New Family of Discriminating Molecules for Neutron and Gamma Rays and Ionic Liquids

• US 20160145214A1
• Filed: 03/18/2014
• Published: 05/26/2016
• Est. Priority Date: 03/18/2013
• Status: Active Grant

• Current Assignee: Centre National De La Recherche Scientifique, Universite De Strasbourg (Financière Meeschaert SA)
• Original Assignee: Centre National De La Recherche Scientifique, University of Strasbourg
• Inventors: Douce, Laurent, Stuttge, Louise, Bouajila, Ezeddine, FOUCHET, Julien, HEINRICH, Beno?t
• Granted Patent: US 10,266,498 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 29/146 Y-type faujasite
• CPC Class Codes: C07C 311/48 having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• CPC Class Codes: C07D 233/58 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
• CPC Class Codes: C07D 403/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: G01T 7/00 Details of radiation-measuring instruments

Abstract

The invention concerns a new family of discriminating molecules for neutron rays and gamma rays, and method for preparing the same. These molecules are also useful to detect radiation (X, gamma, electrons, protons, ions), and hence for the manufacture of instruments for radiation detection, industrial or medical dosimetry.

Claims

1-22. -22. (canceled)

23. An imidazolium compound of formula (I):

24. The compound according to claim 23, wherein <

<

Ar>

> and

<

<

U>

>

are present and in that <

<

U>

>

is a straight-chain, saturated hydrocarbon group having 1 to 30 carbon atoms, optionally substituted.

25. The compound according to claim 23, wherein <

<

Ar>

>

is absent.

26. The compound according to claim 23, wherein <

<

U>

>

is a CH₂ group.

27. The compound according to claim 23, wherein <

<

Ar—

U>

>

is a benzyl group.

28. The compound according to claim 23, wherein <

<

Y>

>

is a C_nH_2n+1 or O—

C_nH_2n+1alkyl group where n is a number ranging from 1 to 30.

29. The compound according to claim 23, wherein the <

<

R>

>

group comprises at least one group or consists of a group selected from among;

optionally substituted phenyl, optionally substituted naphthalene, optionally substituted fluorene, optionally substituted methylcarbazole and optionally substituted anthracene, optionally substituted pyrene, optionally substituted tetracene, a fluorescent protein e.g. GFP (GREEN), YFP (yellow) and RFP (red), derivatives of xanthene, cyanine or its derivatives , derivatives of naphthalene, a derivative of coumarin, a derivative of oxadiazole, a derivative of pyrene, a derivative of oxazine, a derivative of benzophenoxazine, in particular a derivative of benzo[a]phenoxazine (Nile blue), a derivative of benzo[b]phenoxazine, (9-dimethylamino-10-methyl-benzo[a]phenoxazin-5-ylidene)ammonium chloride (cresyl violet), 5.9-Bis(ethylamino)-10-methylbenzo[a]phenoxazin-7-ium (oxazine

     170);

a derivative of acridin, a derivative of arylmethin, a derivative of tetrapyrrol.

30. The compound according to claim 23, wherein this compound is selected from among a compound of formula (Ia), (Ib), (Ic), (Id), (Ie) below:

31. The compound according to claim 23, wherein <

<

Y>

>

is selected from the group formed by the following radicals;

methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methylpentyl, 1-methylpentyl and 3-methylheptyl.

32. The compound according to claim 23 associated with an <

<

A>

>

counter-ion.

33. The compound according to claim 32 wherein A⁻

is an anion selected from among a halide, P(R⁴)₆⁻

, B(R⁴)₄⁻

, SCN⁻

, (R⁵SO₂)₂N⁻

, R⁵OSO₃, R⁵SO₃⁻

, carborane, carbonate, hydrogen carbonate, alcoholate, carboxylate, amide, phosphate, SiF₆⁻

, SbF₆⁻

, I₃⁻

, nitrate, halide oxide, silicate, sulfate, sulfonate, cyanide, carbanions or metallate, wherein;

R⁴ on each occurrence is a group independently selected from among a halogen atom, C₁-C₆ alkyl group, C₆-C₁₀ aryl group, an aralkyl group;

R⁵ on each occurrence is a group independently selected from among C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, C₆-C₁₀ aryl, aralkyl.

34. The compound according to claim 32 wherein A⁻

is selected from among Br⁻

, I⁻

, PF₆⁻

, BF₄⁻

, (CF₃SO₂)₂N⁻

, C₁₂H₂₅OSO₃⁻

, C₁₆H₃₃OSO₃⁻

, CF₃SO₃⁻

.

39. A method for discrimination between proton/gamma, proton/X, neutron/gamma, neutron/X, alpha/gamma, alpha/X radiation, said method comprising discrimination between proton/gamma, proton/X, neutron/gamma, neutron/X, alpha/gamma, alpha/X radiation using at least one fluorophore compound as defined in claim 23.

42. The method according to claim 41 to prepare a formula (I) compound as defined according to claim 23, wherein said method comprises:

(i) coupling an <

<

R>

>

aromatic group and an imidazole group via a coupling reaction between said <

<

R>

>

aromatic group and said imidazole group by creating a covalent bond between a sp² carbon atom of the aromatic group and a nitrogen atom of the imidazole group, in the presence of a zeolite NaY containing copper(II) and a base; and

(ii) coupling a <

<

Y-Ar-U>

>

group and an imidazole group via a coupling reaction of said <

<

Y—

Ar—

U>

>

group comprising at least one sp³ carbon atom with asaid imidazole group by creating a covalent bond between the sp³ carbon atom of said <

<

Y—

Ar—

U>

>

group and a nitrogen atom of said imidazole group.

43. The method according to claim 42 wherein step (i) corresponds to the following reaction:

44. The method according to claim 42 wherein step (ii) corresponds to the following reaction:

45. The method according to claim 42 wherein the compound:

35. A fluorophore solid or liquid material comprising or consisting of a fluorophore compound, the said fluorophore compound comprising an imidazolium group directly attached to an aromatic fluorophore group via a covalent bond between a nitrogen atom of the imidazolium group and a carbon atom of the said aromatic group.

36. The fluorophore solid or liquid material according to claim 35, wherein the material is a transparent plastic material.

40. An instrument for radiation detection, industrial or medical dosimetry comprising a fluorophore compound comprising an imidazolium group directly attached to an aromatic group via a covalent bond between a nitrogen atom of the imidazolium group and a sp² carbon atom of the said aromatic group, or of a material as defined according to claim 35.

37. A method for the detection of gamma, X, neutron, or proton radiation, said method comprising detecting gamma, X, neutron, or proton radiation using at least one fluorophore compound comprising an imidazolium group directly attached to an aromatic fluorophore group via a covalent bond between a nitrogen atom of the imidazolium group and a sp² carbon atom of the said aromatic group.

38. The method according to claim 37 for discrimination between proton/gamma, proton/X, neutron/gamma, neutron/X, alpha/gamma, alpha/X radiation.

41. A method to prepare a compound comprising an imidazolium group directly attached to an aromatic group via a covalent bond between a nitrogen atom of the imidazolium group and a carbon atom of said aromatic group, the said method comprising a coupling reaction of an aromatic group with an imidazole group by creating a covalent bond between a sp² carbon atom of the aromatic group and a nitrogen atom of the imidazole group in the presence of a zeolite NaY containing copper(II) and a base.