THAI MALE A ATUS009951094B2 HINDI LANTAITTUR (12 ) United States Patent ( 10 ) Patent No. : US 9 ,951 , 094 B2 Yamaguchi et al. (45 ) Date of Patent: Apr. 24 , 2018 ( 54 ) PHOSPHOLE COMPOUND AND (56 ) References Cited FLUORESCENT DYE CONTAINING THE SAME U . S . PATENT DOCUMENTS 2010 /0253212 Al 10 /2010 Cheng et al. @( 71) Applicant: NATIONAL UNIVERSITY CORPORATION NAGOYA FOREIGN PATENT DOCUMENTS UNIVERSITY , Nagoya - shi, Aichi (JP ) JP 2012 - 191031 A 10 /2012 ( 72 ) Inventors : Shigehiro Yamaguchi, Nagoya ( JP ) ; Aiko Fukazawa, Nagoya ( JP ) ; Eriko OTHER PUBLICATIONS Yamaguchi, Nagoya ( JP ) ; Chenguang Wang , Nagoya ( JP ) Jul . 28 , 2016 International Preliminary Report on Patentability issued in Patent Application No. PCT/ JP2015 /051636 . ( 73 ) Assignee : NATIONAL UNIVERSITY Mar. 10 , 2015 International Search Report issued in International CORPORATION NAGOYA Patent Application No . PCT/ JP2015 /051636 . Yoshihiro Matano et al. “ Synthesis of 2 - Alkenyl- and 2 - Alkynyl UNIVERSITY , Nagoya ( JP ) Benzo [b ] Phospholes by Using Pallladium -Catalyzed Cross- Cou pling Reactions" . Organic Letters, 2013 , vol . 15 , No. 17 , pp . @( * ) Notice : Subject to any disclaimer, the term of this 4458 - 4461 . patent is extended or adjusted under 35 Aiko Fukazawa et al. “ Benzo [ b ] Phosphole - Containing p - Electron U . S . C . 154 (b ) by 0 days . Systems: Synthesis Based on an Intramolecular Trans Halophosphanylation and Some Insights Into Their Properties” . (21 ) Appl. No. : 15 /112 , 499 Chemistry , An Asian Journal, 2009 , vol. 4 , pp . 1729 - 1740 . Yuto Unoh et al . “ An Approach to Benzophosphole Oxides Through (22 ) PCT Filed : Jan . 22, 2015 Silver - or Manganese -Mediated Dehydrogenative Annulation Involving C - C and C - P Bond Formation ” . Angewandte Chemie , (86 ) PCT No. : PCT/ JP2015 / 051636 International Edition , 2013 , vol . 52, No . 49 , pp . 12975 - 12979 . $ 371 ( c ) ( 1 ) , (Continued ) ( 2 ) Date : Jul. 19 , 2016 ( 87 ) PCT Pub . No. : WO2015 / 111647 Primary Examiner — Rita J Desai PCT Pub . Date : Jul. 30 , 2015 ( 74 ) Attorney , Agent, or Firm — Oliff PLC (65 ) Prior Publication Data (57 ) ABSTRACT US 2016 / 0333037 A1 Nov . 17 , 2016 The following formula is an example of a phosphole com pound of the present invention . The phosphole compound of ( 30 ) Foreign Application Priority Data the present invention has the characteristic of maintaining a high fluorescence quantum yield in a wide range of solvents Jan . 24 , 2014 (JP ) .. .. .. 2014 -011473 from low - polarity solvents to high - polarity solvents , as well as the characteristic in which the fluorescence wavelength (51 ) Int . Ci. shifts to the longer wavelength side as the polarity of the CO7F 9 /6568 ( 2006 . 01 ) solvent increases . Because of these characteristics, the phos C09K 11 /06 ( 2006 .01 ) phole compound of the present invention is expected to be C09B 57700 ( 2006 . 01 ) used , for example , for quantitatively determining the polar HOIL 51/ 00 ( 2006 .01 ) ity in the environment therearound by using the absorption C09B 69 / 10 ( 2006 .01 ) wavelength and fluorescence wavelength thereof, or used as HOIL 51 / 50 ( 2006 . 01 ) a new fluorescent probe dye or a highly efficient luminescent ( 52 ) U . S . CI. material in organic electronic devices . CPC . .. .. C07F 9 /65685 (2013 .01 ) ; C09B 57 / 00 ( 2013. 01 ) ; C09B 57/ 008 ( 2013 .01 ) ; C09B 69 / 10 (2013 .01 ) ; C09K 11 / 06 ( 2013 .01 ) ; HOIL [Chem . 1] 51/ 0061 ( 2013 .01 ) ; HOIL 51 /0071 (2013 .01 ) ; HOIL 51/ 0072 ( 2013 .01 ) ; COOK 2211 / 1007 PhPh O ( 2013 .01 ) ; CO9K 2211 / 1011 ( 2013 .01 ) ; COOK II 2211 / 1014 ( 2013 .01 ) ; CO9K 2211/ 1029 NPh2 ( 2013 .01 ) ; COOK 2211/ 1096 (2013 .01 ) ; HOIL 51/ 5012 (2013 .01 ) (58 ) Field of Classification Search Ph CPC .. C07F 9 /65685 ; C09B 57 /008 ; C09B 69/ 10 ; COOK 11/ 06 USPC . .. 546 / 23 See application file for complete search history . 4 Claims, 1 Drawing Sheet US 9 , 951 ,094 B2 Page 2 (56 ) References Cited OTHER PUBLICATIONS Katsuaki Baba et al . “ Palladium -Catalyzed Direct Synthesis of Phosphole Derivatives From Triarylphosphines Through Cleavage of Carbon - Hydrogen and Carbon - Phosphorus Bonds” . Angewandte Chemie , International Edition , 2013, vol. 52 , No. 45 , pp . 11892 11895 . Leon D . Freedman et al. “ Preparation and Ultraviolet Absorption Spectra of Some Derivatives of Phosphafluorinic Acid ” . Journal of Organic Chemistry, 1959 , vol. 24 , pp . 638 -641 . Jun . 27 , 2017 Search Report issued in European Patent Application No . 15741089 . 5 . Quin , Louis D . et al ., “ Synthesis of 1 , 2 - Dihydro - 1 Phenylindeno [ 2 , 1 - b ] - Phosphole as a Potential Precursor of a Phosphapentalenyl Anion ,” Tetrahedron , 1983 , vol. 39 , No . 3 , pp . 401 -407 . U . S . Patent Apr . 24 , 2018 US 9 , 951 ,094 B2 FIG . 1 € - 1 n - from Orientation Polarizability Af - 2€ + 1 2n2 + 1 (Parameter of Polarity of Solvent ) - 9000 posto y = 16782x + 2557. 7 . Compound 2 - 8000 R2 = 0 . 91732 - 7000 y = 8401. 3x + 4469. 7 ???? shift/cm-1Stokes - - 6000 R ? = 0 .93988 ELOH - - 5000 e commenf . 1. 1837 * * 30215 enero R2 = 0 . 99829 -- - 4000 Compound 1 -- 3000 Me 2000 wa - 0. 05 0 0. 05 0. 1 0. 15 0 .2 0. 25 0 .3 0 .35 V ?? Com orientationa casa polarizability (21 in) sicerCompound 3 FIG . 2 on F - NPh2 Ph PI 20posto SIMUS . Compound 7a Bersama Alexa -430 ) NPN .... .. .. CompoundRR 76R o ofval PhoPano 0. 95 . .. D ONPhaNPh2 AbsorbanceRelative CompoundPh 1 ..... .. .Pha. .. .. .. .. .. Compound 2 ( 6 ) NPh2 CH ,CN Solution ; 403 nm Laser * ** Compound 6b 0 . 90 o 20 40 wwwwwwwwwww60 . 80s pace 100 720 Irradiation Time / Minute US 9 ,951 , 094 B2 PHOSPHOLE COMPOUND AND CITATION LIST FLUORESCENT DYE CONTAINING THE SAME Non - Patent Literature TECHNICAL FIELD 5 [NPL 1 ] Organic Letters , 2013 , vol. 15 , No. 17 , p 4458 - 4461 [NPL 2 ] Chem . Asian J. , 2009 , vol. 4 , p 1729 - 1740 The present invention relates to a phosphole compound and a fluorescent dye containing the same. SUMMARY OF INVENTION BACKGROUND ART 10 Technical Problem Fluorescent organic compounds are important chemicals Many of the known compounds whose fluorescent color used as a luminescent material of organic light- emitting dramatically changes depending on the polarity of the sol diodes and a fluorescent dye for biological fluorescence vent exhibit strong fluorescence in low - polarity solvents , but imaging . Therefore , numerous fluorescent organic com - 15 do not in highly polar protic solvents such as alcohols . pounds have been reported in the field of both basic and applied researches. In particular , dyes ( for example , acrylo Accordingly , it has been desired to develop an environmen dan ) whose fluorescent color dramatically changes depend tally responsive fluorescent compound having novel optical ing on the surrounding environment are practically used as characteristics . fluorescent probes for site -specific visualization . It is often 20 The present invention is intended to solve this issue , and reported that the molecular design of combining a highly a major object of the invention is to provide a phosphole electron - donating (donor type ) - conjugated unit with a compound having novel optical characteristics . highly electron - accepting ( acceptor type ) i - conjugated unit is effective in obtaining such fluorescent characteristics . The Solution to Problem luminescent color , luminescence efficiency of a fluorescent 25 dye , and the degree of solvent effect highly depend on the To solve the above issue, the present inventors synthe choice of a -conjugated units as the donor and the acceptor. sized a variety of new phosphole compounds, examined Recently , phosphole compounds have been attracting atten their optical characteristics , and accomplished the present tion as a new type of electron - accepting i - conjugated unit . invention by finding that some of the phosphole compounds For example , NPL 1 reports synthesis examples of 2 - alk - 30o exhibit novel optical characteristics . enyl -benzo [ b ] phosphole oxide and 2 - alkynyl- benzo [ b ] phos More specifically , the phosphole compound of the present phole oxide and optical data thereof . Also , NPL 2 reports invention is represented by the following formula ( 1 ) or synthesis examples of 2 - aryl- benzo [ b ]phosphole oxide and formula ( 2 ): the electrochemical properties thereof. The following are examples of the compounds described in NPLs 1 and 2 : 35 [Chem . 2 ] [Chem . 1 ] RI [NPL 1 ] 40 Ph 0 + NR3R4 N ( 2 ) R ] a *45 Ph Z = - CH = CH - , - C = C — - NR3R4 X = OMe, H , CI Ar! Ph 0 [NPL 2 ] 50 R5 R8 more In formula ( 1 ) , R ' represents an alkyl group , a substituted alkyl group , an aryl group , a substituted aryl group , an 55 alkoxy group , a hydroxy group , an amino group , or a a substituted amino group . R² represents a hydrogen atom , an X = C1, Br, H alkyl group , a substituted alkyl group , an aryl group , a Ph o substituted aryl group , a carbonyl group , an imino group , a cyano group , or a fluorine atom . R and R4 may be the same 60 or different and are each a hydrogen atom , an alkyl group , a substituted alkyl group , an aryl group , or a substituted aryl group . Ar represents a hydrocarbon aromatic ring , a substi tuted hydrocarbon aromatic ring , a heteroaromatic ring , or a Br substituted heteroaromatic ring . n represents 0 or 1 . ' and R = Me, OMe, CF3 , NMe2 65 T represent n - conjugated units that may be the same or different and are each a divalent alkenyl group , a substituted de divalent alkenyl group , a divalent alkynyl group