CN103788138A - Binuclear-cobalt-containing carborane derivative and preparation method thereof - Google Patents
Binuclear-cobalt-containing carborane derivative and preparation method thereof Download PDFInfo
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- CN103788138A CN103788138A CN201410020214.5A CN201410020214A CN103788138A CN 103788138 A CN103788138 A CN 103788138A CN 201410020214 A CN201410020214 A CN 201410020214A CN 103788138 A CN103788138 A CN 103788138A
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- carborane
- cobalt
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- binuclear
- derivative
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 17
- 239000010941 cobalt Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 6
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 125000002524 organometallic group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- XXMFEVRCWJPFBR-SKDRFNHKSA-N C[C@H]1C=C([C@@H]2C=C(C)C=C2)C=C1 Chemical compound C[C@H]1C=C([C@@H]2C=C(C)C=C2)C=C1 XXMFEVRCWJPFBR-SKDRFNHKSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Abstract
The invention relates to a binuclear-cobalt-containing carborane derivative and a preparation method thereof. According to the binuclear-cobalt-containing carborane derivative, the molecular formula is C14H24B10O2S3Co2 and the molecular weight is 482.44. A synthesis method of the compound comprises the following steps: in the presence of argon, dissolving o-carborane into ethyl ether; adding butyl lithium and agitating and reacting for 20-30 minutes; then adding monomer sulfur and reacting for 15-25 minutes; dripping a tetrahydrofuran solution of MeCpCo(CO)I2 into a reaction solution at 0 DEG C and finishing dripping within 20-30 minutes; agitating in an ice batch for 0.5-1 hour and then agitating at a room temperature for 2-3 hours; decompressing and pumping a reaction solvent; separating and purifying a rough product by using a column chromatography; eluting by taking a mixed solvent of petroleum ether and dichloromethane (with the volume ratio of 2:1) as an eluting solution to obtain a target product.
Description
Technical field
The present invention relates to a kind of containing Binuclear Cobalt carborane derivative and preparation method thereof.
Background technology
Carborane is almost to be reported (as: Bregadze V I.Chem.Rev., 1992,92,209-223.) by the U.S. and USSR (Union of Soviet Socialist Republics) the end of the year 1963 simultaneously.Due to its unique physics and chemistry character, carborane has a wide range of applications (as: Pindado G J, Lancaster S J in fields such as catalyzer, supramolecule and polymkeric substance, Thomton-Pett M, et al.J.Am.Chem.Soc., 1998,120,6816-6817; Larsen A S, Holbrey J D, Tham F S, et al.J.Am.Chem.Soc., 2000,122,7264-7272; Blandford I, Jeffery J C, Jelliss P A, et al.Organometallics, 1998,17,1402-1411; Curtis M A, Finn M G, Grimes R N.J.Organomet.Chem., 1998,550,469-472;
j.Chem.Rev., 1992,92,269-278.).Ortho position carborane is one of field of studying thorough the most completely in carborane and assorted carborane field.Hydrogen atom on the carborane carbon atom of ortho position has certain acidity, can react with n-Butyl Lithium.Principle accordingly, can synthesize half sandwich type 16 electronics carborane compounds (as: Herberhold M, Jin G X, Yan H, et al.J.Organomet.Chem., 1999,587, the 252-257 that contains transition metal iron group and cobalt family metal ion center; Kim D H, Ko J, Park K, et al.Organometallics, 1999,18,2738-2740; Herberhold M, Yan H, Milius W.J.Organomet.Chem., 2000,598,142-147; Herberhold M, Yan H, Milius W.Organometallics, 2000,19,4289-4294; Bae J Y, Lee Y J, Kim S J, et al.Organometallics, 2000,19,1,514 one 1521.).At synthetic half sandwich type 16 electronics carborane Compound C pCoS
2c
2b
10h
10process in, separate and obtained a carborane Compound C p with two Cp rings and two cobalt ion centers
2co
2s
2c
2b
10h
10(Kim D H, Ko J, Park K, et al.Organometallics, 1999,18,2738-2740.).We are at synthetic half sandwich type 16 electronics carborane compound MeCpCoS recently
2c
2b
10h
10process in, successfully separate obtained a new texture containing Binuclear Cobalt carborane derivative.
The invention discloses a kind of containing Binuclear Cobalt carborane derivative and preparation method thereof, for design with syntheticly there is multinuclear cobalt carborane derivative and accumulated test material and foundation.
Summary of the invention
The object of the invention is to open one containing Binuclear Cobalt carborane derivative and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
Of the present invention is the compound of following molecular formula: C containing Binuclear Cobalt carborane derivative
14h
24b
10s
2co
2; Its molecular structure skeleton symbol is as follows:
The basic structure of described carborane derivative is a kind of containing Binuclear Cobalt carborane derivative.In this molecule, contain two cobalt ion centers and two MeCp rings simultaneously; In addition in molecule, also contain a carborane cage body.
The preparation method of described carborane derivative: under argon shield; make solvent with ether; be 1: 2 stirring reaction 20-30 minute by ortho position carborane and n-Butyl Lithium by amount of substance ratio, then add and the elemental sulfur of the amount of substance such as n-Butyl Lithium reaction 15-25 minute.At 0 ℃, drip MeCpCo (CO) I with the amount of substance such as ortho position carborane
2tetrahydrofuran solution, in 20-30 minute, dropwise; In ice bath, stir afterwards and after 0.5-1 hour, at room temperature stir again 2-3 hour.Decompressing and extracting reaction solvent, crude product column chromatography separating-purifying, mixed solvent (volume ratio=2: 1), for elutriant carries out wash-out, obtain target product of sherwood oil and methylene dichloride.
Embodiment
Embodiment 1
Under argon shield, containing in the 10mL diethyl ether solution of ortho position carborane (57.7mg, 0.4mmol); adding concentration is the n-Butyl Lithium 0.4mL of 2.0mol/L, stirs 20 minutes, then adds elemental sulfur (25.6mg; 0.8mmol), reaction 15 minutes.At 0 ℃, drip MeCpCo (CO) I
2the 20mL tetrahydrofuran solution of (O.168g, 0.4mmol), dropwised in 20 minutes; In ice bath, stir after 0.5 hour and at room temperature stir again 2 hours.Decompressing and extracting reaction solvent, crude product column chromatography separating-purifying, mixed solvent (volume ratio=2: 1), for elutriant carries out wash-out, obtain target product of sherwood oil and methylene dichloride.
1H?NMR(CDCl
3)：δ4.99(s，MeC
sH
4)，4.74(s，MeC
5H
4)，1.91(s，CH
3).EI-MS(70eV)：m/z482.2(M
+，100.00％).Anal.calcd?for?C
14H
24B
10S
2Co
2：C，34.85；H，5.01.Found：C，34.80；H，4.98％.
Embodiment 2
Under argon shield, containing in the 15mL diethyl ether solution of ortho position carborane (72.1mg, 0.5mmol); adding concentration is the n-Butyl Lithium 0.5mL of 2.0mol/L, stirs 25 minutes, then adds elemental sulfur (32.0mg; 1.0mmol), reaction 20 minutes.At 0 ℃, drip MeCpCo (CO) I
2the 25mL tetrahydrofuran solution of (0.210g, 0.5mmol), dropwised in 25 minutes; In ice bath, stir after 0.7 hour and at room temperature stir again 2.5 hours.Decompressing and extracting reaction solvent, crude product column chromatography separating-purifying, mixed solvent (volume ratio=2: 1), for elutriant carries out wash-out, obtain target product of sherwood oil and methylene dichloride.
1HNMR(CDCl
3)：δ4.99(s，MeC
5H
4)，4.74(s，MeC
sH
4)，1.91(s，CH
3).EI-MS(70eV)：m／z482.2(M
+，100.00％).Anal.calcd?for?C
14H
24B
10S
2Co
2：C，34.85；H，5.01.Found：C，34.80；H，4.98％.
Embodiment 3
Under argon shield, containing in the 20mL diethyl ether solution of ortho position carborane (86.6mg, 0.6mmol); adding concentration is the n-Butyl Lithium 0.6mL of 2.0mol/L, stirs 30 minutes, then adds elemental sulfur (38.4mg; 1.2mmol), reaction 25 minutes.At 0 ℃, drip MeCpCo (CO) I
2the 30mL tetrahydrofuran solution of (0.252g, 0.6mmol), dropwised in 30 minutes; In ice bath, stir after 1 hour and at room temperature stir again 3 hours.Decompressing and extracting reaction solvent, crude product column chromatography separating-purifying, mixed solvent (volume ratio=2: 1), for elutriant carries out wash-out, obtain target product of sherwood oil and methylene dichloride.
1HNMR(CDCl
3)：δ4.99(s，MeC
5H
4)，4.74(s，MeC
sH
4)，1.91(s，CH
3).EI-MS(70eV)：m／z482.2(M
+，100.00％).Anal.calcd?for?C
14H
24B
10S
2Co
2：C，34.85；H，5.01.Found：C，34.80；H，4.98％。
Claims (5)
1. one kind contains Binuclear Cobalt carborane derivative and preparation method thereof, it is characterized in that: its molecular formula is C
14h
24b
10s
2co
2, molecular weight is 482.45, molecular structure skeleton symbol is as follows:
2. contain Binuclear Cobalt carborane derivative by one claimed in claim 1, it is characterized in that: in this molecule, contain two cobalt ion centers.
3. contain Binuclear Cobalt carborane derivative by one claimed in claim 1, it is characterized in that: in this molecule, contain two MeCp rings.
4. contain Binuclear Cobalt carborane derivative by one claimed in claim 1, it is characterized in that: in this molecule, contain a carborane cage body.
5. a preparation method who prepares Binuclear Cobalt carborane derivative described in claim 1, is characterized in that: under argon shield, ortho position carborane is dissolved in ether, adds butyllithium, and stirring reaction 20-30 minute, then add elemental sulfur, reaction 15-25 minute.At 0 ℃, drip MeCpCo (CO) I
2tetrahydrofuran solution, in 20-30 minute, dropwise; In ice bath, stir and after 0.5-1 hour, at room temperature stir again 2-3 hour.Decompressing and extracting reaction solvent, crude product column chromatography separating-purifying, mixed solvent (volume ratio=2: 1), for elutriant carries out wash-out, obtain target product of sherwood oil and methylene dichloride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105404A (en) * | 2019-05-07 | 2019-08-09 | 上海应用技术大学 | The ruthenium complex of the benzoxazoles structure of carborane radical containing ortho position and its preparation and application |
| CN110117299A (en) * | 2019-05-30 | 2019-08-13 | 上海应用技术大学 | The rhodium complex of the benzimidazole structure of carborane radical containing ortho position and its preparation and application |
| CN110240620A (en) * | 2019-06-12 | 2019-09-17 | 上海应用技术大学 | A kind of double-core rhodium complex of the structure of carborane containing ortho position and its preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250203A (en) * | 2008-03-25 | 2008-08-27 | 南京大学 | Method for preparing thio-1,2-dicarbo-closo-dodecacarborane organic derivatives and product thereof |
-
2014
- 2014-01-08 CN CN201410020214.5A patent/CN103788138A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250203A (en) * | 2008-03-25 | 2008-08-27 | 南京大学 | Method for preparing thio-1,2-dicarbo-closo-dodecacarborane organic derivatives and product thereof |
Non-Patent Citations (4)
| Title |
|---|
| BAO-HUA XU ET AL.: "Reactivity of CpCo 16e Half-Sandwich Complexes Containing a Chelating 1，2-Dicarba-closo-dodecaborane-1，2-dichalcogenolate Ligand toward Phenylacetylene", 《ORGANOMETALLICS》 * |
| DAE-HYUN KIM ET AL.: "Addition Reactions of the Novel Mononuclear Dithio-o-carboranylcobalt（III） Complex（η5-C5H5）Co（η2-S2C2B10H10）", 《ORGANOMETALLICS》 * |
| DAE-HYUN KIM ET AL.: "Addition Reactions of the Novel Mononuclear Dithio-o-carboranylcobalt（III） Complex（η5-C5H5）Co（η2-S2C2B10H10）", 《ORGANOMETALLICS》, vol. 18, no. 15, 25 June 1999 (1999-06-25), pages 2738 - 2740 * |
| JAE-HONG WON ET AL.: "Investigation of New Coordination Modes for Coordinatively Unsaturated （Dithiolato）cobalt（III） Complex [（η5-Cp）Co（1,2-S2C2B10H10-S，S’）]", 《ORGANOMETALLICS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105404A (en) * | 2019-05-07 | 2019-08-09 | 上海应用技术大学 | The ruthenium complex of the benzoxazoles structure of carborane radical containing ortho position and its preparation and application |
| CN110117299A (en) * | 2019-05-30 | 2019-08-13 | 上海应用技术大学 | The rhodium complex of the benzimidazole structure of carborane radical containing ortho position and its preparation and application |
| CN110117299B (en) * | 2019-05-30 | 2021-05-11 | 上海应用技术大学 | Rhodium complex containing ortho-carbon boron alkyl benzimidazole structure and preparation and application thereof |
| CN110240620A (en) * | 2019-06-12 | 2019-09-17 | 上海应用技术大学 | A kind of double-core rhodium complex of the structure of carborane containing ortho position and its preparation and application |
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Application publication date: 20140514 |