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WO2011071360A2 - Synthèse de 8-aminoborodipyrrométhènes à fluorescence bleue - Google Patents

Synthèse de 8-aminoborodipyrrométhènes à fluorescence bleue Download PDF

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Publication number
WO2011071360A2
WO2011071360A2 PCT/MX2010/000151 MX2010000151W WO2011071360A2 WO 2011071360 A2 WO2011071360 A2 WO 2011071360A2 MX 2010000151 W MX2010000151 W MX 2010000151W WO 2011071360 A2 WO2011071360 A2 WO 2011071360A2
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WO
WIPO (PCT)
Prior art keywords
synthesis
compound
compounds
blue
aminoborodipyrrometenes
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/MX2010/000151
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English (en)
Spanish (es)
Other versions
WO2011071360A3 (fr
Inventor
Eduardo PEÑA CABRERA
César Fernando Azael GÓMEZ DURAN
Juan Orlando Flores Rizo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidad de Guanajuato
Original Assignee
Universidad de Guanajuato
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 Universidad de Guanajuato filed Critical Universidad de Guanajuato
Priority to EP10836252.6A priority Critical patent/EP2511277B1/fr
Priority to ES10836252.6T priority patent/ES2595212T3/es
Priority to US13/512,734 priority patent/US8710220B2/en
Publication of WO2011071360A2 publication Critical patent/WO2011071360A2/fr
Publication of WO2011071360A3 publication Critical patent/WO2011071360A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages

Definitions

  • the object of this invention is the innovation of the synthesis of 8-aminoborodipyrrometenes.
  • These types of compounds have the special characteristic of blue fluorescence, especially the propargilaminoborodipyrrometene (1) that does it with greater intensity, this characteristic makes them unique in their type since there is no record of any compound derived from borodipyrrometenes that it possesses This characteristic of fluorescing in the blue region of the electromagnetic spectrum.
  • Patent number WO20041 1 1236 European Patent office
  • the present invention consists of a method to be able to displace the thiomethyl group, from the starting material (Formula 5), thiomethylborodipyrrometene, which is the basis for obtaining several borodipyrrometenes derivatives with fluorescence, this methodology had been the displacement of thiomethyl by a carbon-carbon coupling of Liebskind-Srogl, in the synthesis of these compounds a great variety of fluorescent compounds were obtained in different areas of the region of the electromagnetic spectrum, this displacement has been achieved in our working group only by a nucleophilic substitution with some amino-derivative that by the electronegativity of nitrogen and that electronic pair that it has without sharing confers nucleophilia to the substitution of thiomethyl and form the aminoborodipyrrometene.
  • Another advantage of the compounds that are presented is its structure, which has no bulky functional groups, that is, it does not have molecules with a large number of atoms anchored to position 8 which translates into its ease of synthesis.
  • the invention to be protected is a family of 8-aminoborodipyrrometenes (4 examples: 8-propargylaminoborodipyrrometene (Formula 1), 8-allylaminoborodipyrrometene (Formula 2), 8-methylaminoborodipyrrometene (Formula 3), 8-aminoborodipyrrometene and its Formula (Formula synthesis method, since it is very general and simple, It is important to mention that there is no general synthesis reported to obtain 8-aminoborodipyrrometenes and much less to compounds with these fluorescent characteristics in the blue region of the electromagnetic spectrum.
  • nucleophilia is the ability to an atom to donate electron pairs, in this case the nitrogen of the amines used is more electronegative and more nucleophilic by the pair of electrons that it has available and replaces the sulfur that is less electronegative and has no available electron pairs that provide it nucleophilia, this reaction is carried out, at a temperature of 25 ° C (except for the aminoBDP) and without any external agent as a catalyst, in dichloromethane as a wet solvent, that is, use it without any treatment to eliminate the small amount of water that the water could contain.
  • solvent molecular mesh is commonly used to dry the water and the container d is preserved Where the solvent is held under a nitrogen atmosphere, apart from using this wet solvent, it is common in reactions where some group is placed in position 8 that the reaction is carried out in an inert atmosphere, this is the vessel where the reaction is carried. in nitrogen atmosphere.
  • the novelty of this invention is to have synthesized the aminoborodipyrrometenes, especially the propargilaminoborodipirrometene that has characteristics suitable for use as a laser and unique fluorescence properties in the blue, of which there was no record, and is important for its absorption and emission characteristics, not known in borodipyrrometenes derivatives.
  • Formula 1 represents 8-propargylaminoborodipyrrometene, this compound is obtained from a substitution of the thiomethyl group, as shown in Figure 1 this compound has fluorescence blue fluorescence emitting at 469.3 nm with a quantum yield of 0.94.
  • Formula 2 represents 8-allylaminoborodipyrrometene which, as seen in Figure 2, shows blue fluorescence emitting at 456 nm.
  • Formula 3 corresponds to 8-methylaminoborodipyrrometene shown in Figure 3 which shows blue fluorescence at 440 nm.
  • Formula 4 corresponds to 8-aminoborodipyrrometene which is shown in Figure 4 having blue fluorescence at 437.5 and with a quantum yield of 0.92.
  • Formula 6 represents the borodipyrrometne derived from the methyl ester of leucine and formula 7 represents the analogue of the stereyl borodipyrrometenes of beta-alanine Figure 7.
  • Figure 5 corresponds to the absorption and emission graphs of formula 1, where each line represents a different solvent.
  • Figure 6 indicates the fluorescence of the thiomethylborodipyrrometene starting material.
  • Figure 7 depicts the structure of the methyl ester of 8-Z-Leucinoborodipyrrometene
  • Figure 8 depicts the structure of the ethyl ester of 8- -alanineborodipyrrometene Note: Fluorescence is caused by UV lamp short wavelength at 254nm
  • the family of 8-aminoborodipyrrometenes is obtained as follows:
  • thiomethyl group is substituted with an amino derivative, in this case 4 amino-derivatives, propargilamine, allylamine, methylamine and ammonium acetate were used as a source of ammonia, to perform the substitution at position 8 of the thiomethylborodipyrrometene, to give rise to the corresponding aminoborodipyrrometene.
  • an amino derivative in this case 4 amino-derivatives, propargilamine, allylamine, methylamine and ammonium acetate were used as a source of ammonia, to perform the substitution at position 8 of the thiomethylborodipyrrometene, to give rise to the corresponding aminoborodipyrrometene.
  • the Table shows the behavior of the compound when dissolved in a variety of solvents, it is observed that the fluorescence varies from 463 nm to 481.5 nm, obtaining the highest quantum yield in ethyl acetate of 0.94.
  • Reaction 5 In a new vial provided with a magnetic stirrer, thiomethylborodipyrrometene (100.00 mg, 0.42 mmol, 1.0 eq.), L-Leucine methyl ester hydrochloride (1 14.49 mg, 0.63 mmol, 1.50 eq) was added. mL of Dichloromethane (CH2CI2), and the system is kept under stirring until completely dissolved. Finally, Triethylamine (TEA) (63.78 mg, 0.63 mmol, 1.50 eq.) was added. The reaction is kept under constant and vigorous stirring, keeping the vial closed with a lid to prevent evaporation of the solvent. It has a reaction time of 135 min with a yield of 94%.
  • TEA Triethylamine
  • Reaction 6 In a new vial provided with a magnetic stirrer, thiomethylborodipyrrometene (100.00 mg, 0.42 mmol, 1.0 eq.), The ethyl ester hydrochloride of ⁇ -Alanine (96.81 mg, 0.63 mmol, 1.50 eq) was added. Subsequently, 3 mL of Dichloromethane (CH 2 C1 2 ) was added, and the system is kept under stirring until completely dissolved. Finally, Triethylamine (TEA) (63.78 mg, 0.63 mmol, 1.50 eq.) was added. The reaction is kept under constant and vigorous stirring, keeping the vial closed with a lid to prevent evaporation of the solvent.
  • TEA Triethylamine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Peptides Or Proteins (AREA)

Abstract

Notre groupe de recherche a trouvé que le groupe thioalkyle qui se trouve dans la position 8 du corps du borodipyrrométhène pouvait être remplacé par un amino dérivé. Il a été découvert que le fait d'avoir cet amino dérivé ancré modifie le comportement qu'ont normalement les borodipyrrométhènes, faisant que ce nouveau composé avec l'amino dérivé antré dans la position 8, présente une fluorescence de couleur bleue, ce qui permet d'obtenir des composés avec des caractéristiques de fluorescence pour lesquelles jusqu'à présent il n'avait été fait mention de quelque composé à fluorescence bleue, et un autre sujet important est la stratégie de synthèse, laquelle s'avère très simple et avec des rendements très élevés, et en outre l'étude photophysique réalisée à la propargylamine révèle que le composé a des propriétés qui sont très intéressantes et qui lui donnent une utilisation potentielle dans différents domaines de la science, celle qui ressort le plus étant notamment l'utilisation comme laser. De même, les dérivés 6 et 7 peuvent être utilisés pour incorporer des peptides et des protéines et obtenir ainsi des biomolécules marquées avec des fragments fluorescents.
PCT/MX2010/000151 2009-12-10 2010-12-10 Synthèse de 8-aminoborodipyrrométhènes à fluorescence bleue Ceased WO2011071360A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10836252.6A EP2511277B1 (fr) 2009-12-10 2010-12-10 Synthèse de 8-aminoborodipyrrométhènes à fluorescence bleue
ES10836252.6T ES2595212T3 (es) 2009-12-10 2010-12-10 Síntesis de 8-aminoboro-dipirrometenos con fluorescencia azul
US13/512,734 US8710220B2 (en) 2009-12-10 2010-12-10 Synthesis of 8-amino boron dipyrromethenes having blue fluorescence

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MX2009013486A MX2009013486A (es) 2009-12-10 2009-12-10 Sintesis de 8-aminoborodipirrometenos con fluorescencia azul.
MXMX/A/2009/013486 2009-12-10

Publications (2)

Publication Number Publication Date
WO2011071360A2 true WO2011071360A2 (fr) 2011-06-16
WO2011071360A3 WO2011071360A3 (fr) 2011-09-22

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Country Status (5)

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US (1) US8710220B2 (fr)
EP (1) EP2511277B1 (fr)
ES (1) ES2595212T3 (fr)
MX (1) MX2009013486A (fr)
WO (1) WO2011071360A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019532912A (ja) * 2016-09-02 2019-11-14 エルジー・ケム・リミテッド 化合物およびこれを含む色変換フィルム
CN112940021A (zh) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 一类高亮度、多色免洗脂滴荧光探针

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102157933B1 (ko) * 2017-12-27 2020-09-18 주식회사 엘지화학 함질소 고리 화합물 및 이를 포함하는 색변환 필름
CN112940020A (zh) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 一类405nm激发的高亮度免洗脂滴荧光探针及其合成方法与应用

Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2004111236A1 (fr) 2003-06-16 2004-12-23 Riken Proteine fluorescente
WO2005118606A1 (fr) 2004-06-04 2005-12-15 National Institute Of Advanced Industrial Science And Technology Complexe d’iridium substitué de fluor et matériau luminescent realise avec ledit complexe

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US3857793A (en) 1973-05-01 1974-12-31 Gte Laboratories Inc Fluorescent organic compound laser
US4916711A (en) * 1988-09-29 1990-04-10 Boyer Joseph H Lasing compositions and methods for using the same
US5446157A (en) * 1990-04-23 1995-08-29 Morgan; Lee R. Boron difluoride compounds useful in photodynamic therapy and production of laser light
ATE495247T1 (de) 2002-08-23 2011-01-15 Riken Chromoprotein und fluoroproteine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004111236A1 (fr) 2003-06-16 2004-12-23 Riken Proteine fluorescente
WO2005118606A1 (fr) 2004-06-04 2005-12-15 National Institute Of Advanced Industrial Science And Technology Complexe d’iridium substitué de fluor et matériau luminescent realise avec ledit complexe

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HETEROAT. CHEM, vol. 4, 1993, pages 609
HETEROAT. CHEM., vol. 4, 1993, pages 603
See also references of EP2511277A2

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019532912A (ja) * 2016-09-02 2019-11-14 エルジー・ケム・リミテッド 化合物およびこれを含む色変換フィルム
CN112940021A (zh) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 一类高亮度、多色免洗脂滴荧光探针

Also Published As

Publication number Publication date
US20120253050A1 (en) 2012-10-04
WO2011071360A3 (fr) 2011-09-22
EP2511277A4 (fr) 2013-04-17
EP2511277B1 (fr) 2016-07-13
MX2009013486A (es) 2011-06-14
US8710220B2 (en) 2014-04-29
EP2511277A2 (fr) 2012-10-17
ES2595212T3 (es) 2016-12-28

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