NL2031174B1 - Boron-containing compound useful for the isotope separation of boron, method for synthesis thereof and uses thereof - Google Patents
Boron-containing compound useful for the isotope separation of boron, method for synthesis thereof and uses thereof Download PDFInfo
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- NL2031174B1 NL2031174B1 NL2031174A NL2031174A NL2031174B1 NL 2031174 B1 NL2031174 B1 NL 2031174B1 NL 2031174 A NL2031174 A NL 2031174A NL 2031174 A NL2031174 A NL 2031174A NL 2031174 B1 NL2031174 B1 NL 2031174B1
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- boron
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- boric acid
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 22
- 238000005372 isotope separation Methods 0.000 title abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004327 boric acid Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 claims description 24
- ZOXJGFHDIHLPTG-IGMARMGPSA-N boron-11 atom Chemical compound [11B] ZOXJGFHDIHLPTG-IGMARMGPSA-N 0.000 claims description 21
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 16
- GKDCWKGUOZVDFX-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)butane-2,3-diol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C(O)(C(F)(F)F)C(F)(F)F GKDCWKGUOZVDFX-UHFFFAOYSA-N 0.000 claims description 9
- 229910015900 BF3 Inorganic materials 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000012429 reaction media Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010503 protodeborylation reaction Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 17
- 238000001514 detection method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000009206 nuclear medicine Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- KTMKRRPZPWUYKK-UHFFFAOYSA-N methylboronic acid Chemical compound CB(O)O KTMKRRPZPWUYKK-UHFFFAOYSA-N 0.000 description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000005494 condensation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000000155 isotopic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- -1 boron trifluoride Chemical compound 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005369 laser isotope separation Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000100 multiple collector inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 1
- JFALSRSLKYAFGM-OIOBTWANSA-N uranium-235 Chemical compound [235U] JFALSRSLKYAFGM-OIOBTWANSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C07F5/025—Boronic and borinic acid compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
Abstract
The invention relates to a boron—containing compound adapted to serve as a vector to an isotope separation of boron, in. particular‘ by cascade gas centrifugation, and which, once enriched with 10B or 11B, can be easily converted 5 into other boron—containing compounds such as boric acid. This compound meets the formula (I) hereinafter: F3C CF3 Fáà—ËCFB Ck\ //O T R (I) wherein R represents a linear or branched, C1 to C4 alkyl or alkoxy group. 10 The invention also relates to the synthesis of the compound of formula (I) as well as to the enrichment thereof with_10B or 11B. It further relates to the conversion of the compound of formula (I) enriched with 10B or 11B into boric acid. 15 Applications: in particular nuclear industry (manufacture of neutron shielding materials, neutron detection system, devices for controlling the reactivity of the reactors, etc.) and in nuclear medicine.
Description
THEREOF Description Technical field The invention relates to the field of isotope separation of boron.
More specifically, the invention relates to a boron- containing compound adapted to serve as a vector to an isotope separation of boron, in particular by cascade gas centrifugation, and which, once enriched with boron-10 or boron-11, can be easily converted into other boron- containing compounds (which therefore are also enriched with boron-10 or boron-11) such as boric acid or boron trifluoride.
The invention also relates to the synthesis of this compound as well as the enrichment thereof with boron-10 or boron-11.
It further relates to the conversion of said compound, once enriched with boron-10 or boron-11, into boric acid or into boron trifluoride.
Given the neutron-absorbing properties of boron-10, the invention finds application in particular: — in the nuclear industry, for example for the manufacture of neutron shielding materials intended for the protection of people and equipment, the manufacture of neutron detection system such as sensors or scintillators, the manufacture of devices for controlling the reactivity of reactors such as control rods which are present in the core of the reactors, or as a neutron poison in the primary circuits of reactors, in the water of the pools of reactors or in the water of the spent nuclear fuel storage pools; and — in nuclear medicine, in particular for the treatment of malignant tumours by Boron Neutron Capture Therapy {or BNCT), also called boroneutrotherapy.
The invention also finds application in all fields where boron-containing compounds enriched with boron-11, such as boron trifluoride, are used, which is, for example, the case of the semiconductor industry.
Prior art Natural boron consists of two stable isotopes having a mass of 10 and 11 in the respective proportions of 19,9 + 0,7 2 and 80,1 + 0,7 % depending on deposits.
Boron, like zirconium and gadolinium, belongs to the elements of Mendeleev's table that have a larger neutron- absorbing effective surface.
Therefore, some boron-containing compounds, such as boric acid, zinc borates, boron carbide, boron nitride and boron oxide, have been used since a very long time as neutron-absorbers in the nuclear industry.
Boron-10 actually has a neutron-absorbing effective section that is much larger than that of boron-11.
Hence, it would be desirable to be able to enrich with boron-10 the boron-containing compounds that might be used for boron-absorbing properties if one wish to optimise the neutron-absorbing efficiency of these compounds.
There are different isotope separation techniques such gas-phase isotope separation, atomic vapour laser isotope separation, molecular laser isotope separation, chemical isotope separation and isotope separation by cascade gas centrifugation, also called cascade gas ultra- centrifugation.
Today, this last technique is the primarily used one to enrich uranium hexafluoride (UFs} with uranium-235 on an industrial scale.
It consists in subjecting, in a plurality of centrifuges mounted in cascade, molecules having an identical chemical composition but with different molecular masses to a very high centrifugal force, which makes the molecules to separate according to their molecular mass, the heaviest molecules (25SUFs) being projected towards the wall of the centrifuges whereas the lightest ones (2>UFs) migrate towards the centre of the centrifuges.
Given the advantages of cascade gas centrifugation, in particular in terms of energy consumption, it would be desirable to be able to carry out an isotope separation of boron by this technique.
Nonetheless, carrying out an isotope separation of boron by cascade gas centrifugation requires having a boron- containing compound that meets the following requirements: — be volatile, i.e. have a saturation vapour pressure of at least 600 Pa at 20°C, — be thermodynamically stable at temperatures lower than 200°C in standard pressure condition (10° Pa), — have a molar mass comprised between 100 g/mol and 500 g/mol, and — be neither toxic nor corrosive.
Furthermore, it would be desirable that this compound is air stable for ease of handling, can be synthesised through a “soft chemistry” process and that once enriched with boron-10 or boron-11, it can be easily converted into boron-containing compounds with an industrial value such as boric acid or boron trifluoride.
Disclosure of the invention The invention precisely aims to provide a boron- containing compound that meets all of these requirements.
This compound is a fluorinated pinacolate of boronic acid meeting the formula (I) hereinafter:
FC CF Le
B a wherein R represents a linear or branched alkyl or alkoxy group, comprising from 1 to 4 carbon atoms.
By linear or branched alkyl group, comprising from 1 to 4 carbon atoms, it should be understood a group selected amongst the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl groups, whereas by linear or branched alkoxy group, comprising from 1 to 4 carbon atoms, it should be understood any group selected amongst the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec- butoxy, isobutoxy and tert-butoxy. In accordance with the invention, R is advantageously an alkyl group, which is preferably linear. Amongst the linear alkyl groups, the methyl and ethyl groups are preferred, the methyl group being more preferable. The compound of formula (I) could be obtained through a condensation reaction between hexafluoro-2, 3- bis (trifluoromethyl) -2,3-butanediol (or perfluoropinacol) and a boronic acid of formula: R-B{0H)}: wherein R represents a linear or branched alkyl or alkoxy group, comprising from 1 to 4 carbon atoms, according to the scheme hereinafter:
FC CF HO OH FC CF Le + hd ww en + 2H,0 HO OH R _ A
B | {t) Hence, another object of the invention is a method for synthesising the compound of formula (I) which comprises: a) the reaction hereinbefore which is preferably carried out at a temperature ranging from 15°C to 45°C, preferably between 25°C and 35°C and under inert atmosphere, for example in a reactor rendered inert beforehand or swept by an inert gas such as argon; then b) the separation of the compound from the reaction medium obtained upon completion of step a). Advantageously, the reaction of step a) is conducted in an ether solvent which is non-volatile at the selected reaction temperature, i.e. typically having a saturation vapour pressure at most equal to 500 Pa at 20°C, preferably at most equal to 200 Pa at 20°C and still preferably at most equal to 10 Pa at 20°C, and in the presence of a desiccant, the latter being intended to capture the water molecules released by said reaction.
In accordance with the invention, the ether solvent 5 is preferably diphenyl ether (or phenoxybenzene) whose saturation vapour pressure is 8 Pa at 20°C. Nonetheless, other diphenyl ethers substituted, for example, with one or several halogen(s) and/or alkyl group(s), could also be used.
As regards the desiccant, it may consist of any compound capable of capturing water present in a reaction medium, even in traces, which is insoluble in the ether solvent and which is incapable of chemically reacting with this solvent as well as with perfluoropinacol and boronic acid. In particular, this compound may be anhydrous magnesium sulphate (MgSOa), anhydrous sodium sulphate (Na;S0Q4) or a molecular sieve such as an aluminosilicate or a zeolite.
Preferably, the separation of step b) is carried out by evaporation-condensation of the compound under vacuum, preferably under static vacuum.
In accordance with the invention, the method may further comprise, between steps a) and b), a filtering of the medium obtained upon completion of step a), which filtering is also carried out, preferably, under inert atmosphere.
Another object of the invention is a compound of formula (I) enriched with boron-10 or boron-11, preferably with boron-10.
In the context of the invention, it is considered that a compound is enriched with boron-10 when this compound or a compound derived from the conversion thereof (such as boric acid) has a '"B/!'B isotopic ratio higher than or equal to 0.260 whereas it is considered that a compound is enriched with boron-11 when this compound or a compound derived from the conversion thereof has a +°B/1B isotopic ratio lower than or equal to 0.236.
As is known per se, the +9B/14B isotopic ratio could be determined in particular by multicollector inductively coupled plasma mass spectrometry (ICP-MS-MC), for example, as described by J.K. Aggarwal et al. (Chemical Geology 2003, 199, 331-342) and by B. Wang et al. (Talanta 2010, 82, 1378- 1384).
Another object of the invention is a method for enriching with boron-10 or boron-11 a compound of formula (I), which method comprises a cascade gas centrifugation of this compound.
Another object of the invention is a method for preparing boric acid enriched with boron-10 or boron-11, which method comprises a conversion of a compound of formula (I) enriched with boron-10 or boron-11 into boric acid, the compound of formula (I) enriched with boron-10 or boron-11 may be obtained in particular through a method for enrichment with boron-10 or boron-11 as defined before.
In accordance with the invention, the conversion of the compound of formula (I) enriched with boron-10 or boron- 11 into boric acid preferably comprises: — a hydrolysis of the compound into a boronic acid of formula: R-B(OH}); wherein R represents a linear or branched alkyl or alkoxy group, comprising from 1 to 4 carbon atoms; then — a protodeboronation {(protodeborylation) of the boronic acid into boric acid.
According to the invention, it is also possible to prepare boron trifluoride enriched with boron-10 or boron- 11, for example by conversion of a compound of formula (I) enriched with boron-10 or boron-11 into boric acid - this conversion may in particular be carried out as described hereinabove — then by conversion of the boric acid thus obtained into boron trifluoride, for example by reaction of the boric acid with hydrofluoric acid.
Other features of the invention will appear from the following complementary description which is made with reference to the appended figures.
Of course, this complementary description is given as an illustration of the object of the invention and does not form in any case a limitation of this object. Brief description of the figures Figure 1 schematically illustrates the evaporation- condensation setup under static vacuum having been used by the Inventors in the context of the synthesis of compounds of the invention. Figure 2 illustrates the :H NMR spectrum of a compound of the invention, in this instance the fluorinated pinacolate of methylboronic acid (spectrum A), and those of perfluoropinacol (spectrum B) and of methylboronic acid (spectrum C) from which this compound has been synthesised; in these spectrum, the letter s refers to the peak of deuterated tetrahydrofuran (THF-d8) having been used as a solvent to make these spectra. Figure 3 illustrates the B NMR spectra of the fluorinated pinacolate of methylboronic acid (spectrum A) and of methylboronic acid (spectrum C) whose !H NMR spectra are shown in Figure 2. Figure 4 illustrates the °F NMR spectra of the fluorinated pinacolate of methylboronic acid (spectrum A) and of perfluoropinacol (spectrum B) whose :H NMR spectra are shown in Figure 2. Detailed disclosure of an embodiment of the invention The fluorinated pinacolate of methylboronic acid {compound of formula (I) wherein R = methyl) is synthesised according to the following operative procedure.
1.0026 g (0.01665 mol) of 97% pure methylboronic acid (Sigma-Aldrich), 5.595 g of 96% pure hexafluoro-2,3- bis (trifluoromethyl) -2, 3-butanediol (Sigma-Aldrich) and 20 mL of 99% pure diphenyl ether (Sigma-Aldrich), heated up beforehand to 27°C so as to be in the liquid form and into which argon has been put to bubble, are introduced by means of a cannula into a Schlenk tube rendered inert beforehand with argon.
The Schlenk tube is placed in an oil bath heated up to 30°C and the reaction medium is kept under stirring for 30 minutes. Then, an anhydrous MgSO4 equivalent is added and the reaction medium is kept under stirring for 48 more hours, still at 30°C.
After that, the reaction medium is filtered by means of a cannula in another Schlenk tube rendered inert beforehand with argon.
Afterwards, the filtrate is subjected to an evaporation-condensation under static vacuum to separate the reaction product from the remainder of this filtrate and recover this product. This evaporation-condensation under vacuum is carried out using the setup that is illustrated in Figure 1.
In this setup, denoted 10 in Figure 1, the Schlenk tube 1 containing the filtrate is connected via an evaporation fitting 5 to another Schlenk tube 6 which is empty.
The Schlenk tube 1 is immersed in an oil bath 3 thermostated at 30°C thanks to a hot plate 4 also serving as a magnetic stirrer and the filtrate present in this tube is stirred so as to obtain a homogeneous evaporation, whereas the Schlenk tube 2 is immersed in a Dewar flask, denoted 2, filled with liquid nitrogen (-196°C). This temperature gradient causes the creation of a static vacuum within the setup 10 and this static vacuum enables, without having to resort to an external vacuum, the evaporation of the most volatile compound present in the filtrate and the condensation thereof in the Schlenk tube 6.
In this case, since the diphenyl ether is not volatile, it is the reaction product that condensates in the Schlenk tube 6 in the form of a solid, which remains in this form as long as the Schlenk tube 6 remains immersed in liquid nitrogen but melts down very quickly when the temperature rises and is totally gaseous at room temperature and atmospheric pressure.
The reaction product is subjected to a multicore NMR analysis (iH, °F and B) after having dissolved the solid present in the Schlenk tube 6 in deuterated tetrahydrofuran (THF-d8) under argon stream in order to avoid water condensation.
This NMR analysis is carried out with a Brüker Avance™ 300 MHz apparatus.
The obtained NMR spectra are illustrated in Figures 2 to 4 in which they are compared with those obtained in the same conditions for methylboronic acid (Figures 2 and 3) and perfluoropinacol (Figures 2 and 4). In these figures, the spectra denoted A correspond to the reaction product, the spectra denoted B are those of perfluoropinacol whereas the spectra C are those of methylboronic acid.
These spectra confirm that the reaction product is actually the fluorinated pinacolate of methylboronic acid.
Thus, in Figure 2, one could observe in the spectrum A: — the absence of the peak at 6.7 ppm present in the spectrum C and corresponding to the hydrogen atom of the hydroxyl groups carried by the boron atom (B-(0H):), and — the presence of the peak at 0.04 ppm characterising the hydrogen atoms of the methyl group carried by the boron atom (B-CH:3). Mentioned references J.K.
Aggarwal et al., Chemical Geology 2003, 199, 331- 342 B.
Wang et al., Talanta 2010, 82, 1378-1384
Claims (11)
1. Verbinding, met het kenmerk dat deze voldoet aan de formule (I) hierna: F3C CF, Le 0
NI | R (I) waarbij R een lineaire of vertakte alkyl- of alkoxygroep, omvattende 1 tot 4 koolstofatomen, voorstelt.
2. Verbinding volgens conclusie 1, waarbij R een methyl- of ethyl-, bij voorkeur methylgroep voorstelt.
3. Werkwijze voor het synthetiseren van een verbin- ding volgens conclusie 1 of conclusie 2, met het kenmerk dat deze de volgende stappen omvat: a) reactie van perfluorpinacol met een boorzuur met formule: R-B(OH)., waarbij R staat voor een lineaire of vertakte alkyl- of alkoxygroep, omvattende 1 tot 4 kool- stofatomen, in een etheroplosmiddel met een verzadigings- dampdruk die ten hoogste gelijk is aan 500 Pa bij 20°C en in aanwezigheid van een droogmiddel; en b) scheiding van de verbinding uit het reactiemedium dat is verkregen na voltooiing van stap a).
4, Werkwijze volgens conclusie 3, waarbij stap a) wordt uitgevoerd bij een temperatuur variërend van 15°C tot 45°C en onder een inerte atmosfeer.
5. Werkwijze volgens conclusie 3 of 4, waarbij stap b) wordt uitgevoerd door verdamping-condensatie van de verbinding onder vacuüm, bij voorkeur onder statisch vacu- um.
6. Werkwijze volgens één van de conclusies 3 tot 5, die verder omvat, tussen stappen a) en b), een filtratie van het reactiemedium dat is verkregen na voltooiing van stap a).
7. Verbinding volgens conclusie 1 of conclusie 2, met het kenmerk dat deze verrijkt is met boor-10 of boor- 11, bij voorkeur met boor-10.
8. Werkwijze voor het met borium-10 of borium-11 verrijken van een verbinding volgens conclusie 1 of con- clusie 2, met het kenmerk, dat deze een cascadegascentri- fugatie van de verbinding omvat.
9. Werkwijze voor het bereiden van boorzuur ver- rijkt met boor-10 of boor-11, met het kenmerk dat het een omzetting omvat van een verbinding volgens conclusie 7 of van een verbinding verkregen met een werkwijze volgens conclusie 8 in boorzuur.
10. Werkwijze voor het bereiden van boortrifluoride verrijkt met boor-10 of boor-11, met het kenmerk dat deze omvat: - een omzetting van een verbinding volgens conclu- sie 7 of van een verbinding verkregen met een werkwijze volgens conclusie 8 in boorzuur; en dan - een omzetting van het boorzuur in boortrifluori- de.
11. Werkwijze volgens conclusie 9 of conclusie 10, waarbij de omzetting van de verbinding in boorzuur omvat:
- een hydrolyse van de verbinding tot een boorzuur met formule: R-B{OH)., waarbij R een lineaire of vertakte alkyl- of alkoxygroep voorstelt, die 1 tot 4 koolstofato- men omvat; en dan - een protodeboronering van het boorzuur tot boor- ZUUr. -0-0-0-
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