CS201191B1 - 8,8'-dibromo-3,3'-como-3-cobalto-bis/decahydro-1,2-dicarba-closo-dodecaborate/ and process for preparing thereof - Google Patents
8,8'-dibromo-3,3'-como-3-cobalto-bis/decahydro-1,2-dicarba-closo-dodecaborate/ and process for preparing thereof Download PDFInfo
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- CS201191B1 CS201191B1 CS144678A CS144678A CS201191B1 CS 201191 B1 CS201191 B1 CS 201191B1 CS 144678 A CS144678 A CS 144678A CS 144678 A CS144678 A CS 144678A CS 201191 B1 CS201191 B1 CS 201191B1
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- Czechoslovakia
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- bis
- cobalto
- como
- dibromo
- decahydro
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- 238000004519 manufacturing process Methods 0.000 title 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- LJBHYCBOOYAVFP-UHFFFAOYSA-N bromoform 1,4-dioxane Chemical compound BrC(Br)Br.C1COCCO1 LJBHYCBOOYAVFP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 2
- TVBISCWBJBKUDP-UHFFFAOYSA-N borate Chemical compound [O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] TVBISCWBJBKUDP-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920005654 Sephadex Polymers 0.000 description 1
- PMHCSCQXRLVFNR-UHFFFAOYSA-N [Br].[Co] Chemical compound [Br].[Co] PMHCSCQXRLVFNR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229940093635 tributyl phosphate Drugs 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Description
(54) 8,8 _ Dibrómo-3,3 -komo-3-kobalto-bis/dekahydro-l,2-dikerba-kloso-dodekabor/át a sposob jeho přípravy(54) 8,8-Dibromo-3,3-como-3-cobalto-bis (decahydro-1,2-dicabicyclo-dodecaborate) and process for its preparation
Vynález sa týká 8,8'-dibrómo-3,3*-komo-3-kobalto-bis-/dekehydro-l,2-diksrba-kloso-dodekabor/átu sumárneho vzorca / /C^B^H^Br^Co / Cs a sposobu jeho přípravy.The present invention relates to 8,8'-dibromo-3,3'-como-3-cobalto-bis- (decehydro-1,2-dicarbacadiosodecaborate) of the general formula (C ^B ^H HBr ^O). / Cs and the way of its preparation.
Jedná se o selektívne extrakčné činidlo, patriace do skupiny metalokarboránov, na extrakciu jednomocných katiónov najma 133Cs, Sr, ako cenných rádionuklidov z rádioaktívnych odpadových roztokov po spracovaní jádrového paliva.It is a selective extraction agent belonging to the group of metalocarboranes for the extraction of monovalent cations, in particular 133 Cs, Sr, as valuable radionuclides from radioactive effluents after treatment of the nuclear fuel.
Doterajšie extrakčné činidla, používané na selektívnu extrakciu jednomocných alebo dvojmocných katiónov zo zásaditého prostredia ako napr. 8-hydroxychinolín, 2-thenoyltrifluóracetón, tributylfosfát, tetraboritán a iné, sú radiačně nestabilně, nemožno ich použiť na extrakciu priamo z kyslých odpadových roztokov pri spracovaní jádrového paliva, pretože rozdelovacie poměry sú nízké, resp. separsčné faktory sú nevyhovujíce. Lepáie vlastnosti majú činidlá karboránového typu, například ktorých východisková zlúčenina je cézna sol bis/1,2dikarbollyl/kobaltu. Toto činidlo extrahuje jednomocné kationy z kyslého prostredia, kinetika reextrakcie je rýchla, ale sú chemicky radiačně nestabilně.Existing extracting agents used to selectively extract monovalent or divalent cations from a basic medium such as e.g. 8-hydroxyquinoline, 2-thenoyltrifluoroacetone, tributylphosphate, tetraborate and others are unstable in radiation, they cannot be used to extract directly from acid waste solutions in the processing of core fuel, since the partition ratios are low, respectively. separation factors are unsatisfactory. Carborane-type reagents, for example whose starting compound is cesium bis (1,2-dicarbollyl) cobalt, have better properties. This agent extracts monovalent cations from an acidic medium, the reextraction kinetics are fast, but are chemically radiation unstable.
Tieto nedostatky v podatatnej miere odstraňuje nové extrakčné činidlo a sposob jeho přípravy pódia vynálezu.These drawbacks are substantially eliminated by the new extraction agent and the process for its preparation according to the invention.
Podstata sposobu přípravy 8,8*-dibrómo-3,3’’-komo-3-kobalto-bis/dekahydro-l,2-dikarbakloso-dodekabor/átu sumárneho vzoroe /Vc^BgH^QBr/^CCj/Cs spočívá v tom, že sa na céznu soíSUMMARY OF THE INVENTION The preparation of 8,8 * -dibromo-3,3 '- como-3-cobalto-bis (decahydro-1,2-dicarbaclosododecaborate) of the general formula (Vc (BgH4 QBr) (CCl) Cs) consists in: being on the cesium salt
3,3*-komo-3-kobalto-bis/undekehydro-l,2-dikarba-kloso-dodekabor/ótu v metanole pósobi mole2011913,3'-Como-3-cobalto-bis / undecehydro-1,2-dicarbabasododecaborate / methanol in mole201191
201 191 kulárnym brómom v množstve 2 moly brómu na 1 mól céznej soli, alebo na céznu sol 3,3-komo3-kobalto-bia/undekahydro-l,2-dikarba-kloso-dodekabor/átu v zmeai dioxán-brómoform sa posobí UV žiarením po dobu 210 až 270 minút, pričom zlúčenina sa očistí gélovou chromatografiou,201 191 cobalt bromine in an amount of 2 moles of bromine per mole of cesium salt, or per cesium salt of 3,3-como-3-cobalobobia / undecahydro-1,2-dicarbabasododecaborate in dioxane-bromoform mixed with UV irradiation for 210 to 270 minutes, the compound being purified by gel chromatography,
Příklad 1Example 1
K 20 ml 0,1 M roztoku céznej soli 3,3ť-komo-3-kobaltu-bis/undekahydro-l,2-dlkarba-kloso-dodekabor/átu v metanole sa přidá 0,35 ml brómu, čo odpovedá 1 molu céznej soli na 2 mól; brómu. Vzniknutý 8,8'-dibrómo-3,3*komo-kobalto-bis/dekahydro-l,2-dikarba-kloso-dodekabor/át sa dočisti kryštalizáciou.To 20 ml of a 0.1 M solution of cesium salt of 3,3 ' -komo-3-cobalt-bis / undecahydro-1,2-dlcarbocarbododecaborate in methanol is added 0.35 ml of bromine corresponding to 1 mole cesium salt per mole; Br. The resulting 8,8'-dibromo-3,3 * como-cobalto-bis / decahydro-1,2-dicarbabasododecaborate is purified by crystallization.
Příklad 2Example 2
5.10-¾ roztok céznej soli 3,3'-komo-3-kobalto-bis/undekahydro-l,2-dikarba-klosp-dodekabor/átu v zmesi dioxán-bromoform /v pomere 3 : 1/ sa ožiari UV žiarením /horským slnkom/. Po 240 minútach ožiarovania vznikne cézna sol 8,8,-dibrómo-3,3z-komo-3-kobaltu-bis/dekahydro-l,2-dikarba-kloso-dodekabor/átu, ktorá se dočistí gélovou chromatografiou, například na deliacom činidle Sephadex LH-20, čo je esterifikovaný-dextranový gél a kryštalizáciou.5.10 - ¾ solution of cesium salt of 3,3'-como-3-cobalto-bis (undecahydro-1,2-dicarbba-clospododecaborate) in dioxane-bromoform (3: 1) is irradiated with UV radiation (mountain) sun /. After 240 minutes of irradiation, the cesium salt of 8,8 , -dibromo-3,3 is formed from -komo-3-cobalt-bis / decahydro-1,2-dicarbabasododecaborate, which is purified by gel chromatography, for example on a separating agent. Sephadex LH-20 which is an esterified-dextran gel and crystallized.
Látka podlá vynálezu 8,8'-dibrómomo-3,3-komo-3-kobalto-bis/dekahydro-l,2-dikarba-kloso-dodekabor/át sumárneho vzorca //C2BgL^0Br/gCu/Cs je nová zlúčenina patriaca do skupiny metalkalboránov. Existencis a spósob přípravy tejto zlúčeniny neboli ešte popísené.The compound according to the invention 8,8'-dibromo-3,3-como-3-cobalto-bis / decahydro-1,2-dicarbabasododecaborate of the general formula // C 2 BgL 4 O Br / gCu / Cs is a new compound belonging to the group of metalkalboranes. The existence and method of preparation of this compound have not yet been described.
Struktura zlúčeniny podlá vynálezu je na pripojenom obrázku. Xdentifikácia zlúčeniny podlá vynálezu bola převedená naeledovnymi metodami:The structure of the compound of the invention is shown in the attached figure. Xdentification of the compound of the invention was carried out by the following methods:
, Elementárna analýza: Cí- 7,87Elemental Analysis: C, 7.87
H % - 3,38 fir í - 27,58H% - 3.38 companies - 27.58
IC spektrum bolo merané v nujolle na spektrofotometr! /Éerkin-Elmer, model 567, USA/. Vzorky sa merali KBr-technikou /tj. 1 mg vzorky a 300 mg KBr/.The IC spectrum was measured in nujolle on a spectrophotometer! (Éerkin-Elmer, model 567, USA). Samples were measured by the KBr technique / i. 1 mg sample and 300 mg KBr /.
040 m, 2 520 - 253 s, 1 184 s, 1 110 s, 1 080 m,< 1 010 m, 980 s, 940 w, 915 w, 900 w, 880 m, 810 w, 850 w, 830 m, 812 s, 790 w, 735 w, 710 w, 690 m, 650 m, 610 m, 380 m, 360 w. Symbol s vyjadřuje silný pás, w slabý pás a m stredný pás. V IČ spektre látky podlá vynálezu je vidiet intenzívny pás pri 800 a 812 cm~\ ktorý prislúcha B-Br vazbě.040 m, 2 520-253 s, 1 184 s, 1 110 s, 1 080 m, <1 010 m, 980 s, 940 w, 915 w, 900 w, 880 m, 810 w, 850 w, 830 m, 812 s, 790 W, 735 W, 710 W, 690 m, 650 m, 610 m, 380 m, 360 w. The symbol s denotes a strong belt, w a weak belt and m a middle belt. In the IR spectrum of the compound of the present invention, an intense band at 800 and 812 cm @ -1 is associated with the B-Br bond.
NMR spektrum bolo merané na spektrofotometri /íelsa Univeraal Counter BM-44§Z při teplote 25 °C, pracovněj frekvencie 80 wlHz. Vzorky sa rozpúšíali v deuterovanom acetone, vnútorný Standard hexamethyldisiloxán. V i.MR spektre látky podlá vynálezu se pozoroval jediný singelt s řT= 4,33 ppm, prislúchajúci G-H karboránu, čo dokazuje, že substitácia. nastala na atómoch bóru.The NMR spectrum was measured on a Univeraal Counter BM-44 ° Z spectrophotometer at 25 ° C, operating at 80 wlHz. The samples were dissolved in deuterated acetone, internal Standard hexamethyldisiloxane. In the i.MR spectrum of the compound of the invention, a single singelt with δ T = 4.33 ppm, associated with G-H carborane, was observed, indicating that substitution. occurred on boron atoms.
Teplota topenia zlúčeniny podlá vynálezu je vyššia ako 360 °C. V UV-opektre látky podlá vynálezu sú dve maximá pri A = 277 a 323 run.The melting point of the compound of the invention is above 360 ° C. In the UV-spectrum of the substance of the invention, there are two maxima at A = 277 and 323 runes, respectively.
uátka podlá vynálezu je nové selektivně extrakčné činidlo na extrakciu jednomocných kationov najma 'Ca a Sr, ako cenných rádionuklidov z rádioaktívnych odpadov po spracovaní jádrového paliva. Činidlo extrahuje z kyelého prostredia, alnetika extrakcxe je rýchla.The present invention is a novel selectively extracting agent for extracting monovalent cations, in particular Ca and Sr, as valuable radionuclides from radioactive waste after processing nuclear fuel. The reagent extracts from acidic environment, the extraction extraction is fast.
201 191201 191
Je ovela vhodnéjáie na .extrakciu ^37Ca a 39sr z odpadových radioaktívnych roztokov ako doterajáie používané činidlá karboránového typu, nakoíko je radiačně aj chemicky veími stabilně, asi stonásobné stabilnejSie ako doteraz používané činidlá.It is much more suitable for the extraction of < 37 Ca < 3 > and < 39 > from waste radioactive solutions as the prior art carborane type reagents, since it is very stable in radiation and chemistry, about 100 times more stable than the reagents used hitherto.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS144678A CS201191B1 (en) | 1978-03-08 | 1978-03-08 | 8,8'-dibromo-3,3'-como-3-cobalto-bis/decahydro-1,2-dicarba-closo-dodecaborate/ and process for preparing thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS144678A CS201191B1 (en) | 1978-03-08 | 1978-03-08 | 8,8'-dibromo-3,3'-como-3-cobalto-bis/decahydro-1,2-dicarba-closo-dodecaborate/ and process for preparing thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS201191B1 true CS201191B1 (en) | 1980-10-31 |
Family
ID=5348846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS144678A CS201191B1 (en) | 1978-03-08 | 1978-03-08 | 8,8'-dibromo-3,3'-como-3-cobalto-bis/decahydro-1,2-dicarba-closo-dodecaborate/ and process for preparing thereof |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS201191B1 (en) |
-
1978
- 1978-03-08 CS CS144678A patent/CS201191B1/en unknown
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