고, 상온에서 0.1 ~ 2 시간 동안 교반한 후 상기 유기용매를 rotary evaporator을 이용하여 제거한 다음 혼합물을 triethyl amine으로 중화된 silica gel 컬럼을 이용하여 fresh 컬럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))으로 정제하는 과정을 포함할 수 있다.In a preferred embodiment, in step g), 0.1 to 10 g of the compound of Formula 7 and an organic solvent are mixed and dissolved, and then stirred using dry ice and aceone at -78 to -40° C. while circulating N 2 gas, and halogen One selected from N- bromosuccinimide (NBS), N- chlorosuccinimide (NCS), and N -iodosuccinimide (NIS), which is a reaction product, is quickly added in a solid state using 2.0 to 2.5 equivalents compared to the compound of Formula 7 and 1 to The temperature was gradually raised to room temperature for 2 hours, stirred at room temperature for 0.1 to 2 hours, the organic solvent was removed using a rotary evaporator, and then the mixture was neutralized with triethyl amine and a silica gel column was used to obtain a fresh column (Ethyl acetate: hexane = 0.5: 9.5 (volume ratio)) may include a purification process.

상기와 같은 특징을 갖는 본 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체는 전자끄는기를 포함함으로써 기존 황을 포함하는 싸이아졸 단량체보다 어셉터로써의 역할이 커져 도너-억셉터 고분자를 만들때 유용하게 사용될 수 있다. 즉 황을 도입함으로써 원자 크기가 커져 Pz 오비탈의 결합이 약해져 밴드 갭(band gap)을 감소시킬 수 있다는 장점을 가진다.The novel thiazole monomer containing a fluorine atom according to the present invention having the above characteristics increases its role as an acceptor than the conventional thiazole monomer containing sulfur by including an electron withdrawing group, so it is useful when making a donor-acceptor polymer can be used That is, by introducing sulfur, the atomic size is increased and the Pz orbital bond is weakened, thereby reducing the band gap.

또한 컨쥬게이션 길이의 확장으로 인한 전도도의 증가, 근적외선 영역의 파장 흡수와 같은 성질이 좋아져 전도성 고분자에 응용성을 높일 수 있다는 장점을 가진다. In addition, properties such as increase in conductivity due to the extension of the conjugation length and absorption of wavelengths in the near-infrared region are improved, which has the advantage of increasing applicability to conductive polymers.

또한 본 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체는 도너-억셉터(donor-acceptor) 구조를 갖는 공액 고분자 합성을 통해 향후 태양전지, 투명 전도체(transparent conductor), 박막 트랜지스터, 유기발광소자(OLED: Organic Light Emitting Diodes 또는 유기 EL) 등에 이용될 수 있다는 장점을 가진 유용한 발명으로 산업상 그 이용이 크게 기대되는 발명인 것이다.In addition, the novel thiazole monomer containing a fluorine atom according to the present invention can be synthesized in a conjugated polymer having a donor-acceptor structure in the future for solar cells, transparent conductors, thin film transistors, organic light emitting devices ( OLED: It is a useful invention that has the advantage that it can be used for Organic Light Emitting Diodes or organic EL), and its use is highly expected in industry.

도 1은 본 발명의 실시예 2에 따른 diethyl 2-aminothiazole-4,5- dicarboxylate의 1H-NMR 스팩트럼도이고,
도 2는 본 발명의 실시예 2에 따른 diethyl 2-aminothiazole-4,5- dicarboxylate의 13C-NMR 스팩트럼도이고,
도 3은 본 발명의 실시예 2에 따른 diethyl 2-aminothiazole-4,5- dicarboxylate의 FT-IR 스팩트럼도이고,
도 4는 본 발명의 실시예 3에 따른 diethyl 2-fluorothiazole-4,5- dicarboxylate의 1H-NMR 스팩트럼도이고,
도 5는 본 발명의 실시예 3에 따른 diethyl 2-fluorothiazole-4,5- dicarboxylate의 13C-NMR 스팩트럼도이고,
도 6은 본 발명의 실시예 3에 따른 diethyl 2-fluorothiazole-4,5- dicarboxylate의 FT-IR 스팩트럼도이고,
도 7은 본 발명의 실시예 4에 따른 (2-fluorothiazole-4,5-diyl)dimethanol의 1H-NMR 스팩트럼도이고,
도 8은 본 발명의 실시예 4에 따른 (2-fluorothiazole-4,5-diyl)dimethanol의 13C-NMR 스팩트럼도이고,
도 9는 본 발명의 실시예 4에 따른 (2-fluorothiazole-4,5-diyl)dimethanol의 FT-IR 스팩트럼도이고,
도 10은 본 발명의 실시예 5에 따른 4,5-bis(bromomethyl)-2-fluorothiazole의 1H-NMR 스팩트럼도이고,
도 11은 본 발명의 실시예 5에 따른 4,5-bis(bromomethyl)-2-fluorothiazole의 13C-NMR 스팩트럼도이고,
도 12는 본 발명의 실시예 5에 따른 4,5-bis(bromomethyl)-2-fluorothiazole의 FT-IR 스팩트럼도이고,
도 13은 본 발명의 실시예 6에 따른 2-fluoro-4,6-dihydrothieno[3,4-d] thiazole의 1H-NMR 스팩트럼도이고,
도 14는 본 발명의 실시예 6에 따른 2-fluoro-4,6-dihydrothieno[3,4-d] thiazole의 13C-NMR 스팩트럼도이고,
도 15는 본 발명의 실시예 6에 따른 2-fluoro-4,6-dihydrothieno[3,4-d] thiazole의 UV-vis 스팩트럼도이고,
도 16은 본 발명의 실시예 7에 따른 2-fluorothieno[3,4-d]thiazole의 1H-NMR 스팩트럼도이고,
도 17은 본 발명의 실시예 7에 따른 2-fluorothieno[3,4-d]thiazole의 13C- NMR 스팩트럼도이고,
도 18은 본 발명의 실시예 7에 따른 2-fluorothieno[3,4-d]thiazole의 UV- vis 스팩트럼도이고,
도 19는 본 발명의 실시예 8에 따른 4,6-dibromo-2-fluorothieno [3,4-d] [1,3]thiazole의 1H-NMR 스팩트럼도이고,
도 20은 본 발명의 실시예 8에 따른 4,6-dibromo-2-fluorothieno [3,4-d] [1,3]thiazole의 13C-NMR 스팩트럼도이고,
도 21은 본 발명의 실시예 8에 따른 4,6-dibromo-2-fluorothieno [3,4-d] [1,3]thiazole의 UV-vis 스팩트럼도이다. 1 is a 1 H-NMR spectrum diagram of diethyl 2-aminothiazole-4,5-dicarboxylate according to Example 2 of the present invention;
2 is a 13 C-NMR spectrum diagram of diethyl 2-aminothiazole-4,5-dicarboxylate according to Example 2 of the present invention;
3 is an FT-IR spectrum diagram of diethyl 2-aminothiazole-4,5-dicarboxylate according to Example 2 of the present invention;
4 is a 1 H-NMR spectrum diagram of diethyl 2-fluorothiazole-4,5-dicarboxylate according to Example 3 of the present invention;
5 is a 13 C-NMR spectrum diagram of diethyl 2-fluorothiazole-4,5-dicarboxylate according to Example 3 of the present invention;
6 is an FT-IR spectrum diagram of diethyl 2-fluorothiazole-4,5-dicarboxylate according to Example 3 of the present invention;
7 is a 1 H-NMR spectrum diagram of (2-fluorothiazole-4,5-diyl)dimethanol according to Example 4 of the present invention;
8 is a 13 C-NMR spectrum diagram of (2-fluorothiazole-4,5-diyl)dimethanol according to Example 4 of the present invention;
9 is an FT-IR spectrum diagram of (2-fluorothiazole-4,5-diyl)dimethanol according to Example 4 of the present invention;
10 is a 1 H-NMR spectrum diagram of 4,5-bis(bromomethyl)-2-fluorothiazole according to Example 5 of the present invention;
11 is a 13 C-NMR spectrum diagram of 4,5-bis(bromomethyl)-2-fluorothiazole according to Example 5 of the present invention;
12 is an FT-IR spectrum diagram of 4,5-bis(bromomethyl)-2-fluorothiazole according to Example 5 of the present invention;
13 is a diagram according to Embodiment 6 of the present invention; 1 H-NMR spectrum diagram of 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole,
14 is a diagram according to Embodiment 6 of the present invention; 13 C-NMR spectrum diagram of 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole,
15 is a diagram according to Embodiment 6 of the present invention; UV-vis spectrum diagram of 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole,
16 is a 1 H-NMR spectrum diagram of 2-fluorothieno[3,4-d]thiazole according to Example 7 of the present invention;
17 is a 13 C-NMR spectrum diagram of 2-fluorothieno[3,4-d]thiazole according to Example 7 of the present invention;
18 is a UV-vis spectrum diagram of 2-fluorothieno[3,4-d]thiazole according to Example 7 of the present invention;
19 is a diagram according to Example 8 of the present invention; 1 H-NMR spectrum diagram of 4,6-dibromo-2-fluorothieno [3,4-d] [1,3] thiazole,
20 is a diagram according to Example 8 of the present invention; 13 C-NMR spectrum diagram of 4,6-dibromo-2-fluorothieno [3,4-d] [1,3] thiazole,
21 is a diagram according to Example 8 of the present invention; UV-vis spectrum diagram of 4,6-dibromo-2-fluorothieno[3,4-d][1,3]thiazole.

이하 본 발명의 실시 예인 구성과 그 작용을 첨부도면에 연계시켜 상세히 설명하면 다음과 같다. 또한 본 발명을 설명함에 있어서, 관련된 공지기능 혹은 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명은 생략한다. Hereinafter, the configuration and operation of the embodiment of the present invention will be described in detail in connection with the accompanying drawings. Also, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

본 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체는 하기 화학식 1로 표현되는 단량체이다.The novel thiazole monomer containing a fluorine atom according to the present invention is a monomer represented by the following formula (1).

<화학식 1><Formula 1>

Figure pat00008
Figure pat00008

상기 화학식에서 A는 H, Br, Cl, I 중 어느 하나이다.In the above formula, A is any one of H, Br, Cl, and I.

상기 화학식 1로 표시되는 본 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법은 아래와 같은 단계를 거쳐 합성된다.The method for preparing a novel thiazole monomer containing a fluorine atom according to the present invention represented by Formula 1 is synthesized through the following steps.

a) Thiourea에 diethyl 2-chloro-3-oxosuccinate를 가하여 하기 화학식 2로 표현되는 화합물을 제조하는 단계;a) preparing a compound represented by the following Chemical Formula 2 by adding diethyl 2-chloro-3-oxosuccinate to Thiourea;

b) 화학식 2의 화합물에 Nitrosonium tetrafluoroborate을 이용한 할로젠화로 화학식 3으로 표현되는 화합물을 제조하는 단계;b) preparing a compound represented by Formula 3 by halogenating the compound of Formula 2 with Nitrosonium tetrafluoroborate;

c) 화학식 3의 화합물에 diisobutylaluminum hydride를 사용하여 ester 그룹을 alcohol 그룹으로 환원시켜 하기 화학식 4로 표현되는 화합물을 제조하는 단계;c) reducing the ester group to an alcohol group using diisobutylaluminum hydride in the compound of Formula 3 to prepare a compound represented by the following Formula 4;

d) 화학식 4로 표현되는 화합물을 이루는 alcohol 그룹을 치환하여 하기 화학식 5로 표현되는 화합물을 제조하는 단계;d) preparing a compound represented by the following formula (5) by substituting an alcohol group constituting the compound represented by formula (4);

e) ethly alcohol에 sodium sulfide nonahydrate를 녹여서 화학식 5의 화합물과 함께 적가하여 하기 화학식 6으로 표현되는 화합물을 제조하는 단계;e) dissolving sodium sulfide nonahydrate in ethly alcohol and adding it dropwise together with the compound of formula 5 to prepare a compound represented by the following formula (6);

f) 화학식 6의 화합물에 용매와 함께 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 첨가하여 하기 화학식 7로 표현되는 화합물을 제조하는 단계; 및f) preparing a compound represented by the following formula 7 by adding 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) to the compound of formula 6 with a solvent; and

g) 화학식 7의 화합물을 용매에 녹인 후 할로젠화 반응시키는 단계;g) dissolving the compound of Formula 7 in a solvent, followed by halogenation;

<화학식 2><Formula 2>

Figure pat00009
Figure pat00009

<화학식 3><Formula 3>

Figure pat00010
Figure pat00010

<화학식 4><Formula 4>

Figure pat00011
Figure pat00011

<화학식 5><Formula 5>

Figure pat00012
Figure pat00012

상기 화학식 5에서 A는 Br, Cl, I 중에서 선택된 어느 하나이다.In Formula 5, A is any one selected from Br, Cl, and I.

<화학식 6><Formula 6>

Figure pat00013
Figure pat00013

<화학식 7><Formula 7>

Figure pat00014
Figure pat00014

상기 a)단계는 합성시약 diethyl 2-chloro-3- oxosuccinate를 화학식 2의 화합물 대비 당량기준으로 1.1 ~ 1.2 당량을 사용한다. 1.1 당량 미만으로 사용시 반응이 진행되나 전부 진행되지 않아 당량수를 맞춰 줘야하고, 1.2 당량을 초과하여 첨가시에 HCl 가스가 지속적으로 생성되어 인체에 해롭게 되고 부반응 또한 진행하게 되기 때문이다In step a), 1.1 to 1.2 equivalents of the synthetic reagent diethyl 2-chloro-3-oxosuccinate are used on an equivalent basis compared to the compound of Formula 2. When used in less than 1.1 equivalents, the reaction proceeds, but not all proceeds, so the equivalent number must be adjusted. When added in excess of 1.2 equivalents, HCl gas is continuously generated, which is harmful to the human body and causes side reactions to proceed.

구체적으로 상기 a)단계는 thiourea 1 ~ 50g을 2-neck round bottom flask에 넣어준 후 무수물 형태의 ehtylaclohol 20 ~ 500mL와 섞고 N2 가스하에서 교반한다. 교반한 후에 합성시약 diethyl-2-chloro-3- oxosuccinate를 상온에서 thiourea 화합물 대비 당량기준으로 1.1 ~ 1.2 당량을 첨가해 주고 1시간 교반한다. 이후 60 ~ ７0℃에서 교반한다. 반응이 종료된 혼합물을 상온으로 내려 결정이 생기는 것을 확인 한 후, ethylalcohol로 워싱 및 필터링을 한후 필터링하고 남은 고체를 상온에 1시간 정도 건조 시킨 후 건조된 혼합물을 ethylalcohol을 가열 후 냉각 시켜 재결정을 통해 흰색 고체 형태의 화합물을 얻는 과정을 포함할 수 있다.Specifically, in step a), 1 to 50 g of thiourea is put into a 2-neck round bottom flask, mixed with 20 to 500 mL of anhydrous ethylaclohol, and stirred under N 2 gas. After stirring, 1.1 to 1.2 equivalents of the synthetic reagent diethyl-2-chloro-3-oxosuccinate are added at room temperature based on equivalents compared to the thiourea compound, and the mixture is stirred for 1 hour. After that, the mixture is stirred at 60 ~ 70 °C. After confirming that crystals are formed by lowering the reaction mixture to room temperature, wash and filter with ethylalcohol, filter, and dry the remaining solid at room temperature for about 1 hour. Then, the dried mixture is heated with ethylalcohol and cooled to undergo recrystallization. and obtaining the compound in the form of a white solid.

상기 b)단계는 NOBF4를 화학식 2의 화합물 대비 당량 기준으로 1.2 ~ 1.5 당량을 사용한다. 1.2 당량 미만 시용 시 반응이 미진행 되며, 1.5 당량을 초과하여 첨가시 더 이상의 효율 증대가 없고 비용만 더 소요되게 된다.In step b) , 1.2 to 1.5 equivalents of NOBF 4 are used based on equivalents compared to the compound of Formula 2. When less than 1.2 equivalents are applied, the reaction does not proceed, and when more than 1.5 equivalents are added, there is no further increase in efficiency and only cost is increased.

구체적으로 상기b)단계는 화학식 2의 화합물 1 ~ 10g을 2-neck round bottom flask에 넣어준 후 8 wt% HBF4 (tetrafluoroboric acid) 1 ~ 11 mL와 섞고 N2 가스하에서 교반한다. 교반한 후에 합성 시약 NOBF4를 -10℃에서 화학식 2의 화합물 대비 당량기준으로 1.2 ~ 1.5 당량을 첨가해 주고 0℃에서 20분 동안 교반한다. 이후 diethyl ether(C4H10O) 15 ~ 150mL 첨가한 후 dry ice와 acetonitrile을 이용하여 -42℃에서 30분 ~ 1시간 교반한다. 이 후 생성 된 고체를 diethylether로 워싱 및 필터링을 한 후 필터링 하고 남은 고체 생성물을 10 ~ 100mL의 toluene에 녹인 후 1 ~ 2시간 동안 90℃에서 교반한다. 이후 상온으로 온도를 낮춘 후 rotary evaporation을 통해 용매를 모두 제거하고 건조된 혼합물을 silica gel column chromatography(Methylene chloride : Hexane = 5 : 5(부피비))를 통하여 flash 컬럼을 통해 노란색 액체 형태의 화합물을 얻는 과정을 포함할 수 있다.Specifically, in step b), 1 to 10 g of the compound of Formula 2 is put into a 2-neck round bottom flask, mixed with 8 wt% HBF 4 (tetrafluoroboric acid) 1 to 11 mL, and stirred under N 2 gas. After stirring, 1.2 to 1.5 equivalents of the synthesis reagent NOBF 4 are added at -10°C based on equivalents compared to the compound of Formula 2 and stirred at 0°C for 20 minutes. After adding 15 ~ 150 mL of diethyl ether (C 4 H 10 O), use dry ice and acetonitrile to stir at -42°C for 30 minutes to 1 hour. After washing and filtering the resulting solid with diethylether, the remaining solid product is dissolved in 10 to 100 mL of toluene and stirred at 90° C. for 1 to 2 hours. After lowering the temperature to room temperature, all solvents were removed through rotary evaporation, and the dried mixture was subjected to silica gel column chromatography (Methylene chloride: Hexane = 5: 5 (volume ratio)) to obtain a yellow liquid compound through a flash column. process may be included.

상기 c)단계는 DIBAL-H(diisobutyl aluminium hudrid)를 화학식 3의 화합물 대비 당량 기준으로 4.2 ~ 4.8 당량을 사용할 수 있다. 4.2 당량 미만 사용 시 반응이 미진행 되며, 4.8 당량을 초과하여 첨가시는 효율증대는 없고 부반응이 생성되어 비효율적이다. In step c), 4.2 to 4.8 equivalents of diisobutyl aluminum hudrid (DIBAL-H) may be used based on the equivalent weight of the compound of Formula 3 When less than 4.2 equivalents are used, the reaction does not proceed, and when more than 4.8 equivalents are added, there is no efficiency increase and side reactions are generated, which is inefficient.

구체적으로 상기 c)단계는 화학식 4의 화합물 1.0 ~ 20g을 3-neck round bottom flask에 넣은 후 정제된 toluene을 넣어 녹인 후 N2 가스 하에서 반응용기의 온도를 dry ice와 acetone(C3H6O)을 이용하여 -78℃로 내려준 후, 액체상태의 DIBAL-H(diisobutyl aluminium hudrid)를 화학식 3의 화합물 대비 당량 기준으로 4.2 ~ 4.8 당량을 적가한 다음 이후 천천히 온도를 올려 상온에서 12시간 동안 교반하여 반응시키고, 이후 반응이 끝난 반응용기의 온도를 0 ~ -10℃로 다시 내려준 후 methanol과 potassium sodium tartrate 용액을 넣어 반응을 종결하고 Ethyl acetate(EA)를 이용하여 유기물을 추출하며, 추출된 유기층에 남아있는 소량의 물을 MgSO4를 넣어 제거한 다음 rotary evaporator를 이용하여 용매를 모두 제거하고 흰색 가루 형태의 화합물을 얻어내는 과정을 포함한다.Specifically, in step c), 1.0 to 20 g of the compound of Formula 4 was put into a 3-neck round bottom flask, purified toluene was added to dissolve it, and then the temperature of the reaction vessel was adjusted to dry ice and acetone (C 3 H 6 O) under N 2 gas. ) to -78°C, 4.2 to 4.8 equivalents of DIBAL-H (diisobutyl aluminum hudrid) in liquid state based on the equivalent weight relative to the compound of Formula 3 were added dropwise, and then slowly raised the temperature to room temperature for 12 hours. After the reaction was stirred, the temperature of the reaction vessel was lowered to 0 ~ -10℃ again, methanol and potassium sodium tartrate solution were added to terminate the reaction, and organic matter was extracted using ethyl acetate (EA), followed by extraction. A small amount of water remaining in the organic layer is removed by adding MgSO 4 , and then the solvent is removed using a rotary evaporator to obtain a white powdery compound.

상기 d)단계는 N2 가스 하에서 phosphorus tribromide, phosphorous trichloride(PCl3), phosphorous triiodide(PI3) 중에서 할로젠화 반응물로 선택된 어느 하나를 화학식 4의 화합물 대비 당량기준으로 0.5 ~ 1.5 당량을 사용할 수 있다. 이들의 수치를 한정한 이유는 화합물 1 대비 0.5 당량 보다 적으면 반응이 덜 진행되어 출발 물질이 남게 되고 1.5 당량 보다 많이 넣게 되면 부반응 생성물이 많아지게 되고 이로 인하여 수율이 감소되기 때문이다. 특히 할로젠화 반응은 반응성이 뛰어나기 때문에 천천히 적가하여야 한다.In step d), 0.5 to 1.5 equivalents of any one selected as a halogenation reactant from among phosphorus tribromide, phosphorous trichloride (PCl 3 ), and phosphorous triiodide (PI 3 ) under N 2 gas can be used as an equivalent basis compared to the compound of Formula 4 have. The reason for limiting these values is that when less than 0.5 equivalents compared to compound 1, the reaction proceeds less and the starting material remains, and when more than 1.5 equivalents are added, side reaction products increase, thereby reducing the yield. In particular, since the halogenation reaction is highly reactive, it should be slowly added dropwise.

구체적으로 상기 d)단계는 화학식 4의 화합물 1 ~ 20g을 2-neck round bottom flask에 넣어준 후 정제된 tetrahydrofuran(THF)를 사용하여 녹인 다음, 반응용기의 온도를 얼음과 acetone(C3H6O)을 이용하여 0 ~ -10℃로 내려준 후 반응 용기 내부의 온도가 외부의 온도와 같아 질 때까지 방치한 다음, pyridine을 1.0 ~ 1.5 당량을 넣고 30 ~ 120분 동안 교반한다. 이와 같이 pyridine의 수치를 한정한 이유는 화합물 1 대비 1.0 당량 보다 적으면 반응이 덜 진행되기 때문에 출발 물질이 남게 되기 때문이다. 또한 1.5 당량 보다 많이 넣게 되면 염기성 용액의 성질이 강해지기 때문에 반응 조건이 달라 지게 되기 때문이다. 시간은 용매에 따라 pyridine이 섞이는 정도의 시간을 나타낸 것이다. 반응용기 온도가 0 ~ -10 ℃로 유지된 상태에서 할로젠화 반응을 위하여 액체 상태의 phosphorous tribromide(PBr3) phosphorous trichloride(PCl3), phosphorous triiodide(PI3) 중에서 선택된 어느 하나를 화학식 4의 화합물 대비 0.5 ~ 1.5 당량비를 실린지 펌프를 이용해 천천히 적가한다. 이 때 혼합물의 색깔이 투명한 색에서 흰색 또는 바나나 색으로 변한다. 이후 0 ~ -10 ℃에서 상온까지 서서히 온도를 올리면서 6 ~ 12 시간 동안 교반한다. 반응이 끝난 후 반응용기의 온도를 -10 ~ 0℃로 다시 내려준 후 차가운 물을 넣어 반응을 종결하고 추출용매 Dichloromethane(DCM)를 이용하여 유기물을 추출한다. 이때 추출 용매는 dichloromethane(DCM) 뿐만 아니라 다른 유기 용매인 diethyl ether(Et2O도 이용 가능하다. 추출된 유기층에 남아있는 소량의 물을 MgSO4를 넣어 제거 후 필터링 하고 유기층을 vacuum evaporator를 이용하여 용매를 모두 제거한 후 crude 형태의 혼합물을 얻을 수 있다. 이렇게 얻어진 혼합물을 silica gel column chromatography(Ethyl acetate : hexane = 1 : 9(부피비))를 통해 노란색 액체 형태의 5의 화합물을 합성하였다.Specifically, in step d), 1 to 20 g of the compound of Formula 4 was put into a 2-neck round bottom flask, dissolved using purified tetrahydrofuran (THF), and then the temperature of the reaction vessel was cooled with ice and acetone (C 3 H 6 ). O), lower it to 0 ~ -10℃, leave it until the temperature inside the reaction vessel becomes the same as the temperature outside, then add 1.0 ~ 1.5 equivalents of pyridine and stir for 30 ~ 120 minutes. The reason for limiting the level of pyridine as described above is that if the amount is less than 1.0 equivalent compared to Compound 1, the reaction proceeds less, and the starting material remains. In addition, when more than 1.5 equivalents are added, the properties of the basic solution are strengthened, and thus the reaction conditions are changed. The time indicates the amount of time the pyridine is mixed according to the solvent. For the halogenation reaction while the reaction vessel temperature is maintained at 0 ~ -10 ℃, any one selected from phosphorous tribromide (PBr 3 ) phosphorous trichloride (PCl 3 ), phosphorous triiodide (PI 3 ) in the liquid state is 0.5 ~ 1.5 equivalent ratio of the compound is slowly added dropwise using a syringe pump. At this time, the color of the mixture changes from transparent to white or banana color. After that, the mixture is stirred for 6 to 12 hours while gradually raising the temperature from 0 to -10 ℃ to room temperature. After the reaction is finished, the temperature of the reaction vessel is lowered to -10 ~ 0℃ again, cold water is added to terminate the reaction, and the organic matter is extracted using the extraction solvent Dichloromethane (DCM). At this time, the extraction solvent is dichloromethane (DCM) as well as other organic solvents, diethyl ether (Et 2 O). A small amount of water remaining in the extracted organic layer is removed by adding MgSO 4 , and then filtered, and the organic layer is vacuum evaporator. After removing all the solvent, a crude mixture can be obtained.The compound 5 was synthesized as a yellow liquid through silica gel column chromatography (Ethyl acetate : hexane = 1 : 9 (volume ratio)).

상기 화학식 5에서 A는 Br, Cl, I 중 어느 하나로, 하기 화학식 5-1, 화학식 5-2, 화학식 5-3과 같이 표현된다.In Formula 5, A is any one of Br, Cl, and I, and is represented by Formula 5-1, Formula 5-2, and Formula 5-3.

<화학식 5-1><Formula 5-1>

Figure pat00015
Figure pat00015

<화학식 5-2><Formula 5-2>

Figure pat00016
Figure pat00016

<화학식 5-3><Formula 5-3>

Figure pat00017
Figure pat00017

상기 e)단계는 화학식 5의 화합물을 sodium sulfide nonahydrate(Na2S·9H2O) 대비 당량기준으로 1.0 ~ 1.3 당량을 사용한다. 1.0 당량 미만 사용 시 반응이 깨끗하게 진행되지 아니하고, 1.3 당량보다 많으면 친핵성이 매우 큰 sodium sulfide nonahydrate(Na2S·9H2O)에 의한 부반응이 원하는 물질보다 많이 생성되어 수율이 현저하게 떨어지는 문제가 있기 때문이다. 친핵체인 S2-가 thiazole을 깨버릴 수 있다. Ethanol은 sodium sulfide nonahydrate(Na2S·9H2O)와 화학식 5의 화합물을 녹이는 용매로 사용된 것인데, 친핵성 치환반응(SN2)을 통한 고리닫힘 반응이 활발하게 일어나게 하기 위해서는 용매를 과량으로 사용하여 묽게 만들거나 반응 온도를 낮추는 것이 일반적이다. sodium sulfide nonahydrate(Na2S·9H2O)을 녹이기 위한 ethanol의 수치를 한정한 이유는 1 mL 보다 적게 사용하면 잘 녹지 않아 녹이는데 시간이 오래걸린다. 50 mL보다 많으면 고리화 반응 보다 부산물이 더 생성된다. In step e), 1.0 to 1.3 equivalents of the compound of Formula 5 are used on an equivalent basis compared to sodium sulfide nonahydrate (Na 2 S·9H 2 O). When less than 1.0 equivalent is used, the reaction does not proceed cleanly, and when more than 1.3 equivalent , a side reaction caused by sodium sulfide nonahydrate (Na 2 S 9H 2 O), which has very high nucleophilicity, is generated more than the desired material, and the yield is significantly reduced. because there is The nucleophile S 2 - can break thiazole. Ethanol is used as a solvent to dissolve sodium sulfide nonahydrate (Na 2 S 9H 2 O) and the compound of Formula 5. In order to activate the ring closure reaction through the nucleophilic substitution reaction (S N 2), an excess of the solvent is used. It is generally used to dilute or lower the reaction temperature. The reason for limiting the level of ethanol for dissolving sodium sulfide nonahydrate (Na 2 S 9H 2 O) is that if you use less than 1 mL, it does not dissolve well, so it takes a long time to dissolve. More than 50 mL produces more by-products than the cyclization reaction.

구체적으로 상기 e)단계는 고리 닫힘 반응으로 준비된 1000 mL 2-neck round bottom flask에 정제된 sodium sulfide nonahydrate을 화합물 5 대비 당량 기준으로 1.0 ~ 1.2 당량을 N2 가스하에서 정제된 무수 ethyl alcohol을 넣어 녹인 후 반응용기의 얼음과 acetone(C3H6O)을 이용하여 -10 ~ 0℃로 낮추어 주었다. 이때 모두 녹는데 대략 2 시간 정도의 시간이 요구된다. 또 다른 1-neck round bottom flask에 화학식 5의 화합물 1.0g ~ 4.0g을 70mL ~ 500mL의 ethyl alcohol을 넣어 녹인 후 이를 N2 가스하에서 교반되는 sodium sulfide nonahydrate 용액에 실린지 펌프를 이용하여 6 ~ 18시간 동안 천천히 적가한다. 상기 ethyl alcohol의 양을 한정한 이유는 70 mL보다 적게 사용하면 친핵성 화합물 1 두 분자가 결합되는 다이머 형태의 부산물이 생성되는 문제점이 있으며 500 mL보다 많이 사용하면 반응 시간이 필요 이상으로 길어진다는 문제점이 있기 때문이다. 온도는 얼음과 acetone(C3H6O)을 이용하여 0 ~ -10 ℃ 로 반응이 끝날 때까지 맞춰준다. 이때, 플라스크 주위에 흰색의 고체가 형성 된다. 적가가 끝난 이후 1 ~ 2시간동안 -10 ~ 5℃에서 교반한 후 상온으로 온도를 서서히 올려 2 ~ 6시간동안 교반하여 반응시킨다. 이는 충분히 반응가는 시간을 주기 위한 것 이다. 반응이 종료된 후 용매를 ethyl alcohol을 vacuum evaporator를 통해 제거하여 화합물을 얻고, 이 화합물을 n-hexane으로 녹여서 안녹는 고체를 필터링을 한 후 n-hexane에 녹은 화합물을 TEA로 Neutralization 처리 된 silica gel 컬럼(Ethyl acetate : Hexane = 1 : 9(부피비)) 으로 하얀색 고체 형태의 합성 된 화합물 6을 얻었다.Specifically, in step e), 1.0 to 1.2 equivalents of purified sodium sulfide nonahydrate compared to compound 5 were dissolved in anhydrous ethyl alcohol purified under N 2 gas in a 1000 mL 2-neck round bottom flask prepared by a ring closing reaction. Then, using ice and acetone (C 3 H 6 O) in the reaction vessel, the temperature was lowered to -10 ~ 0 °C. At this time, it takes about 2 hours to melt all of them. In another 1-neck round bottom flask, 1.0g ~ 4.0g of the compound of Formula 5 is dissolved in 70mL ~ 500mL of ethyl alcohol, and then 6 ~ 18 using a syringe pump in sodium sulfide nonahydrate solution stirred under N 2 gas. Slowly add dropwise over time. The reason for limiting the amount of ethyl alcohol is that when less than 70 mL is used, a by-product in the form of a dimer in which two molecules of nucleophilic compound 1 are combined is generated, and when used more than 500 mL, the reaction time becomes longer than necessary. because there is The temperature is adjusted to 0 ~ -10 ℃ using ice and acetone (C 3 H 6 O) until the reaction is complete. At this time, a white solid is formed around the flask. After the dropwise addition is completed, the mixture is stirred at -10 to 5°C for 1 to 2 hours, then the temperature is gradually raised to room temperature and stirred for 2 to 6 hours to react. This is to give enough time to react. The reaction was terminated by removing the solvent and then the ethyl alcohol through a vacuum evaporator to obtain a compound, the compound is a Neutralization process the melted compound in n -hexane was not a filter melting solid is dissolved in n -hexane to silica gel TEA The synthesized compound 6 was obtained in the form of a white solid by column (Ethyl acetate: Hexane = 1 : 9 (volume ratio)).

상기 f)단계는 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 화학식 6의 화합물 대비 당량기준으로 1.0 ~ 1.2 당량을 사용한다. 1.0 당량 미만으로 사용 시 반응이 미진행 되어 완전히 산화가 진행되지 않고, 1.2 당량을 초과하여 첨가시 부반응물의 생성이 촉진되며, 또한 금액적인 문제가 생긴다.In step f), 1.0 to 1.2 equivalents of 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) are used on the basis of equivalents compared to the compound of Formula 6. When used in less than 1.0 equivalent, the reaction does not proceed and oxidation does not proceed completely. When added in excess of 1.2 equivalent, the production of side reactants is accelerated, and there is also a problem in terms of money.

구체적으로, 상기 f)단계는 화학식 6의 화합물 0.3 ~ 0.5 g을 100 mL 2-neck round bottom flask에 넣은 후 N2 gas를 흘려준다. 이 반응용기에 건조된 유기용매 benzene을 넣어 준 후 5 ~ 30분 동안 교반한다. 이때 반응은 benzene 뿐만 아니라 다른 유기 용매인 toluene, chlorobenzene 에서도 반응 진행 가능하다. 완전히 섞이는 것을 확인 한 후 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 화학식 6의 화합물 대비 당량기준으로 1.0 ~ 1.2 당량을 넣은 후 50 ~ 70 ℃에서 8 ~ 36시간 동안 교반하여 반응을 진행 시켰다. 교반시 빨강색에서 황토색으로 변한다. 반응 온도를 50 ~ 70 ℃로 한정한 이유는 50℃보다 낮으면 반응이 진행되지 않으며 70 ℃이상의 경우 thiazole ring을 공격하여 다른 부반응이 생성 될 수 있기 때문이다. 반응이 끝난 용액을 silica gel 칼럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))을 이용하여 노란색 고체 형태인 화합물 7을 합성하였다.Specifically, in step f), 0.3 to 0.5 g of the compound of Formula 6 was put into a 100 mL 2-neck round bottom flask, and then N 2 gas was flowed. After adding the dried organic solvent benzene to the reaction vessel, it is stirred for 5 to 30 minutes. In this case, the reaction can proceed not only with benzene, but also with toluene and chlorobenzene, which are other organic solvents. After confirming that the mixture is completely mixed, add 1.0 to 1.2 equivalents of 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) based on the equivalent of the compound of Formula 6, and then add 8 to 36 at 50 to 70 ℃. The reaction was allowed to proceed by stirring for an hour. It changes from red to ocher when stirred. The reason for limiting the reaction temperature to 50 ~ 70 ℃ is that if it is lower than 50 ℃, the reaction does not proceed, and if it is above 70 ℃, other side reactions may be generated by attacking the thiazole ring. Compound 7 in the form of a yellow solid was synthesized from the reaction solution using a silica gel column (Ethyl acetate: hexane = 0.5: 9.5 (volume ratio)).

상기 g)단계는 할로젠화 반응물인 N-bromosuccinimide(NBS), N-chlorosucc inimide(NCS), N-iodosuccinimide(NIS)중에서 선택된 어느 하나를 화학식 7의 화합물 대비 당량기준으로 2.0 ~ 2.3 당량을 사용한다.In step g) , 2.0 to 2.3 equivalents of any one selected from the halogenation reactants N- bromosuccinimide (NBS), N- chlorosucc inimide (NCS), and N- iodosuccinimide (NIS) are used as an equivalent basis compared to the compound of Formula 7 do.

구체적으로, 상기 g)단계는 화학식 7의 화합물을 반응 flask에 0.2 ~ 0.3g과 유기용매 THF를 혼합하여 용해한 후 dry ice와 acetone을 이용하여 -78℃ ~ -40℃에서 N2 가스를 순환시키면서 교반하였다. 이후 할로젠화 반응물인 N-bromosuccinimide(NBS), N-chlorosuccinimide(NCS), N-iodosuccinimide(NIS) 중에서 선택된 어느 하나를 화학식 7의 화합물 대비 당량기준으로 2.0 ~ 2.3 당량 사용하여 고체 상태로 빠르게 첨가하고 온도를 서서히 상온으로 올린다. 상온에서 0.1 ~ 2 시간 동안 교반한 후 THF용매를 rotary evaporator을 이용하여 제거한 후 혼합물을 triethyl amine으로 중화된 silica gel 컬럼을 이용하여 fresh 컬럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))으로 정제하는 과정으로 노란색 고체 형태로 화학식 1의 화합물을 얻을 수 있다.Specifically, in step g), 0.2 to 0.3 g of the compound of Formula 7 and organic solvent THF are mixed and dissolved in a reaction flask, and then N 2 gas is circulated at -78°C to -40°C using dry ice and acetone. stirred. Afterwards, the halogenation reactant N -bromosuccinimide (NBS), N -chlorosuccinimide (NCS), or N -iodosuccinimide (NIS) selected from among those selected from the group consisting of 2.0 to 2.3 equivalents compared to the compound of Formula 7 was used and rapidly added in a solid state. and gradually raise the temperature to room temperature. After stirring at room temperature for 0.1 to 2 hours, the THF solvent was removed using a rotary evaporator, and the mixture was purified with a fresh column (Ethyl acetate : hexane = 0.5 : 9.5 (volume ratio)) using a silica gel column neutralized with triethyl amine. In this process, the compound of Formula 1 can be obtained in the form of a yellow solid.

상기와 같은 단계를 거친 본 발명은 하기 화학식 1-1, 화학식 1-2, 화학식 1-3, 화학식 1-4와 같이 표현되는 플루오린 원자가 포함된 신규 싸이아졸 단량체를 얻게 된다.In the present invention through the above steps, a novel thiazole monomer containing a fluorine atom represented by the following Chemical Formulas 1-1, 1-2, 1-3, and 1-4 is obtained.

상기에서 유기용매는 예시된 THF 뿐만 아니라 N,N-dimethylformamide(DMF), Dichloromethane(DCM)와 같은 유기용매가 가능하다. 이 반응에서는 반응 온도를 낮추는 것이 친핵성 치환반응이 활발하게 일어나게 하는 조건 중 하나인데 상기와 같이 수치를 한정한 이유는 -78 ℃보다 낮으면 ethanol 하에 화합물과 반응 시약이 용해되지 않는 문제점이 있으며 -40℃보다 높으면 친핵성 치환반응이 활발하게 일어나게 하기 위한 적정한 온도보다 너무 높은 온도이기 때문에 불필요한 부반응이 쉽게 일어날 수 있기 때문이다. In the above, organic solvents such as N,N-dimethylformamide (DMF) and dichloromethane (DCM) are possible as well as the exemplified THF. In this reaction, lowering the reaction temperature is one of the conditions for the nucleophilic substitution reaction to occur actively. The reason for limiting the numerical value as described above is that when it is lower than -78 ° C, there is a problem that the compound and the reaction reagent are not dissolved in ethanol. This is because, if it is higher than 40° C., unnecessary side reactions may easily occur because the temperature is too high than the appropriate temperature for the nucleophilic substitution reaction to occur actively.

<화학식 1-1><Formula 1-1>

Figure pat00018
Figure pat00018

<화학식 1-2><Formula 1-2>

Figure pat00019
Figure pat00019

<화학식 1-3><Formula 1-3>

Figure pat00020
Figure pat00020

<화학식 1-4><Formula 1-4>

Figure pat00021
Figure pat00021

상기와 같은 과정을 거쳐 합성된 본 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체를 이용하여 단일결합과 이중결합이 반복되는 탄소로 이루어진 공액 전도성 고분자들을 합성하면 전기 변색장치, 트랜지스터, 센서(sensor) 등의 전자 장치(electronic device)에 좋은 특성을 가진 것을 제조할 수 있다. 그 이유는 도너(donor)와 억셉터(acceptor)의 반복 구조로 이루어진 고분자는 도너(donor)의 높은 HOMO(Highest Occupied Molecular Orbital) 에너지와 acceptor의 낮은 LUMO(Lowest Unoccupied Molecular Orbital) 에너지의 혼성화로 인해서 그 차이를 나타내는 값인 밴드갭이 낮아지는 경향이 있기 때문이다.When the conjugated conductive polymers composed of carbon with repeated single bonds and double bonds are synthesized using the novel thiazole monomer containing fluorine atoms according to the present invention synthesized through the above process, electrochromic devices, transistors, and sensors ), etc., can be manufactured with good properties for electronic devices. The reason is that a polymer composed of a repeating structure of a donor and an acceptor is due to the hybridization of the high HOMO (Highest Occupied Molecular Orbital) energy of the donor and the Lowest Unoccupied Molecular Orbital (LUMO) energy of the acceptor. This is because the band gap, which is a value representing the difference, tends to decrease.

또한 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체를 이용하여 도너-억셉터(donor-acceptor) 구조를 갖는 공액 고분자 합성시 좋은 전기적 특성과 광학적 특성을 가지기 때문에 태양전지, 투명 전도체(transparent conductor), 박막 트랜지스터, 유기발광소자(OLED: Organic Light Emitting Diodes 또는 유기 EL)에 이용될 수 있다.In addition, since it has good electrical and optical properties when synthesizing a conjugated polymer having a donor-acceptor structure using the novel thiazole monomer containing a fluorine atom according to the present invention, a solar cell, a transparent conductor , thin film transistors, and organic light emitting diodes (OLEDs: Organic Light Emitting Diodes or organic EL).

이하 본 발명의 바람직한 실시예이다. Hereinafter are preferred embodiments of the present invention.

단, 하기 실시예는 구체적인 합성 과정 설명을 위한 것으로, 본 발명이 하기 실시예 만으로 한정되는 것은 아니다. However, the following examples are for description of a specific synthesis process, and the present invention is not limited only to the following examples.

(실시예 1) thiourea와 diethyl 2-chloro-3-oxosuccinate를 가하여 합성되는 diethyl 2-aminothiazole-4,5-dicarboxylate의 합성(Example 1) Synthesis of diethyl 2-aminothiazole-4,5-dicarboxylate synthesized by adding thiourea and diethyl 2-chloro-3-oxosuccinate

Figure pat00022
Figure pat00022

시중에서 쉽게 구할 수 있는 thiourea(50g, 657.0mmol) 파우더를 무수물 300mL의 ethyl alcohol(EtOH) 용매가 들어있는 1000 mL round bottom flask에 넣고 stirring bar를 이용해 잘 섞어 주면서 N2 gas를 넣으면서 온도를 상온에서 30℃까지 올려 출발 물질을 완전히 용해시켜 주면서 교반시킨다. 이 후 반응 용기 안에 합성시약인 2-chloro-3-oxo-succinic acid diethyl ester(160.1g, 723.1mmol)을 천천히 가하여 준 후 4시간 동안 70℃에서 교반한다. 반응이 종료된 혼합물을 온도를 상온으로 낮춘 상태에서 2시간 동안 교반한다. 이후 생성된 흰색 고체를 차가운 ethyl alcohol을 이용하여 워싱 및 필터를 진행한다.Put thiourea (50g, 657.0mmol) powder, which is easily available in the market, into a 1000 mL round bottom flask containing 300 mL of anhydrous ethyl alcohol (EtOH) solvent and mix well using a stirring bar while adding N 2 gas to the temperature at room temperature. Raise to 30° C. and stir while completely dissolving the starting material. After that, 2-chloro-3-oxo-succinic acid diethyl ester (160.1 g, 723.1 mmol), a synthetic reagent, was slowly added into the reaction vessel and stirred at 70° C. for 4 hours. After the reaction was completed, the mixture was stirred for 2 hours while the temperature was lowered to room temperature. Afterwards, wash and filter the generated white solid using cold ethyl alcohol.

필터링하고 남은 고체를 상온에 1시간 정도 건조 시킨 후 건조된 혼합물을 ethylalcohol을 가열 후 냉각 시켜 재결정을 통해 흰색 고체 형태의 diethyl 2-aminothiazole-4,5-dicarboxylate(151.97g, 94.71%)을 합성하였다.After filtering and drying the remaining solid at room temperature for about 1 hour, the dried mixture was heated with ethylalcohol, cooled, and recrystallized to synthesize diethyl 2-aminothiazole-4,5-dicarboxylate (151.97g, 94.71%) in the form of a white solid. .

도 1은 본 발명의 실시예 1에 따른 diethyl 2-aminothiazole-4,5- dicarboxylate의 1H-NMR 스팩트럼도로, 도시된 바와 같이 1H-NMR (400 MHz, DMSO) δ7.10 (s, 2H), 3.27 (q, 2H), 3.18 (q, 2H), 0.29 (t, 3H), 0.23 (t, 3H) ppm임을 알 수 있다. 7.10 ppm (s, 2H)를 통하여 NH2가 싸이아졸 고리에 치환 된 것을 알 수 있다.1 is a 1H-NMR spectrum diagram of diethyl 2-aminothiazole-4,5-dicarboxylate according to Example 1 of the present invention, as shown in 1 H-NMR (400 MHz, DMSO) δ7.10 (s, 2H) , 3.27 (q, 2H), 3.18 (q, 2H), 0.29 (t, 3H), 0.23 (t, 3H) ppm. Through 7.10 ppm (s, 2H), it can be seen that NH 2 is substituted on the thiazole ring.

도 2는 본 발명의 실시예 1에 따른 diethyl 2-aminothiazole-4,5- dicarboxylate의 13C-NMR 스팩트럼도로 도시된 바와 같이 13C-NMR (100 MHz, DMSO) δ 170.48, 156.46, 145.76 143.61, 135.01, 67.93, 59.91, 31.50, 22.23, 20.90, 14.10 ppm임을 알 수 있다. 2 is 13 C-NMR (100 MHz, DMSO) δ 170.48, 156.46, 145.76 143.61, as shown in 13 C-NMR spectrum diagram of diethyl 2-aminothiazole-4,5-dicarboxylate according to Example 1 of the present invention; It can be seen that 135.01, 67.93, 59.91, 31.50, 22.23, 20.90, and 14.10 ppm.

도 3은 본 발명의 실시예 1에 따른 diethyl 2-aminothiazole-4,5- dicarboxylate의 FT-IR 스팩트럼도로, 도시된 바와 같이 FT-IR (neat) ν max 3225, 3186, 2986, 2924, 1744, 1713, 1636, 1242, 1080, 1003, 849, 733, 663 cm-1임을 알 수 있다.3 is an FT-IR spectrum diagram of diethyl 2-aminothiazole-4,5-dicarboxylate according to Example 1 of the present invention, as shown FT-IR (neat) ν max 3225, 3186, 2986, 2924, 1744, It can be seen that 1713, 1636, 1242, 1080, 1003, 849, 733, 663 cm -1 .

(실시예 2) diethyl 2-fluorothiazole-4,5-dicarboxylate의 합성(Example 2) Synthesis of diethyl 2-fluorothiazole-4,5-dicarboxylate

Figure pat00023
Figure pat00023

상기 실시예 1에서 합성된 고체 상태의 2-aminothiazole-4,5-dicarboxylate (10g, 40.9 mmol)를 준비하여 250mL round bottom flask에 넣어준다. 이후 HBF4 (11mL , 163.8 mmol)을 넣은 후 5℃로 낮추어 10분간 교반한다. 이후 합성시약인 NOBF4( 5.74g, 49.2 mmol)을 천천히 넣은 후 0℃에서 20분 동안 교반한다. 이후 diethyl ether 45mL를 넣어 준후 dry ice와 acetonitrile을 이용하여 -50℃를 맞춘 후 30분 동안 교반한다. 반응이 종결 된 후 상온으로 올린 후 diethyl ether를 이용하여 워싱 및 필터를 진행한 후 필터지 위에 남아있는 고체를 1시간 동안 상온에서 건조한다. 석출된 고체를 250mL round bottom flask에 담아 45mL의 toluene과 함께 90℃에서 1시간 동안 교반한다.Prepare 2-aminothiazole-4,5-dicarboxylate (10g, 40.9 mmol) in a solid state synthesized in Example 1, and put it in a 250mL round bottom flask. After adding HBF 4 (11mL, 163.8 mmol), the temperature was lowered to 5℃ and stirred for 10 minutes. After that, a synthetic reagent, NOBF4 (5.74 g, 49.2 mmol) was slowly added and stirred at 0° C. for 20 minutes. After adding 45 mL of diethyl ether, set the temperature to -50°C using dry ice and acetonitrile and stir for 30 minutes. After completion of the reaction, after the reaction is brought to room temperature, washing and filtering are performed using diethyl ether, and the solid remaining on the filter paper is dried at room temperature for 1 hour. The precipitated solid is put in a 250mL round bottom flask and stirred with 45mL of toluene at 90℃ for 1 hour.

반응이 종결 된 후 용매를 vaccum evaporation을 통해 건조시킨 후, 건조된 혼합물을 silica gel 컬럼(MC : hexane = 5 : 5(부피비))을 통하여 정제된 연한 노란색 고체 형태의 diethyl 2-fluorothiazole-4,5-dicarboxylate (2.5 g, 25 %)를 합성하였다. After the reaction was completed, the solvent was dried through vacuum evaporation, and the dried mixture was purified through a silica gel column (MC : hexane = 5 : 5 (volume ratio)), diethyl 2-fluorothiazole-4 in the form of a pale yellow solid, 5-dicarboxylate (2.5 g, 25 %) was synthesized.

도 4은 본 발명의 실시예 2에 따른 diethyl 2-fluorothiazole-4,5- dicarboxylate의 1H-NMR 스팩트럼도로, 도시된 바와 같이 1H-NMR (400 MHz, DMSO) δ 3.44 (m, 4H), 0.39 (m, 6H) ppm임을 알 수 있다. 상기 실시예 1에서의 7.10 ppm (s, 2H)이 사라진 것을 통하여 NH2의 치환기가 F로 싸이아졸 고리에 치환 된 것을 알 수 있다. 4 is a 1 H-NMR spectrum diagram of diethyl 2-fluorothiazole-4,5-dicarboxylate according to Example 2 of the present invention, as shown in 1 H-NMR (400 MHz, DMSO) δ 3.44 (m, 4H) , it can be seen that 0.39 (m, 6H) ppm. Through the disappearance of 7.10 ppm (s, 2H) in Example 1, it can be seen that the substituent of NH 2 is substituted with F to the thiazole ring.

도 5는 본 발명의 실시예 2에 따른 diethyl 2-fluorothiazole-4,5- dicarboxylate의 13C-NMR 스팩트럼도로 도시된 바와 같이 13C-NMR (100 MHz, DMSO) δ 161.12, 158.62, 147.89, 130.85, 124.71, 62.57, 62.24 13.61 ppm임을 알 수 있다. 271.6 ppm를 통하여 Selelnium이 도입이 된 카본임을 알 수 있다. 5 is 13 C-NMR (100 MHz, DMSO) δ 161.12, 158.62, 147.89, 130.85 as shown as a 13 C-NMR spectrum diagram of diethyl 2-fluorothiazole-4,5-dicarboxylate according to Example 2 of the present invention. , it can be seen that 124.71, 62.57, 62.24 and 13.61 ppm. Through 271.6 ppm, it can be seen that Selenium is the introduced carbon.

도 6은 본 발명의 실시예 2에 따른 diethyl 2-fluorothiazole-4,5- dicarboxylate의 FT-IR 스팩트럼도로, 도시된 바와 같이 FT-IR (neat) ν max 2986, 1736, 1628, 1412, 1327, 1273, 1203, 1080, 1018, 949, 864, 748, 517 cm-1임을 알 수 있다.6 is an FT-IR spectrum diagram of diethyl 2-fluorothiazole-4,5-dicarboxylate according to Example 2 of the present invention, as shown FT-IR (neat) ν max 2986, 1736, 1628, 1412, 1327, It can be seen that 1273, 1203, 1080, 1018, 949, 864, 748, 517 cm -1 .

(실시예 3) (2-fluorothiazole-4,5-diyl)dimethanol의 합성(Example 3) Synthesis of (2-fluorothiazole-4,5-diyl)dimethanol

Figure pat00024
Figure pat00024

상기 실시예 2에서 합성한 diethyl 2-fluorothiazole-4,5-dicarboxylate(5 g, 20.02mmol)을 100 mL 2-neck round bottom flask에 넣은 후 N2 gas를 흘려준 후, 정제된 용매인 tetrahydrofuran(THF) 60 mL을 넣어 완전히 녹여 준 후 N2 gas를 흘려준다.Diethyl 2-fluorothiazole-4,5-dicarboxylate (5 g, 20.02 mmol) synthesized in Example 2 was put into a 100 mL 2-neck round bottom flask and N 2 gas was flowed thereafter, and then the purified solvent tetrahydrofuran ( THF) 60 mL is added, completely dissolved, and then N 2 gas is flowed.

반응용기의 온도를 dry ice와 acetone(C3H6O)을 이용하여 -78 ℃로 내려준 후 반응용기 내부 온도가 외부의 온도와 같아 질 때까지 10분간 방치한다. After lowering the temperature of the reaction vessel to -78 ℃ using dry ice and acetone (C 3 H 6 O), leave it for 10 minutes until the inside temperature of the reaction vessel becomes the same as the outside temperature.

반응용기 내부 온도가 충분히 내려갔을 때 액체상태의 Diisobutyl aluminum hydride(DIBAL-H)(14.6 mL, 84.94 mmol)을 천천히 적가 한다. When the internal temperature of the reaction vessel has decreased sufficiently, liquid diisobutyl aluminum hydride (DIBAL-H) (14.6 mL, 84.94 mmol) is slowly added dropwise.

diisobutyl aluminum hydride(DIBAL-H의 적가가 끝난 후 천천히 온도를 올려 상온에서 12 시간 동안 교반한다. 이후 반응이 끝난 반응용기의 온도를 0 ~ -10℃로 다시 내려준 후 methanol 10mL과 potassium sodium tartrate과 차가운 물을 1:1의 비율로 순서대로 넣어 반응을 종결하고 생성되는 고체를 Ethyl acetate(EA)를 이용하여 필터링 한다. 필터링 한 후 Ethyl acetate(EA)를 이용하여 유기물을 추출한다. 그 후에 brine solution으로 유기층을 씻어준다.After the dropwise addition of diisobutyl aluminum hydride (DIBAL-H) is finished, raise the temperature slowly and stir at room temperature for 12 hours. After that, lower the temperature of the reaction vessel to 0 ~ -10℃ again after the reaction is completed, and then mix with 10mL of methanol and potassium sodium tartrate. After terminating the reaction by adding cold water in a 1:1 ratio, the resulting solid is filtered using ethyl acetate (EA) After filtering, organic matter is extracted using ethyl acetate (EA). Wash the organic layer with the solution.

추출된 유기층에 남아있는 소량의 물을 제거하기 위해 MgSO4를 넣어준 후 필터링 하고 유기 층을 rotary evaporator를 이용하여 용매를 모두 제거한다. 흰색 가루 형태의 (2-fluorothiazole-4,5-diyl)dimethanol (3.24 g, 98 %)를 합성 하였다.In order to remove a small amount of water remaining in the extracted organic layer, MgSO 4 was added and filtered, and the organic layer was removed by using a rotary evaporator to remove all solvents. White powder (2-fluorothiazole-4,5-diyl)dimethanol (3.24 g, 98%) was synthesized.

도 7은 본 발명의 실시예 4에 따른 (2-fluorothiazole-4,5-diyl)dimethanol의 1H-NMR 스팩트럼도로 도시된 바와 같이,1H-NMR (400 MHz, DMSO) δ 4.93 (t, 1H), 4.42 (t, 1H), 3.86 (d, 2H), 3.59 (d, 2H)ppm.임을 알 수 있다. 7 is 1 H-NMR (400 MHz, DMSO) δ 4.93 (t, as shown in 1 H-NMR spectrum diagram of (2-fluorothiazole-4,5-diyl) dimethanol according to Example 4 of the present invention; 1H), 4.42 (t, 1H), 3.86 (d, 2H), and 3.59 (d, 2H) ppm.

diethyl 2-fluorothiazole-4,5-dicarboxylate의 0.39 (m, 6H)이 4.93 (t, 1H), 4.42 (t, 1H)로 이동한 것을 통하여 (2-fluorothiazole-4,5-diyl)dimethanol이 합성됨을 알 수 있다.(2-fluorothiazole-4,5-diyl)dimethanol was synthesized through the transfer of 0.39 (m, 6H) of diethyl 2-fluorothiazole-4,5-dicarboxylate to 4.93 (t, 1H), 4.42 (t, 1H) it can be seen that

도 8은 본 발명의 실시예 4에 따른 (2-fluorothiazole-4,5-diyl)dimethanol의 13C-NMR 스팩트럼도로 도시된 바와 같이, 13C-NMR (100 MHz, DMSO) δ 158.40, 145.34, 139.88, 60.15, 58.08 ppm.임을 알 수 있다. 8 is 13 C-NMR spectrum diagram of (2-fluorothiazole-4,5-diyl)dimethanol according to Example 4 of the present invention , 13 C-NMR (100 MHz, DMSO) δ 158.40, 145.34, It can be seen that 139.88, 60.15, 58.08 ppm.

도 9는 본 발명의 실시예 4에 따른(2-fluorothiazole-4,5-diyl)dimethanol의 FT-IR 스팩트럼도로 도시된 바와 같이, FT-IR (neat) ν max 3263, 3149, 2924, 2847, 1558, 1427, 1386cm-1.임을 알 수 있다. 3263cm-1과 3149cm-1를 통하여 알콜기의 고유 피크를 확인 하였다. 이를 통하여 (2-fluorothiazole-4,5-diyl)dimethanol이 합성됨을 알 수 있다.9 is as shown in the FT-IR spectrum diagram of (2-fluorothiazole-4,5-diyl) dimethanol according to Example 4 of the present invention, FT-IR (neat) ν max 3263, 3149, 2924, 2847, 1558, 1427, 1386cm -1 . Intrinsic peaks of alcohol groups were identified through 3263 cm -1 and 3149 cm -1 . Through this, it can be seen that (2-fluorothiazole-4,5-diyl)dimethanol is synthesized.

(실시예 4) 4,5-bis(bromomethyl)-2-fluorothiazole의 합성(Example 4) Synthesis of 4,5-bis(bromomethyl)-2-fluorothiazole

Figure pat00025
Figure pat00025

실시예 3에서 합성된 (2-fluorothiazole-4,5-diyl)dimethanol(1.0g, 6.13mmol)을 준비된 1-neck round bottom flask에 넣고 정제된 THF 50 mL 에 N2 gas 하에서 완전히 녹인다.Put the (2-fluorothiazole-4,5-diyl)dimethanol (1.0g, 6.13mmol) synthesized in Example 3 into the prepared 1-neck round bottom flask and completely dissolve it in 50 mL of purified THF under N 2 gas.

반응용기의 온도를 얼음과 acetone(C3H6O)을 이용하여 -10 ℃로 내려준 후 반응용기 내부 온도가 외부 온도와 같아질 때까지 20분간 방치 한다.After lowering the temperature of the reaction vessel to -10 ℃ using ice and acetone (C 3 H 6 O), leave it for 20 minutes until the inside temperature of the reaction vessel becomes the same as the outside temperature.

반응용기 내부 온도가 충분히 내려갔을 때, pyridine(0.485g, 6.14 mmol)을 넣고 5 ~ 10분 동안 교반한다. When the temperature inside the reaction vessel has sufficiently decreased, pyridine (0.485 g, 6.14 mmol) is added and stirred for 5 to 10 minutes.

반응용기 온도가 -10 ℃로 유지된 상태에서 액체 상태의 phosphorous tribromide(PBr3)(2.8 mL, 9.3 mmol)을 천천히 적가 한다. 이 때 혼합물의 색깔이 투명한 색에서 흰색 또는 바나나 색으로 변한다. -10 ℃에서 상온까지 서서히 온도를 올리면서 12 시간 동안 교반한다. While the reaction vessel temperature is maintained at -10 ℃, liquid phosphorous tribromide (PBr 3 ) (2.8 mL, 9.3 mmol) is slowly added dropwise. At this time, the color of the mixture changes from transparent to white or banana color. Stir for 12 hours while gradually raising the temperature from -10 °C to room temperature.

반응이 끝난 후 반응용기의 온도를 -10 ℃로 다시 내려준 후 차가운 물을 넣어 반응을 종결하고 methylene chloride(MC)를 이용하여 유기물을 추출한다. After the reaction is finished, lower the temperature of the reaction vessel to -10 ℃ again, add cold water to terminate the reaction, and extract organic matter using methylene chloride (MC).

추출된 유기 층에 남아있는 소량의 물을 제거하기 위해 MgSO4를 넣어준 후 필터링하고 유기 층을 vacuum evaporator를 이용하여 용매를 모두 제거한 후 crude 형태의 혼합물을 얻을 수 있다. 이렇게 얻어진 혼합물을 silica gel column chromatography(Ethyl acetate : hexane = 1 : 9(부피비))를 통해 노란색 액체 형태의 4,5-bis(bromomethyl)-2-fluorothiazole을 (1.54g, 87%)를 합성하였다. After adding MgSO 4 to remove a small amount of water remaining in the extracted organic layer, the organic layer is filtered and the solvent is removed using a vacuum evaporator to obtain a crude mixture. The obtained mixture was subjected to silica gel column chromatography (Ethyl acetate : hexane = 1 : 9 (volume ratio)) to synthesize 4,5-bis(bromomethyl)-2-fluorothiazole (1.54 g, 87%) in a yellow liquid form. .

도 10은 본 발명의 실시예 5에 따른4,5-bis(bromomethyl)-2-fluorothiazole의 1H-NMR 스팩트럼도로 도시된 바와 같이, 1H-NMR (400 MHz, CDCl3) δ 4.64 (s, 2H), 4.53 (s, 2H)임을 알 수 있다. (2-fluorothiazole-4,5-diyl)dimethanol의 4.93 (t, 1H), 4.42 (t, 1H)이 4.64 (s, 2H), 4.53 (s, 2H)로 이동한 것을 통하여 4,5-bis(bromomethyl)-2-fluorothiazole이 합성됨을 알 수 있다. 10 is 1 H-NMR (400 MHz, CDCl 3 ) δ 4.64 (s) as shown in 1 H-NMR spectrum diagram of 4,5-bis(bromomethyl)-2-fluorothiazole according to Example 5 of the present invention; , 2H), 4.53 (s, 2H). 4,5-bis through the transfer of 4.93 (t, 1H), 4.42 (t, 1H) of (2-fluorothiazole-4,5-diyl)dimethanol to 4.64 (s, 2H), 4.53 (s, 2H) It can be seen that (bromomethyl)-2-fluorothiazole is synthesized.

도 11은 본 발명의 실시예 5에 따른 4,5-bis(bromomethyl)-2-fluorothiazole의 13C-NMR 스팩트럼도로 도시된 바와 같이, 13C-NMR (100 MHz, CDCl3) δ 158.40, 145.34, 134.11, 23.45, 20.81ppm.임을 알 수 있다. 11 is a 13 C-NMR spectrum diagram of 4,5-bis(bromomethyl)-2-fluorothiazole according to Example 5 of the present invention, as shown in 13 C-NMR (100 MHz, CDCl 3 ) δ 158.40, 145.34 , 134.11, 23.45, and 20.81 ppm.

도 12는 본 발명의 실시예 5에 따른 4,5-bis(bromomethyl)-2-fluorothiazole의 FT-IR 스팩트럼도로 도시된 바와 같이, FT-IR (neat) ν max 2962, 2924, 2862, 1486, 1381,725, 583cm-1.임을 알 수 있다.12 is, as shown in the FT-IR spectrum diagram of 4,5-bis(bromomethyl)-2-fluorothiazole according to Example 5 of the present invention, FT-IR (neat) ν max 2962, 2924, 2862, 1486, It can be seen that 1381,725, 583cm -1 .

(실시예 5) 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole의 합성(Example 5) Synthesis of 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole

Figure pat00026
Figure pat00026

준비된 1000 mL 3-neck round bottom flask에 정제된 ethanol 330mL를 넣어주고 얼음으로 반응 용기의 온도를 0℃를 만들어주고 N2 gas 하에서 교반한다. 그 후에 sodium sulfide nonahydrate(Na2S·9H2O)(3.01 g, 12.5 mmol)을 500mL round flask에 넣고 ethanol 250mL로 N2 gas하에서 녹여준다. 250mL round flask에 상기 실시예 4에서 합성된 (2-fluorothiazole-4,5-diyl)dimethanol(3.00g, 10.38 mol)을 정제된 무수 ethyl alcohol(EtOH) 120mL을 넣어 모두 녹인 후 준비된 1000 mL 3-neck round bottom flask에 천천히 실린지 펌프를 이용하여 12시간동안 적가한다. 이때 또한 ethanol에 녹은 sodium sulfide nonahydrate (Na2S·9H2O)(3.5201 g, 0.01465 mol)를 1000mL 3-neck round bottom flask에 dropping funnel로 천천히 적가한다. (이때, 플라스크 주위에 흰색의 고체가 형성 된다.) Add 330 mL of purified ethanol to the prepared 1000 mL 3-neck round bottom flask, set the temperature of the reaction vessel to 0°C with ice, and stir under N 2 gas. After that, add sodium sulfide nonahydrate (Na 2 S·9H 2 O) (3.01 g, 12.5 mmol) into a 500 mL round flask and dissolve with 250 mL of ethanol under N 2 gas. In a 250 mL round flask, add 120 mL of purified anhydrous ethyl alcohol (EtOH) to (2-fluorothiazole-4,5-diyl)dimethanol (3.00 g, 10.38 mol) synthesized in Example 4 and dissolve them all in 1000 mL 3- It is slowly added dropwise to the neck round bottom flask using a syringe pump for 12 hours. At this time, also sodium sulfide nonahydrate (Na 2 S 9H 2 O) (3.5201 g, 0.01465 mol) dissolved in ethanol is slowly added dropwise to a 1000 mL 3-neck round bottom flask using a dropping funnel. (At this time, a white solid is formed around the flask.)

적가가 모두 끝난 후 3시간동안 0℃에서 교반한 후 상온으로 온도를 서서히 올려주고 상온에서 2시간 동안 교반한다. After completion of the dropwise addition, the mixture was stirred at 0° C. for 3 hours, then the temperature was gradually raised to room temperature and stirred at room temperature for 2 hours.

반응이 종료된 후 용매인 ethyl alcohol을 단순 증류를 통해 제거한 후 연한 노란색의 고체형태의 혼합물을 얻었다. 이렇게 얻은 혼합물을 hexane에 녹는 층과 녹지 않은 층으로 분리한 후 hexane에 녹은 층을 단순증류에 의하여 용매를 제거한 후 이 혼합물을 TEA로 중화시킨 silica gel TEA로 Neutralization 처리 된 silica gel 컬럼(Ethyl acetate : Hexane = 1 : 9(부피비)) 하얀색 고체 형태의 2-fluoro- 4,6-dihydrothieno[3,4-d]thiazole (0.5001g, 17.95%)를 합성하였다.After the reaction was completed, ethyl alcohol, a solvent, was removed through simple distillation to obtain a light yellow solid mixture. After separating the resulting mixture into a hexane-soluble layer and an insoluble layer, the solvent was removed from the hexane-soluble layer by simple distillation. Then, the mixture was neutralized with TEA and neutralized with silica gel TEA on a silica gel column (Ethyl acetate: Hexane = 1 : 9 (volume ratio)) 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole (0.5001 g, 17.95%) as a white solid was synthesized.

도 13은 본 발명의 실시예 6에 따른 2-fluoro-4,6-dihydrothieno [3,4-d]thiazole의 1H-NMR 스팩트럼도로 도시된 바와 같이, 1H-NMR (400 MHz, DMSO) δ 4.14 (dd, 2H), 4.09 (dd, 2H) ppm.임을 알 수 있다. 4,5-bis(bromomethyl)-2- fluorothiazole의 4.64 (s, 2H), 4.53 (s, 2H)이 4.14 (dd, 2H), 4.09 (dd, 2H) ppm으로 이동한 것을 통하여 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole이 합성됨을 알 수 있다.13 is a diagram according to Embodiment 6 of the present invention; As shown in 1 H-NMR spectrum diagram of 2-fluoro-4,6-dihydrothieno [3,4-d]thiazole , 1 H-NMR (400 MHz, DMSO) δ 4.14 (dd, 2H), 4.09 (dd , 2H) ppm. Through the transfer of 4.64 (s, 2H), 4.53 (s, 2H) of 4,5-bis(bromomethyl)-2-fluorothiazole to 4.14 (dd, 2H), 4.09 (dd, 2H) ppm, 2-fluoro- It can be seen that 4,6-dihydrothieno[3,4-d]thiazole is synthesized.

도 14는 본 발명의 실시예 6에 따른 2-fluoro-4,6-dihydrothieno[3,4-d] thiazole의 13C-NMR 스팩트럼도로 도시된 바와 같이, 13C-NMR (100 MHz, CDCl3) δ 158.40, 145.34, 134.11, 31.49, 29.60ppm.임을 알 수 있다. 14 is a diagram according to Embodiment 6 of the present invention; As shown in the 13 C-NMR spectrum diagram of 2-fluoro-4,6-dihydrothieno[3,4-d] thiazole , 13 C-NMR (100 MHz, CDCl 3 ) δ 158.40, 145.34, 134.11, 31.49, 29.60 It can be seen that ppm.

도 15는 본 발명의 실시예 6에 따른 2-fluoro-4,6-dihydrothieno[3,4-d] thiazole의 UV-vis 스팩트럼도로 도시된 바와 같이,

Figure pat00027
= 269.4 nm 이다.15 is a diagram according to Embodiment 6 of the present invention; As shown in the UV-vis spectrum diagram of 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole,
Figure pat00027
= 269.4 nm.

(실시예 6) 2-fluoro-thieno[3,4-d]thiazole의 합성(Example 6) Synthesis of 2-fluoro-thieno[3,4-d]thiazole

Figure pat00028
Figure pat00028

실시예 5에서 합성된 화합물 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole (1 g, 6.2 mmol)을 준비된 100 mL 2-neck round bottom flask에 넣은 후 N2 gas를 흘려준다. 이 반응용기에 건조된 Benzene 70 mL를 넣어 준 후 5 분 동안 교반한다.The compound 2-fluoro-4,6-dihydrothieno[3,4-d]thiazole (1 g, 6.2 mmol) synthesized in Example 5 was put into a prepared 100 mL 2-neck round bottom flask, and then N 2 gas was flowed. . After adding 70 mL of dried Benzene to this reaction vessel, it is stirred for 5 minutes.

완전히 섞인 것을 확인한 후 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ)(1.69 g, 7.5 mmol)을 넣어준 후 8시간 동안 70℃에서 교반하였다.(이때, 빨간색에서 황토색으로 변한다.)After confirming that the mixture was completely mixed, 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) (1.69 g, 7.5 mmol) was added and stirred at 70° C. for 8 hours. (At this time, red It turns yellow.)

반응이 끝난 용액을 silica gel 칼럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))을 이용하여 fresh 칼럼하여 하얀색 고체인 2-fluoro-thieno[3,4-d] thiazole(0.97 g, 97.7%)를 합성하였다.The reaction solution was subjected to a fresh column using a silica gel column (Ethyl acetate : hexane = 0.5 : 9.5 (volume ratio)) to give a white solid 2-fluoro-thieno[3,4-d]thiazole (0.97 g, 97.7%). was synthesized.

도 16은 본 발명의 실시예 6에 따른 2-fluoro-thieno[3,4-d]thiazole의 1H-NMR 스팩트럼도로 도시된 바와 같이, 1H-NMR (400 MHz, DMSO) δ 7.99(s, 1H), 7.73 (s, 1H) ppm.임을 알 수 있다. 4.14 (dd, 2H), 4.09 (dd, 2H)이 7.99 ppm(s, 1H), 7.73 ppm(s, 1H)로 이동한 것을 통하여 수소가 산화하여 2-fluoro-thieno [3,4-d]thiazole이 합성됨을 알 수 있다. 16 is a 1 H-NMR spectrum diagram of 2-fluoro-thieno [3,4-d] thiazole according to Example 6 of the present invention, as shown in 1 H-NMR (400 MHz, DMSO) δ 7.99 (s , 1H), 7.73 (s, 1H) ppm. Through the transfer of 4.14 (dd, 2H), 4.09 (dd, 2H) to 7.99 ppm(s, 1H), 7.73 ppm(s, 1H), hydrogen is oxidized to 2-fluoro-thieno [3,4-d] It can be seen that thiazole is synthesized.

도 17은 본 발명의 실시예 6에 따른 2-fluoro-thieno[3,4-d]thiazole의 13C-NMR 스팩트럼도로 도시된 바와 같이,13C-NMR (100 MHz, DMSO) 156.30, 145.31, 134.09, 113.15, 112.46 ppm.임을 알 수 있다. 17 is a 13 C-NMR spectrum diagram of 2-fluoro-thieno[3,4-d]thiazole according to Example 6 of the present invention , 13 C-NMR (100 MHz, DMSO) 156.30, 145.31, It can be seen that 134.09, 113.15, and 112.46 ppm.

도 18은 본 발명의 실시예 6에 따른 2-fluoro-thieno[3,4-d]thiazole의 UV-vis 스팩트럼도로 도시된 바와 같이,

Figure pat00029
= 311.3 nm 임을 알 수 있다. 18 is a UV-vis spectrum diagram of 2-fluoro-thieno[3,4-d]thiazole according to Example 6 of the present invention, as shown in FIG.
Figure pat00029
= 311.3 nm.

(실시예 7) 4,6-dibromo-2-fluorothieno[3,4-d]thiazole의 합성(Example 7) Synthesis of 4,6-dibromo-2-fluorothieno[3,4-d]thiazole

Figure pat00030
Figure pat00030

250 mL 반응 flask에 2-fluoro-thieno[3,4-d]thiazole(0.5 g, 2.29 mmol)과 THF 40 mL를 혼합하여 잘 용해한 후 dry ice와 aceone을 이용한 -78 ℃에서 N2 gas를 순환시키면서 20분간 교반하였다. N-bromosuccinimide(NBS)(0.90g, 5.05 mmol)을 고체 상태로 빠르게 첨가하고 1 시간 동안 온도를 서서히 상온으로 올린다. In a 250 mL reaction flask, mix 2-fluoro-thieno[3,4-d]thiazole (0.5 g, 2.29 mmol) and 40 mL of THF and dissolve it well, then circulate N 2 gas at -78 ℃ using dry ice and aceone. and stirred for 20 minutes. N- bromosuccinimide (NBS) (0.90 g, 5.05 mmol) was added rapidly in a solid state, and the temperature was gradually raised to room temperature for 1 hour.

상온에서 2 시간 동안 교반한 후 온도를 0 ℃로 낮추어 차가운 물로 반응을 종결하고 dichloromethane(DCM)으로 유기층을 추출한다. 유기층에 남아있는 소량의 물을 제거하기 위해 MgSO4를 넣고 필터링을 한 후 용매를 rotary evaporator로 제거한다. 용매를 제거 후 혼합물을 triethyl amine으로 중화된 silica gel 컬럼을 이용하여 fresh 컬럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))으로 정제하는 과정으로 노란색 고체인 4,6-dibromo-2-fluorothieno[3,4-d]thiazole(0.61 g, 84.72%)를 얻었다.After stirring at room temperature for 2 hours, the temperature was lowered to 0 °C, the reaction was terminated with cold water, and the organic layer was extracted with dichloromethane (DCM). To remove a small amount of water remaining in the organic layer, MgSO 4 is added and filtered, and the solvent is removed using a rotary evaporator. After removing the solvent, the mixture was purified by a fresh column (Ethyl acetate : hexane = 0.5 : 9.5 (volume ratio)) using a silica gel column neutralized with triethyl amine. 4,6-dibromo-2-fluorothieno[3,4-d]thiazole (0.61 g, 84.72%) was obtained.

도 19는 본 발명의 실시예 8에 따른 4,6-dibromo-2-fluorothieno[3,4-d] thiazole의 1H-NMR 스팩트럼도로 도시된 바와 같이,1H-NMR (400 MHz, CDCl3) 임을 알 수 있다. 2-fluoro-thieno[3,4-d]thiazole의 7.99 ppm(s, 1H), 7.73 ppm(s, 1H)이 피크가 사라지는 것을 통하여 수소가 브로민으로 치환된 것으로 4,6-dibromo-2-fluorothieno[3,4-d]thiazole이 합성됨을 알 수 있다19 is a diagram according to Example 8 of the present invention; As shown in the 1 H-NMR spectrum of 4,6-dibromo-2-fluorothieno[3,4-d] thiazole , 1 H-NMR (400 MHz, CDCl 3 ) can be seen. The peaks of 7.99 ppm(s, 1H) and 7.73 ppm(s, 1H) of 2-fluoro-thieno[3,4-d]thiazole disappeared, indicating that hydrogen was replaced with bromine. It can be seen that 4,6-dibromo-2-fluorothieno[3,4-d]thiazole is synthesized.

도 20은 본 발명의 실시예 8에 따른 4,6-dibromo-2-fluorothieno[3,4-d] thiazole의 13C-NMR 스팩트럼도로 도시된 바와 같이, 13C-NMR (100 MHz, CDCl3) δ 157.00, 145.84, 133.93, 122.58, 109.42ppm.임을 알 수 있다.20 is a diagram according to Example 8 of the present invention; As shown in the 13 C-NMR spectrum diagram of 4,6-dibromo-2-fluorothieno[3,4-d] thiazole , 13 C-NMR (100 MHz, CDCl 3 ) δ 157.00, 145.84, 133.93, 122.58, 109.42 It can be seen that ppm.

도 21은 본 발명의 실시예 8에 따른 4,6-dibromo-2-fluorothieno[3,4-d] thiazole 의 UV-vis 스팩트럼도로 도시된 바와 같이,

Figure pat00031
= 320.7 nm 임을 알 수 있다.21 is a diagram according to Example 8 of the present invention; As shown in the UV-vis spectrum diagram of 4,6-dibromo-2-fluorothieno[3,4-d]thiazole,
Figure pat00031
= 320.7 nm.

상기와 같은 과정을 거쳐 합성된 본 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체 및 이를 이용해 합성되는 화합물을 이용하여 단일결합과 이중결합이 반복되는 탄소로 이루어진 공액 전도성 고분자들을 합성하면 전기 변색장치, 태양전지, 트랜지스터, 센서(sensor) 등의 전자 장치(electronic device)에 좋은 성질을 가진 것을 제조할 수 있다. When a new thiazole monomer containing a fluorine atom according to the present invention synthesized through the above process and a compound synthesized using the same are synthesized, conjugated conductive polymers composed of carbon in which single bonds and double bonds are repeated are synthesized for an electrochromic device. , solar cells, transistors, and electronic devices such as sensors can be manufactured with good properties.

그 이유는 도너(donor)와 어셉터(acceptor)의 반복 구조로 이루어진 고분자는 도너(donor)의 높은 HOMO(Highest Occupied Molecular Orbital) 에너지와 acceptor의 낮은 LUMO(Lowest Unoccupied Molecular Orbital) 에너지의 혼성화로 인해 그 차이를 나타내는 값인 밴드갭이 낮아지는 경향이 있기 때문이다.The reason is that a polymer composed of a repeating structure of donor and acceptor is due to the hybridization of the high HOMO (Highest Occupied Molecular Orbital) energy of the donor and the Lowest Unoccupied Molecular Orbital (LUMO) energy of the acceptor. This is because the band gap, which is a value representing the difference, tends to decrease.

또한 발명에 따른 플루오린 원자가 포함된 신규 싸이아졸 단량체 및 이를 이용해 합성되는 화합물을 이용하여 도너-억셉터(donor-acceptor) 구조를 갖는 공액 고분자 합성시 좋은 전기적 특성과 광학적 특성을 가지기 때문에 태양전지, 투명 전도체(transparent conductor), 박막 트랜지스터, 유기발광소자(OLED: Organic Light Emitting Diodes)에 이용될 수 있다.In addition, when synthesizing a conjugated polymer having a donor-acceptor structure using a novel thiazole monomer containing a fluorine atom according to the present invention and a compound synthesized using the same, since it has good electrical and optical properties, solar cells, It may be used in transparent conductors, thin film transistors, and organic light emitting diodes (OLEDs).

본 발명은 상술한 특정의 바람직한 실시 예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형실시가 가능한 것은 물론이고, 그와 같은 변경은 청구범위 기재의 범위 내에 있게 된다. The present invention is not limited to the specific preferred embodiments described above, and without departing from the gist of the present invention claimed in the claims, anyone with ordinary skill in the art to which the invention pertains can implement various modifications Of course, such modifications are intended to be within the scope of the claims.

Claims (15)

하기 화학식 1로 표시되는 플루오린 원자가 포함된 신규 싸이아졸 단량체.
<화학식 1>
Figure pat00032

상기 화학식 1에서 A는 H, Br, Cl, I 중 어느 하나이다.
A novel thiazole monomer containing a fluorine atom represented by the following formula (1).
<Formula 1>
Figure pat00032

In Formula 1, A is any one of H, Br, Cl, and I.
 a) Thiourea에 diethyl 2-chloro-3-oxosuccinate를 가하여 하기 화학식 2로 표현되는 화합물을 제조하는 단계;
b) 화학식 2의 화합물에 Nitrosonium tetrafluoroborate을 이용한 할로젠화로 화학식 3으로 표현되는 화합물을 제조하는 단계;
c) 화학식 3의 화합물에 diisobutylaluminum hydride를 사용하여 ester 그룹을 alcohol 그룹으로 환원시켜 하기 화학식 4로 표현되는 화합물을 제조하는 단계;
d) 화학식 4로 표현되는 화합물을 이루는 alcohol 그룹을 치환하여 하기 화학식 5로 표현되는 화합물을 제조하는 단계;
e) ethly alcohol에 sodium sulfide nonahydrate를 녹여서 화학식 5의 화합물과 함께 적가하여 하기 화학식 6으로 표현되는 화합물을 제조하는 단계;
f) 화학식 6의 화합물에 용매와 함께 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 첨가하여 하기 화학식 7로 표현되는 화합물을 제조하는 단계; 및
g) 화학식 7의 화합물을 용매에 녹인 후 할로젠화 반응시키는 단계를 거쳐 청구항 1의 화학식 1로 표시되는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.

<화학식 2>
Figure pat00033


<화학식 3>
Figure pat00034


<화학식 4>
Figure pat00035


<화학식 5>
Figure pat00036

상기 화학식 5에서 A는 Br, Cl, I 중에서 선택된 어느 하나이다.

<화학식 6>
Figure pat00037


<화학식 7>
Figure pat00038

a) preparing a compound represented by the following Chemical Formula 2 by adding diethyl 2-chloro-3-oxosuccinate to Thiourea;
b) preparing a compound represented by Formula 3 by halogenating the compound of Formula 2 with Nitrosonium tetrafluoroborate;
c) reducing the ester group to an alcohol group using diisobutylaluminum hydride in the compound of Formula 3 to prepare a compound represented by the following Formula 4;
d) preparing a compound represented by the following Chemical Formula 5 by substituting an alcohol group constituting the compound represented by Chemical Formula 4;
e) dissolving sodium sulfide nonahydrate in ethly alcohol and adding it dropwise together with the compound of formula 5 to prepare a compound represented by the following formula (6);
f) preparing a compound represented by the following formula 7 by adding 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) to the compound of formula 6 with a solvent; and
g) A method for preparing a novel thiazole monomer containing a fluorine atom represented by Formula 1 of claim 1 through a step of dissolving the compound of Formula 7 in a solvent and then performing a halogenation reaction.

<Formula 2>
Figure pat00033


<Formula 3>
Figure pat00034


<Formula 4>
Figure pat00035


<Formula 5>
Figure pat00036

In Formula 5, A is any one selected from Br, Cl, and I.

<Formula 6>
Figure pat00037


<Formula 7>
Figure pat00038

 청구항 2에 있어서,
상기 a)단계에서 합성시약 diethyl 2-chloro-3-oxosuccinate를 화학식 2의 화합물 대비 당량기준으로 1.1 ~ 1.2당량을 사용하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
A method for preparing a novel thiazole monomer containing a fluorine atom, characterized in that 1.1 to 1.2 equivalents of the synthetic reagent diethyl 2-chloro-3-oxosuccinate in step a) are used on an equivalent basis compared to the compound of Formula 2.
 청구항 2 또는 청구항 3에 있어서,
상기 a)단계는 thiourea 1 ~ 50g을 N2 가스하에서 무수물 ethylalcohol(EtOH)용매를 사용하여 상온에 용해시킨 후, 액체 상태인 diethyl 2-chloro-3-oxosuccinate 1.1 ~ 1.2 당량을 첨가해주고 상온에서 1시간 교반하고, 교반 후에 60∼７0℃에서 교반 후에 반응이 종료된 혼합물을 상온으로 내려 재결정 과정을 거친 후, ethyl alcohol로 워싱 및 필터링하여 필터지 위에 있는 화합물을 상온에 1시간 건조하는 과정으로 아미노기를 갖도록 하는 단계인 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
4. The method according to claim 2 or 3,
In step a), 1 to 50 g of thiourea is dissolved at room temperature using an anhydrous ethylalcohol (EtOH) solvent under N2 gas, and 1.1 to 1.2 equivalents of diethyl 2-chloro-3-oxosuccinate in a liquid state are added thereto, and then at room temperature for 1 hour. After stirring and stirring, the reaction mixture was lowered to room temperature and recrystallized after stirring at 60∼70°C, washed with ethyl alcohol and filtered to dry the compound on filter paper at room temperature for 1 hour. Method for producing a novel thiazole monomer containing a fluorine atom, characterized in that the step to have.
 청구항 2에 있어서,
상기 b)단계는 화학식 2의 화합물에 합성시약 Nitrosonium tetrafluoroborate 1.2 ~ 1.5 당량을 사용하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
Step b) is a method for preparing a novel thiazole monomer containing a fluorine atom, characterized in that 1.2 to 1.5 equivalents of the synthetic reagent Nitrosonium tetrafluoroborate are used in the compound of Formula 2.
 청구항 2 또는 청구항 5에 있어서,
상기 b)단계는 화학식 2의 화합물 1.0 ~ 10g에 48 wt% HBF4 (tetrafluoroboric acid) 용액에 넣어 녹인 후 N2 가스 하에서 반응용기의 온도를 ice와 acetone(C3H6O)을 이용하여 -10℃로 내려준 후, NOBF4를 화학식 2의 화합물 대비 당량 기준으로 1.2 ~ 1.5 당량을 적가한 다음 0℃에서 20분동안 교반한 다음 diethyl eter(C4H10O)를 첨가하여 dry ice와 acetonitrile을 이용하여 -42℃로 내려준 후 30분 동안 교반하여 생성된 고체를 diethyl ether를 이용하여 워싱 및 필터링 후에 생성된 고체를 toluene에 녹여 90℃로 1 ~ 2시간 교반 후 생성된 여액을 rotary evaporator를 이용하여 용매를 모두 제거한 후에 건조된 혼합물을 silica gel column chromato graphy(Methylene chloride : Hexane = 5 : 5(부피비))를 통해 정제하는 과정을 포함하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
6. The method according to claim 2 or 5,
In step b), 1.0 to 10 g of the compound of Formula 2 was dissolved in 48 wt% HBF 4 (tetrafluoroboric acid) solution, and then the temperature of the reaction vessel under N 2 gas was adjusted using ice and acetone (C 3 H 6 O) - After the temperature was lowered to 10°C, 1.2 to 1.5 equivalents of NOBF 4 were added dropwise based on the equivalent weight of the compound of Formula 2, stirred at 0°C for 20 minutes, and then diethyl eter (C 4 H 10 O) was added to dry ice and After lowering the temperature to -42℃ using acetonitrile and stirring for 30 minutes, wash and filter the resulting solid using diethyl ether. Dissolve the resulting solid in toluene, stir at 90℃ for 1 to 2 hours, and rotate the resulting filtrate. After removing all the solvent using an evaporator, the dried mixture is purified through silica gel column chromatography (Methylene chloride: Hexane = 5: 5 (volume ratio)). A method for preparing an azole monomer.
 청구항 2에 있어서,
상기 c)단계는 DIBAL-H(diisobutyl aluminium hudrid)를 화학식 3의 화합물 대비 당량 기준으로 4.4 ~ 4.8 당량을 사용하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
In step c), 4.4 to 4.8 equivalents of DIBAL-H (diisobutyl aluminum hudrid) relative to the compound of Formula 3 are used. Method for producing a novel thiazole monomer containing a fluorine atom, characterized in that it is used.
 청구항 2 또는 청구항 7에 있어서,
상기 c)단계는 화학식 3의 화합물 1.0 ~ 20g에 toluene을 넣어 녹인 후 N2 가스 하에서 반응용기의 온도를 dry ice와 acetone(C3H6O)을 이용하여 -78℃로 내려준 후, 액체상태의 DIBAL-H(diisobutyl aluminium hudrid)을 화학식 3의 화합물 대비 당량기준으로 4.4 ~ 4.8 당량을 적가한 다음, 천천히 온도를 올려 상온에서 12시간 동안 교반하여 반응시키고, 이후 반응이 끝난 반응용기의 온도를 다시 0 ~ -10℃로 다시 내려준 후, methanol과 potassium sodium tartrate 용액을 넣어 반응을 종결하고, Ethyl acetate(EA)를 이용하여 유기물을 추출하며, 추출된 유기층에 남아있는 소량의 물을 MgSO4를 넣어 제거한 다음, rotary evaporator를 이용하여 용매를 모두 제거하고 흰색 고체 화합물을 얻어내는 과정을 포함하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
8. The method according to claim 2 or 7,
In step c), toluene was dissolved in 1.0 to 20 g of the compound of Formula 3, and then the temperature of the reaction vessel was lowered to -78° C. using dry ice and acetone (C 3 H 6 O) under N 2 gas, and then the liquid 4.4 to 4.8 equivalents of DIBAL-H (diisobutyl aluminum hudrid) in the state of the equivalent compared to the compound of Formula 3 were added dropwise, and then the temperature was slowly raised to react by stirring at room temperature for 12 hours, and then the temperature of the reaction vessel where the reaction was completed After lowering the temperature to 0 ~ -10℃ again, methanol and potassium sodium tartrate solution were added to terminate the reaction, ethyl acetate (EA) was used to extract organic matter, and a small amount of water remaining in the extracted organic layer was washed with MgSO. 4 After removal, the method for preparing a novel thiazole monomer containing a fluorine atom, characterized in that it includes the process of removing all the solvent using a rotary evaporator and obtaining a white solid compound.
 청구항 2에 있어서,
상기 d)단계는 화학식 4의 화합물 0.1 ~ 20g을 THF 10 ~ 1000 mL를 사용하여 녹인 다음, 반응용기의 온도를 얼음과 acetone(C3H6O)을 이용하여 0 ~ -10℃로 내려준 후 반응 용기 내부의 온도가 외부의 온도와 같아 질 때까지 방치한 다음, pyridine을 화합물 대비 1.0 ~ 1.5 당량기준으로 0.05 ~ 25 mL을 넣고 30 ~ 120분 동안 교반하고, 이후 반응용기 온도가 0 ~ -10℃로 유지된 상태에서 액체 상태의 phosphorous tribromide(PBr3), phosphorous trichloride(PCl3), phosphorous triiodide(PI3) 중에서 할로젠화 반응물로 선택된 어느 하나를 0.5 ~ 1.5 당량으로 천천히 적가하며, 이후 상온까지 서서히 온도를 올리면서 2 ~ 12 시간 동안 교반하여 반응시키고, 반응이 끝난 후 반응용기의 온도를 0 ~ -10 ℃로 다시 내려준 후 차가운 물을 넣어 반응을 종결하고 Metylene chloride(MC)를 이용하여 유기물을 추출하며, 추출된 유기층에 남아있는 소량의 물을 MgSO4를 넣어 제거 후 필터링 하고 유기층을 vacuum evaporator를 이용하여 용매를 모두 제거하여 화합물을 얻은 후 silica gel column chromatography( Ethyl acetate : hexane = 1 : 9(부피비))를 통해 정제하는 과정을 포함하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
In step d), 0.1 to 20 g of the compound of Formula 4 was dissolved using 10 to 1000 mL of THF, and then the temperature of the reaction vessel was lowered to 0 to -10°C using ice and acetone (C 3 H 6 O). After that, let it stand until the temperature inside the reaction vessel becomes the same as the temperature outside, then add 0.05 ~ 25 mL of pyridine based on 1.0 ~ 1.5 equivalents compared to the compound and stir for 30 ~ 120 minutes, then the reaction vessel temperature is 0 ~ In the state maintained at -10℃, 0.5 ~ 1.5 equivalents of any one selected as a halogenation reactant from among liquid phosphorous tribromide (PBr 3 ), phosphorous trichloride (PCl 3 ), and phosphorous triiodide (PI 3 ) is slowly added dropwise, After that, the reaction is stirred by stirring for 2 to 12 hours while gradually raising the temperature to room temperature. After the reaction is completed, the temperature of the reaction vessel is lowered to 0 ~ -10 ℃ again, cold water is added to terminate the reaction, and the reaction is terminated with methylene chloride (MC) The organic material is extracted using , and a small amount of water remaining in the extracted organic layer is removed by adding MgSO 4 , filtered, and the organic layer is removed using a vacuum evaporator to remove all solvents to obtain a compound, and then silica gel column chromatography ( Ethyl acetate: hexane = 1 : 9 (volume ratio)) for producing a novel thiazole monomer containing a fluorine atom, characterized in that it includes the process of purification.
 청구항 2에 있어서,
상기 e)단계는 화학식 5의 화합물을 sodium sulfide nonahydrate 대비 당량기준으로 1.0 ~ 1.3 당량을 사용하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
Step e) is a method for preparing a novel thiazole monomer containing a fluorine atom, characterized in that 1.0 to 1.3 equivalents of the compound of Formula 5 are used on an equivalent basis relative to sodium sulfide nonahydrate.
 청구항 2 또는 청구항 10에 있어서,
상기 e)단계는 고리 닫힘 반응을 sodium sulfide nonahydrate을 화합물 5 대비 당량 기준으로 1.0 ~ 1.3 당량을 N2 가스하에서 무수물의 ethyl alcohol을 넣어 녹인 후, 화학식 5의 화합물 1.0g ~ 4.0g을 ethyl alcohol을 넣어 녹인 후 빈 반응용기에 ethyl alcohol 70mL ~ 500mL을 넣고 N2 가스하에서 실린지 펌프를 이용하여 6 ~ 22시간 동안 적가하면서, sodium sulfide nonahydrate를 dropping funnel로 천천히 적가하고, 온도는 얼음과 acetone(C3H6O)을 이용하여 0 ~ -10 ℃ 로 낮추어 준 다음, 1 ~ 2 시간 동안 -10 ~ 5℃에서 교반한 후 상온으로 온도를 서서히 올려 2 ~ 6시간동안 교반하여 반응시키고, 반응이 종료된 후 용매를 ethyl alcohol을 vacuum evaporator를 통해 제거하여 화합물을 얻고, 이 화합물을 n-hexane으로 녹여서 안녹는 고체를 필터링을 한 후 n-hexane에 녹은 화합물을 TEA로 Neutralization 처리 된 silica gel 컬럼(Ethyl Acetate : Hexane = 1 : 9(부피비))으로 정제하는 과정을 포함하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
11. The method according to claim 2 or 10,
In step e), 1.0 to 1.3 equivalents of sodium sulfide nonahydrate relative to compound 5 were dissolved in the ring closing reaction by adding ethyl alcohol of anhydride under N 2 gas, and 1.0g to 4.0g of the compound of Formula 5 was added to ethyl alcohol. After dissolving, put 70mL ~ 500mL of ethyl alcohol into an empty reaction vessel and add sodium sulfide nonahydrate dropwise with a dropping funnel while using a syringe pump under N 2 gas dropwise for 6 ~ 22 hours, and the temperature is adjusted to ice and acetone (C 3 H 6 O), lowered to 0 ~ -10 ℃, stirred at -10 ~ 5 ℃ for 1 to 2 hours, then slowly raised the temperature to room temperature and stirred for 2 ~ 6 hours to react, after the end of the solvent by removing the ethyl alcohol through a vacuum evaporator to obtain a compound, the compound was not filtered after the soluble solids dissolved with n -hexane Neutralization the treated silica gel column, the molten compound in n -hexane as TEA ( Ethyl Acetate: Hexane = 1 : 9 (volume ratio)), characterized in that it comprises a process for producing a novel thiazole monomer containing a fluorine atom.
 청구항 2에 있어서,
상기 f)단계는 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 화학식 6의 화합물 대비 당량기준으로 1.0 ~ 1.3 당량을 사용하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
In step f), 1.0 to 1.3 equivalents of 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) are used on an equivalent basis compared to the compound of Formula 6, A method for preparing a novel thiazole monomer.
 청구항 2 또는 청구항 12에 있어서,
상기 f)단계는 화학식 6의 화합물 0.3 ~ 0.5 g을 N2 가스하에서 유기용매를 넣어 교반 후, 2,3-dichloro-5,6-dicynide-1,4- benzoquinone(DDQ)를 화학식 6의 화합물 대비 당량기준으로 1.0 ~ 1.2 당량을 넣어 60 ~ 80 ℃에서 8 ~ 36시간 동안 교반하여 반응시키고, 반응이 끝난 용액을 silica gel 칼럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))을 이용하여 fresh 컬럼하여 정제하는 과정을 포함하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
13. The method according to claim 2 or 12,
In step f), 0.3 to 0.5 g of the compound of Formula 6 is added to an organic solvent under N 2 gas and stirred, and 2,3-dichloro-5,6-dicynide-1,4-benzoquinone (DDQ) is added to the compound of Formula 6 Add 1.0 ~ 1.2 equivalents as a reference equivalent and react by stirring at 60 ~ 80 ℃ for 8 ~ 36 hours. After the reaction, the solution is fresh using a silica gel column (Ethyl acetate : hexane = 0.5 : 9.5 (volume ratio)). A method for producing a novel thiazole monomer containing a fluorine atom, characterized in that it comprises a process of column purification.
 청구항 2에 있어서,
상기 g)단계는 할로젠화 반응물인 N-bromosuccinimide(NBS), N-chlorosuccinimide(NCS), N-iodosuccinimide(NIS) 중에서 선택된 어느 하나를 화학식 7의 화합물 대비 당량기준으로 2.0 ~ 2.5 당량을 사용하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.
3. The method according to claim 2,
In step g) , 2.0 to 2.5 equivalents of one selected from the halogenation reactants N- bromosuccinimide (NBS), N- chlorosuccinimide (NCS), and N- iodosuccinimide (NIS) are used as an equivalent basis compared to the compound of Formula 7 Method for producing a novel thiazole monomer containing a fluorine atom, characterized in that.
 청구항 2 또는 청구항 14에 있어서,
상기 g)단계는 화학식 7의 화합물 0.1 ~ 10g과 유기용매를 혼합하여 용해한 후 dry ice와 aceone을 이용하여 -78 ~ -40℃에서 N2 가스를 순환시키면서 교반하고, 할로젠화 반응물인 N-bromosuccinimide(NBS), N-chlorosuccinimide(NCS), N-iodosuccinimide(NIS) 중에서 선택된 어느 하나를 화학식 7의 화합물 대비 당량기준으로 2.0 ~ 2.5 당량 사용하여 고체 상태로 빠르게 첨가하고 1 ~ 2 시간 동안 온도를 서서히 상온으로 올리고, 상온에서 0.1 ~ 2 시간 동안 교반한 후 상기 유기용매를 rotary evaporator을 이용하여 제거한 다음 혼합물을 triethyl amine으로 중화된 silica gel 컬럼을 이용하여 fresh 컬럼(Ethyl acetate : hexane = 0.5 : 9.5(부피비))으로 정제하는 과정을 포함하는 것을 특징으로 하는 플루오린 원자가 포함된 신규 싸이아졸 단량체의 제조방법.15. The method of claim 2 or 14,
In step g), 0.1 to 10 g of the compound of Formula 7 and an organic solvent are mixed and dissolved, and then stirred using dry ice and aceone at -78 to -40° C. while circulating N 2 gas, and the halogenation reactant N - Using 2.0 to 2.5 equivalents of any one selected from bromosuccinimide (NBS), N- chlorosuccinimide (NCS), and N- iodosuccinimide (NIS) as an equivalent to the compound of Formula 7, quickly add it in a solid state and hold the temperature for 1 to 2 hours. After slowly raising the temperature to room temperature, stirring at room temperature for 0.1 to 2 hours, the organic solvent was removed using a rotary evaporator, and then the mixture was neutralized with triethyl amine and then a fresh column (Ethyl acetate: hexane = 0.5: 9.5) using a silica gel column. (volume ratio)), a method for producing a novel thiazole monomer containing a fluorine atom, characterized in that it comprises a purification process.
KR1020190176354A 2019-12-27 2019-12-27 Manufacturing method of new thiazole monomer including fluorine atoms KR102300998B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020190176354A KR102300998B1 (en) 2019-12-27 2019-12-27 Manufacturing method of new thiazole monomer including fluorine atoms

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020190176354A KR102300998B1 (en) 2019-12-27 2019-12-27 Manufacturing method of new thiazole monomer including fluorine atoms

Publications (2)

Publication Number Publication Date
KR20210083749A true KR20210083749A (en) 2021-07-07
KR102300998B1 KR102300998B1 (en) 2021-09-09

Family

ID=76862016

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020190176354A KR102300998B1 (en) 2019-12-27 2019-12-27 Manufacturing method of new thiazole monomer including fluorine atoms

Country Status (1)

Country Link
KR (1) KR102300998B1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100679777B1 (en) 2002-08-07 2007-02-06 에프. 호프만-라 로슈 아게 Thiazole derivatives
KR100773650B1 (en) 2003-12-08 2007-11-05 에프. 호프만-라 로슈 아게 Novel thiazole derivatives
KR100820935B1 (en) 2006-08-18 2008-04-10 한국화학연구원 Thiazole derivatives, preparation thereof and pharmaceutical compositions comprising the same
JP2012214621A (en) * 2011-03-31 2012-11-08 Fujifilm Corp Organic semiconductor polymer, composition for organic semiconductor material, and photoelectric cell
WO2013056355A1 (en) * 2011-10-20 2013-04-25 UNIVERSITé LAVAL Preparation of high molecular weight polymers 8y direct arylation and heteroarylation
JP2013170187A (en) * 2012-02-17 2013-09-02 Fujifilm Corp Organic photoelectric conversion element composition, thin film containing the same, photoelectric cell, organic semiconductor polymer used for the same, compound and method for producing polymer
KR101597205B1 (en) 2014-04-09 2016-02-25 한국화학연구원 - Benzooxazolone or benzothiazolone derivatives preparation method therof and pharmaceutical composition for use in preventing or treating Urotensin- receptor activity related diseases containing the same as an active ingredient
KR102005863B1 (en) * 2018-11-27 2019-07-31 광운대학교 산학협력단 Compound synthesized from new thiazole monomer including electron withdrawing group and manufacturing method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100679777B1 (en) 2002-08-07 2007-02-06 에프. 호프만-라 로슈 아게 Thiazole derivatives
KR100773650B1 (en) 2003-12-08 2007-11-05 에프. 호프만-라 로슈 아게 Novel thiazole derivatives
KR100820935B1 (en) 2006-08-18 2008-04-10 한국화학연구원 Thiazole derivatives, preparation thereof and pharmaceutical compositions comprising the same
JP2012214621A (en) * 2011-03-31 2012-11-08 Fujifilm Corp Organic semiconductor polymer, composition for organic semiconductor material, and photoelectric cell
WO2013056355A1 (en) * 2011-10-20 2013-04-25 UNIVERSITé LAVAL Preparation of high molecular weight polymers 8y direct arylation and heteroarylation
JP2013170187A (en) * 2012-02-17 2013-09-02 Fujifilm Corp Organic photoelectric conversion element composition, thin film containing the same, photoelectric cell, organic semiconductor polymer used for the same, compound and method for producing polymer
KR101597205B1 (en) 2014-04-09 2016-02-25 한국화학연구원 - Benzooxazolone or benzothiazolone derivatives preparation method therof and pharmaceutical composition for use in preventing or treating Urotensin- receptor activity related diseases containing the same as an active ingredient
KR102005863B1 (en) * 2018-11-27 2019-07-31 광운대학교 산학협력단 Compound synthesized from new thiazole monomer including electron withdrawing group and manufacturing method thereof

Also Published As

Publication number Publication date
KR102300998B1 (en) 2021-09-09

Similar Documents

Publication Publication Date Title
WO2016111277A1 (en) Heterocycle-containing compound, polymer using said compound, and use thereof
CN101747350B (en) Thiazolothiazole derivative
JP2015227457A (en) Water soluble near infrared sensing polymers with low band gaps
EP2681223B1 (en) Compounds and polymers thereof containing fused thiophene rings for use in electronic applications
CN110386930B (en) Aggregation-induced emission compound, preparation method and application thereof
Grandl et al. Electronic and structural properties of N→ B-ladder boranes with high electron affinity
KR20120118497A (en) Method of making coupled heteroaryl compounds via rearrangement of halogenated heteroaromatics followed by oxidative coupling
EP3519386A1 (en) Novel pi-conjugated materials, methods for preparing same and uses thereof as semiconductors
KR102005863B1 (en) Compound synthesized from new thiazole monomer including electron withdrawing group and manufacturing method thereof
Serkova et al. Core/shell hybrid dendrimers: Controllable rigidity determines molecular behaviour
JP6175818B2 (en) NOVEL POLYMER, INK CONTAINING THE SAME, ORGANIC FILM, ELECTRONIC DEVICE, ELECTROLUMINESCENT ELEMENT AND ORGANIC TRANSISTOR
KR102300998B1 (en) Manufacturing method of new thiazole monomer including fluorine atoms
Barłóg et al. Synthesis, characterization and crystal structures of novel fluorinated di (thiazolyl) benzene derivatives
WO2004018488A1 (en) π-CONJUGATED ORGANIC MATERIAL OF POLYCYCLIC FUSED RING TYPE, INTERMEDIATE THEREFOR, AND PROCESS FOR PRODUCING π-CONJUGATED ORGANIC MATERIAL OF POLYCYCLIC FUSED RING TYPE
JP2010202554A (en) Heterocyclic condensed-ring oligothiophene, method for producing the same and polymer
Li et al. Luminescent digold ethynyl thienothiophene and dithienothiophene complexes; their synthesis and structural characterisation
JP6625546B2 (en) Picene derivative, photoelectric conversion material and photoelectric conversion element
KR101943306B1 (en) New selenazole monomer and manufacturing method thereof
CN105017278B (en) One class thiophene condenses Benzheterocyclic derivatives and its polymer
JP6919140B2 (en) Electrochromic complex, electrochromic device containing it, and method for manufacturing electrochromic device
KR102005860B1 (en) conjugated copolymer using selenazole monomer and manufacturing method thereof
Adam et al. Conjugated tris-tetrathiafulvalenes
CN109880065B (en) Conjugated polymer containing trifluoromethyl as well as preparation method and application thereof
KR101678415B1 (en) Novel organic semiconductor compound, preparation method thereof and organic electronic device having the same
JP2011094066A (en) Polymer compound having photoelectronic functional region and method of producing the same

Legal Events

Date Code Title Description
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant