CN101250203A - Method for preparing thio-1,2-dicarbo-closo-dodecacarborane organic derivatives and product thereof - Google Patents
Method for preparing thio-1,2-dicarbo-closo-dodecacarborane organic derivatives and product thereof Download PDFInfo
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- CN101250203A CN101250203A CNA2008100245056A CN200810024505A CN101250203A CN 101250203 A CN101250203 A CN 101250203A CN A2008100245056 A CNA2008100245056 A CN A2008100245056A CN 200810024505 A CN200810024505 A CN 200810024505A CN 101250203 A CN101250203 A CN 101250203A
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- 238000000034 method Methods 0.000 title claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- -1 Acetylenes hydrocarbon Chemical group 0.000 claims description 9
- 229910000765 intermetallic Inorganic materials 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 229940125904 compound 1 Drugs 0.000 abstract description 4
- 150000002736 metal compounds Chemical class 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 abstract 3
- 239000011593 sulfur Substances 0.000 abstract 2
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 30
- 239000000460 chlorine Substances 0.000 description 14
- 239000003814 drug Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004809 thin layer chromatography Methods 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 6
- 229940125898 compound 5 Drugs 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 6
- 238000011275 oncology therapy Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000005840 aryl radicals Chemical class 0.000 description 5
- 206010028980 Neoplasm Diseases 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 201000011510 cancer Diseases 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical group COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 230000001093 anti-cancer Effects 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000001959 radiotherapy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical group OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- 208000003174 Brain Neoplasms Diseases 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 208000032612 Glial tumor Diseases 0.000 description 1
- 206010018338 Glioma Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008499 blood brain barrier function Effects 0.000 description 1
- 210000001218 blood-brain barrier Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- 150000002466 imines Chemical class 0.000 description 1
- 238000007917 intracranial administration Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 125000003835 nucleoside group Chemical group 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
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Images
Abstract
A method for preparing thio-1, 2-dicarbo-closo-dodecarborane (12) organic derivative comprises adding n-butyllithium into the ether solution of 1, 2-C2B10H12, mixing for 0.5-2h, adding sulfur, mixing for 1-3h, to obtain Li2S2C2B10H10, at low temperature, adding tetrahydrofuran solution of metal compound into the ethe solution of Li2E2C2B10H10 (1:1), at low temperature, mixing for 1-3h, naturalling increasing temperature to room temperature, mixing for 2-12h, separating, evaporating out solvent to obtain the plane four-coordination metal compound 1 of thio-1, 2-dicarbo-closo-dodecarborane (12) complex, wherein the metal compound belongs to VIII group. The metal complex 1 of plane four-sulfur coordination and alkyne can be dissolved in organic solvent to be reacted for 1-24h at -20DEG C to 110DEG C, to obtain thio-1, 2-dicarbo-closo-dodecarborane (12) organic derivative. The invention has simple process, which can prepare Fc(CCH)(S2C2B10H10), [(FcC(CH2)S)]2C2B10H10, Ph(CCH)(S2C2B10H10) and (MeOCOCHCHS)2C2B10H10.
Description
Technical field:
The present invention relates to a class sulfo--1, the preparation method of 2-two carbon generation-enclosed-12 carborane (12) organic derivatives, the sulfo--1 of this method preparation, 2-two carbon generation-enclosed-12 carborane (12) organic derivatives.
Background technology:
Cancer is one of principal disease of serious harm human health, for being only second to the second largest killer of cardiovascular diseases.Capture cancer is the research topic of attracting attention in the world always.Requirement to cancer therapy drug is the selectivity height, anti-tumor activity is strong, toxic side effect is low.The most of cancer therapy drugs that use can not have above-mentioned characteristic concurrently at present.Because developed country drops into the research and development that huge fund is used for new drug, and along with the fast development of modern science and technology and to cancer therapy drug to the tumour cell Its Mechanisms, the research level of cancer therapy drug improves rapidly, at medicinal design, the research and development of tumour cell novel targets, many novel cancer therapy drugs have appearred in recent years particularly.The new type anticancer medicine that is used for radiation therapy that one class boracic is wherein arranged promptly is referred to as the cancer therapy drug of BNCT (boron neutron capture therapy for cancer---boron neutron is pounced on and obtained therapy).The anticancer principle of BNCT is to select the nontoxic species that are rich in boron, and it is transported to target cell, shines this zone with thermal beam, but ray and high energy fragment kill cancer cell that nuclear reaction produces.This class medicine can see through have to the in the past intracranial disease of performing the operation of microbial film and penetration rate of blood brain barrier therapeutics.Such medicine is used for brain tumor more at present, mammary cancer, and clinical trials such as melanoma, and be the most effective methods of treatment of cerebral glioma.Drug candidate person mostly is and contains sulfydryl, imines, carboxyl isopolarity functional group or contain nucleosides, the polyhedron borine of polyglycerol, carborane derivative.
At the organometallic chemistry research initial stage, utilize the reaction of metallic compound and alkynes to obtain a large amount of metal complexess, thereby provide possibility for setting up the abundant structures type.Wherein the reaction of alkynes and borine has produced carborane, also has the catalytic activity on certain meaning simultaneously when reacting with metallic assorted borine except obtaining a series of metal carboranes.Typical case representative has a class that Herberhold and co-worker thereof set up that alkynes is introduced the synthetic method of carborane, promptly utilizes the unsatuated metal compound as { Cp
*M (E
2C
2B
10H
10) (M=Rh, Ir; E=S, Se) or { (p-cymene) M (S
2C
2B
10H
10) (M=Ru, Os) with the alkynes reaction, the result has constructed a series of metallic carborane derivatives.Reaction at first is that alkynes is inserted on the M-E key, and B-H activates under the metal center effect then, forms M-B and final fracture thereof at last.As can be seen, though having provided a series of metallic carborane derivatives, this method do not embody its value in organic synthesis.In addition, because the existence of metal center, also there is significant limitation in this compounds aspect storage, application and the further modified with functional group.
The structure of the metallic compound of relevant plane four-coordination and application thereof have report more.With the cobalt is example, the plane four-coordination trivalent cobalt compound that contains acacen and salen part success as chiral catalyst in order to 1 of optionally Diels-Alder reaction of mirror image, carbonylation reaction, nitrate radical, the ring-opening reaction of 3-Dipolar Cycloaddition and epoxy compounds; The another kind of catalyzer that with the chirality porphyrin is the four-coordination cobalt metal compound of part can be used as non-efficiently mapping and enantioselectivity is used in the ethene that a class is contained the diazonium ethyl to carry out in the Cyclopropanated reaction.Metallic compound all is as traditional catalyzer in the above-mentioned reaction, and promptly the entire reaction course catalyzer can recycle.Different therewith is, the catalyzed reaction aquatic foods of the autophage that is participated in by this compounds are report.
Summary of the invention:
The object of the invention provides the synthetic class sulfo--1 that can be used as new type anticancer medicine (BNCT) important intermediate of radiation therapy of a kind of method, 2-two carbon generation-enclosed-12 carborane (12) organic derivatives.
The object of the invention provides a kind of simple and efficient production sulfo--1, the method of 2-two carbon generation-enclosed-12 carborane (12) organic derivatives, with plane sulfenyl coordinate metallic compound and alkynes is starting raw material, can obtain sulfo--1 by simple and effective, 2-two carbon generation-enclosed-12 carborane (12) organic derivatives.
The objective of the invention is to be achieved through the following technical solutions:
The metal center of at first finding the human subject part of a kind of formula (1) expression is the title complex 1 of plane four-coordination, and the alkynes of electron rich is had reactivity.
In the formula (1), n=0-2, M are transition metal, and A is a positively charged ion, and m gets 0-2, makes charge balance, and L can be two unidentate ligands or is a bitooth ligand, and ligating atom can be chlorine, bromine, iodine, oxygen, sulphur, phosphorus, nitrogen.
This metal complexes, wherein L is as long as the part of the compound of the more stable plane four-coordination of metallic ion coordination formation, can be the part of monodentate or bidentate, bitooth ligand is better usually.What market can get usually gets final product.For example [1,2-(HS)
2-1,2-C
2B
10H
10], part such as phenanthrolene.Central metallic ions M requires to form the compound of stable plane four-coordination, still has the ability of accepting electronics after the coordination.From the angle that experiment can be selected, select the transition metal of the 9th, ten families better usually, concrete example such as cobalt, Nie, Palladium or platinum.As long as negatively charged ion A wherein satisfies charge balance and do not react with alkynes, consider and in organic solvent, carry out the synthetic of compound that it is better to be chosen in the organic solvent dissolved negatively charged ion, for example dicyclopentadienylcobalt (Cp
2Co).
Described metallic compound and Li
2S
2C
2B
10H
10The molar weight ratio be: 1: 0.5～4.0;
The structure of synthetic coordination compound is by ultimate analysis, infrared, mass spectrum, nucleus magnetic resonance, and single crystal diffraction characterizes.
Utilize the coordination compound 1 of indication of the present invention and the reaction of alkynes can prepare sulfo--1 easily, 2-two carbon generation-enclosed-12 carborane (12) organic derivatives.The metal complexes and the alkynes of indication of the present invention are dissolved in the organic solvent, reacted 1～24 hour down at-20～110 ℃, obtain demetallated pair of sulphur and replace or sulphur hydrogenant organic product---sulfo--1 2-two carbon generation-enclosed-12 carborane (12) organic derivatives.
Described alkynes comprises Terminal Acetylenes hydrocarbon and disubstituted alkynes, for example HC ≡ CH, RC ≡ CH (R=ferrocenyl, alkyl, alkoxyl group, ester group, aryl radical), R (O) CC ≡ CH (R=alkyl, alkoxyl group, aryl radical), R
1C ≡ CR
2(R
1=R
2Perhaps R
1≠ R
2R
1=ferrocenyl, alkyl, alkoxyl group, ester group, aryl radical, R
2=ferrocenyl, alkyl, alkoxyl group, ester group, aryl radical), Me
3SiC ≡ CSiMe
3, RC ≡ CSiMe
3(R=ferrocenyl, alkyl, alkoxyl group, ester group, aryl radical).
The ratio of the molar weight of described metallic compound and alkynes is: 1: 10～20.
Described organic solvent comprises CH
2Cl
2, THF, toluene or their mixture, be preferably CH
2Cl
2/ THF mixed solvent, the volume ratio of mixed solvent are CH
2Cl
2: THF=2: 1.
The method that the present invention describes is simple to operate, and route is succinct, and the raw material that uses is cheap and easy to get, is the synthetic method with general applicability.Especially realized the transformation of metallic compound, organometallics has been applied to the synthetic of organic compound to organic compound.Products therefrom productive rate height, product is stable, is fit to modify further and modification.
Description of drawings
Fig. 1 is [Co (Cp)
2] Co (S
2C
2B
10H
10)
2Molecular structure;
Fig. 2 is the molecular structure of compound 2;
Fig. 3 is the molecular structure of compound 3;
Embodiment
Below the embodiment by the embodiment form is described in further detail foregoing of the present invention again.But this should be interpreted as that the above-mentioned subject area of the present invention only limits to following examples, all technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1[Li
2S
2C
2B
10H
10] preparation
Containing 1,2-o-C
2B
10H
12(0.05g in 10mL diethyl ether solution 0.35mmol), injects the n-Butyl Lithium of 0.4mL, produces white solid immediately, stirs to add elemental sulfur after 30 minutes (0.02g, 0.77mmol), reaction solution recovers clarification gradually, continues to be stirred to clarify fully to show [Li
2S
2C
2B
10H
10] thoroughly generate.
Embodiment 2[Co (Cp)
2] Co (S
2C
2B
10H
10)
2Preparation
Under 0 ℃ with CpCo (CO) I
2(0.13g, 20mL tetrahydrofuran solution 0.33mmol) are added dropwise to and implement [Li in 1
2S
2C
2B
10H
10] diethyl ether solution in, dropwise half an hour, reaction solution is deep green, stirs in ice bath after 1 hour and at room temperature stirs 2 hours again, reaction solution gradually becomes scarlet from deep green, the decompressing and extracting reaction solution.Column chromatography is separated (100～200 order silicagel column), and methylene dichloride/sherwood oil is elutriant [2: 1 (v/v)], boils off solvent, gets green solid [Co (Cp)
2] Co (S
2C
2B
10H
10)
2Productive rate: 40mg (40%).Fusing point: 210 ℃ of dec.
1H?NMR(CDCl
3)：δ4.19(s，Cp)。
11B{
1H}NMR(CDCl
3)：δ1.5(2B)，-3.8(1B)，-4.8(4B)，-7.1(2B)，-9.3(1B)。ESI-MS：m/z?471([M-(Cp
2Co)]
+，100％)。IR(KBr)：v(cm
-1)2585(B-H)。Ultimate analysis: calculated value (%) C
14H
30B
20Co
2S
4: C 25.45, and H 4.58; Experimental value: C 25.91, H 4.77.X-ray diffraction is analyzed, its crystalline structure as shown in Figure 1, part bond distance
With bond angle parameter [deg]: C (1)-C (2) 1.629 (11), S (1)-C (2) 1.791 (7), S (2)-C (1A) 1.790 (8), Co (1)-S (1) 2.174 (3), Co (1)-S (2) 2.181 (3), S (1) C (2) C (1) 116.0 (5), Co (1) S (1) C (2) 106.3 (3), S (1) Co (1) S (2) 84.71 (8), S (1) Co (1) S (2A) 95.29 (8).
Embodiment 3 Fc (CCH) (S
2C
2B
10H
10) (compound 2 is seen formula 2) and [FcC (CH
2) S]
2C
2B
10H
10The preparation of (compound 3 is seen formula 2)
Under the room temperature, with [Co (Cp)
2] Co (S
2C
2B
10H
10)
2(66mg, 0.1mmol) (210mg 1.0mmol) is dissolved in CH with the ethynyl ferrocene
2Cl
2(20mL), stirring reaction 24 hours.Reaction solution is by the green yellow that becomes, decompressing and extracting reaction solution.Column chromatography is separated (100～200 order silicagel column), and sherwood oil is an elutriant, boils off solvent, gets yellow compound 2 and 3 respectively.
Compound 2 productive rates: 58mg (70%), fusing point: 155 ℃ of dec.
1H?NMR(CDCl
3)：δ4.21(s，5H，Cp)，4.45(m，2H，Fc)，4.40(m，2H，Fc)，6.53(s，1H，HC＝C)。
11B{
1H}NMR(CDCl
3)：δ-6.6(3B)，-6.0(3B)，-4.2(2B)，-1.6(2B)。
13C?NMR(CDCl
3)：δ67.02，69.82，70.48，81.79(Fc)，77.13，112.29(carborane)，112.36(CH＝C)，141.92(＝C-Fc)。EI-MS(70eV)：m/z?416(M
+，100％)。IR(KBr)：v(cm
-1)1633(C＝C)，2587(B-H)。Ultimate analysis, calculated value (%) C
14H
20B
10Fe
1S
2: C 40.38, and H 4.84; Experimental value: C 39.87, H 4.53.X-ray diffraction is analyzed, crystalline structure as shown in Figure 2, part bond distance
With bond angle parameter [deg]: C (1)-C (2) 1.682 (4), S (1)-C (1) 1.815 (3), S (2)-C (2) 1.721 (3), S (1)-C (4) 1.743 (3), S (2)-C (3) 1.806 (3), C (3)-C (4) 1.310 (4), C (4)-C (5) 1.492 (4), S (1) C (4) C (3) 123.2 (2), S (2) C (3) C (4) 123.1 (2), C (1) S (1) C (4) 103.17 (14), C (2) S (2) C (3) 102.67 (15), S (1) C (1) C (2) S (2)/S (1) C (4) C (3) S (2) 128.4.
Compound 3 productive rates: 13mg (10%), fusing point: 183 ℃ of dec.
1H?NMR(CDCl
3)：δ4.16(s，10H，Cp)，4.65(m，4H，Fc)，4.35(m，4H，Fc)，5.78(s，2H，C＝CH
2)，6.13(s，2H，C＝CH
2)。
13C?NMR(CDCl
3)：δ68.36，69.82，69.99，84.26(Fc)，93.52(carborane)，124.99(C＝CH
2)，139.31(＝C-Fc)。
11B{
1H}NMR(CDCl
3)：δ-8.7(1B)，-6.2(7B)，-0.6(2B)。EI-MS(70eV)：m/z?628(M
+，21％)。IR(KBr)：v(cm
-1)1594(FcC＝CH
2)，2575(B-H)。Ultimate analysis, calculated value (%) C
26H
32B
10Fe
2S
2: C 49.69, and H 5.13; Experimental value: C 49.17, H 5.44.X-ray diffraction is analyzed, crystalline structure as shown in Figure 3, part bond distance
With bond angle parameter [deg]: C (1)-C (2) 1.83, S (1)-C (1) 1.733 (6), S (1)-C (3) 1.781 (8), C (3)-C (4) 1.353 (11), C (3)-C (7) 1.461 (10); C (1) S (1) C (3) 103.8 (3), S (1) C (3) C (4) 116.1 (6), S (1) C (3) C (7) 117.4 (5), C (4) C (3) C (7) 126.0 (7).
Embodiment 4 Fc (CCH) (S
2C
2B
10H
10) (compound 2 is seen formula 2) and [FcC (CH
2) S]
2C
2B
10H
10The preparation of (compound 3 is seen formula 2)
Under the room temperature, with Li
2[Ni (S
2C
2B
10H
10)
2] (49mg, 0.1mmol) (210mg 1.0mmol) is dissolved in CH with the ethynyl ferrocene
2Cl
2In/THF (20mL, 1: the 1) mixed solvent, stirring reaction 24 hours.Reaction solution is by the green yellow that becomes, decompressing and extracting reaction solution.Thin-layer chromatography (TLC) separates (JF254 thin-layer chromatography silica gel), and sherwood oil is a developping agent, gets yellow compound 2 (productive rate 50mg (60%)) and yellow compound 3 (productive rate 26mg (20%)) respectively.
Embodiment 5 Ph (CCH) (S
2C
2B
10H
10) preparation of (compound 4 is seen formula 3)
Under the room temperature, with [Co (Cp)
2] Co (S
2C
2B
10H
10)
2(66mg, 0.1mmol) and phenylacetylene (0.22mL 2mmol) is dissolved in CH
2Cl
2(20mL), stirring reaction 24 hours, reaction solution becomes Vandyke brown, the decompressing and extracting reaction solution.TLC separates (JF254 tlc silica gel), and sherwood oil is an elutriant, boils off solvent, gets whitening compound 4.Productive rate: 50mg (81%).
1H?NMR(CDCl
3)：δ6.85(s，1H，C＝CH)，7.41(m，3H，Ph)，7.47(m，2H，Ph)。
13C?NMR(CDCl
3)：δ126.23，129.09，130.09，136.35(Ph)，118.46(CH＝C)，124.87(＝C-Ph)。
11B{
1H}NMR(CDCl
3)：δ-6.4(3B)，-5.1(3B)，-3.6(2B)，-1.2(2B)。EI-MS(70eV)：m/z308.3(M
+，100％)。IR(KBr)：v(cm
-1)1633(C＝CH)，2593(B-H)。Ultimate analysis, calculated value C
10H
16B
10S
2: C 38.94, and H 5.23; Experimental value: C 38.43, H 5.64.
Embodiment 6 Ph (CCH) (S
2C
2B
10H
10) preparation of (compound 4 is seen formula 3)
Under the room temperature, with Li
2[Ni (S
2C
2B
10H
10)
2] (49mg, 0.1mmol) and phenylacetylene (0.22mL 2mmol) is dissolved in CH
2Cl
2In/THF (20mL, 1: the 1) mixed solvent, stirring reaction 24 hours, reaction solution becomes Vandyke brown, the decompressing and extracting reaction solution.TLC separates (JF254 tlc silica gel), and sherwood oil is an elutriant, boils off solvent, gets whitening compound 4 (productive rate, 39mg, 63%).
Embodiment 7 Ph (CCH) (S
2C
2B
10H
10) preparation of (compound 4 is seen formula 3)
Under the room temperature, with [4-MeC
5H
4NMe] [Pd (S
2C
2B
10H
10) I
2] (135mg, 0.2mmol) and phenylacetylene (0.22mL 2mmol) is dissolved in THF (20mL) mixed solvent, stirring reaction 24 hours, reaction solution becomes Vandyke brown, the decompressing and extracting reaction solution.TLC separates (JF254 tlc silica gel), and sherwood oil is an elutriant, boils off solvent, gets whitening compound 4 (productive rate, 43mg, 70%).
Embodiment 8 (MeOCOCHCHS)
2C
2B
10H
10(Z, Z) (compound 5 is seen formula 4), (MeOCOCHCHS)
2C
2B
10H
10(E, Z) (compound 6 is seen formula 4) and (MeOCOCHCHS)
2C
2B
10H
10(E, E) preparation of (compound 7 is seen formula 4)
Under the room temperature, [Co (Cp)
2] Co (S
2C
2B
10H
10)
2(66mg, 0.1mmol) (0.17mL is 2.0mmol) at CH with the propynoic acid methyl esters
2Cl
2Reaction is 24 hours (20mL), and reaction solution becomes scarlet, the decompressing and extracting reaction solution.TLC separates, sherwood oil/CH
2Cl
2(1: 1) is elutriant, gets three kinds of whitening compounds, 5,6,7.
Compound 5 productive rate 23mg (30%).
1H?NMR(CDCl
3)：δ3.76(s，3H，OMe)，6.02(d，J＝10Hz，1H，HC＝CH-C(O))，7.14(d，J＝10Hz，1H，S-CH＝CH)。
13C?NMR(CDCl
3)：δ51.96，(OMe)，89.44(carborane)，116.14(HC＝CH-C(O))，144.33(S-CH＝CH)，166.53(C＝O)。
11B{
1H}NMR(CDCl
3)：δ-11.1(2B)，-8.2(6B)，-1.8(2B)。EI-MS(70eV)：m/z?376.1(M
+，3％)。IR(KBr)：v(cm
-1)1633(C＝C)，1692(C＝O)，2572(B-H)。Ultimate analysis, calculated value (%) C
10H
20B
10O
4S
2: C 31.90, and H 5.35; Experimental value: C 32.53, H 5.89.X-ray diffraction is analyzed, crystalline structure as shown in Figure 4, part bond distance
With bond angle parameter [deg]: C (1)-C (2) 1.790 (4), S (1)-C (1) 1.774 (3), S (1)-C (3) 1.740 (3), C (3)-C (4) 1.316 (4); C (1) S (1) C (3) 101.90 (16).
Compound 6 productive rate 21mg (27%).
1H?NMR(CDCl
3)：δ3.78(s，3H，OMe)，3.79(s，3H，OMe)，6.04(d，J＝10Hz，1H，HC＝CH-C(O)(Z))，6.09(d，J＝16Hz，1H，HC＝CH-C(O)(E))，7.14(d，J＝10Hz，1H，S-CH＝CH(Z)，7.51(d，J＝16Hz，1H，S-CH＝CH(E))。
13C?NMR(CDCl
3)：δ52.06，52.07(OMe)，87.35，89.29(carborane)，116.31(HC＝CH-C(O)(Z)，121.45(HC＝CH-C(O)(E))，140.73(S-CH＝CH(E))，144.33(S-CH＝CH(Z))，164.14，166.53(C＝O)。
11B{
1H}NMR(CDCl
3)：δ-10.8(2B)，-8.3(6B)，-1.7(2B)。EI-MS(70eV)：m/z?376.2(M
+，2％)。IR(KBr)：v(cm
-1)1592(C＝C)，1699，1724(C＝O)，2599(B-H)。Ultimate analysis, calculated value (%) C
10H
20B
10O
4S
2: C 31.90, and H 5.35; Experimental value: C 32.64, H 5.76.
Compound 7 productive rate 26mg (34%).
1H?NMR(CDCl
3)：δ3.79(s，3H，OMe)，6.12(d，J＝16Hz，1H，HC＝CH-C(O))，7.50(d，J＝16Hz，1H，S-CH＝CH)。
13C?NMR(CDCl
3)：δ52.15(OMe)，87.31(carborane)，121.61(HC＝CH-C(O))，140.60(S-CH＝CH)，164.09(C＝O)。
11B{
1H}NMR(CDCl
3)：-10.8(2B)，-8.3(6B)，-1.6(2B)。EI-MS(70eV)：m/z?376.2(M
+，1％)。IR(KBr)：v(cm
-1)1630(C＝C)，1725(C＝O)，2598(B-H)。Ultimate analysis, calculated value C
10H
20B
10O
4S
2: C 31.90, and H 5.35; Experimental value: C 31.43, H 5.83.
Embodiment 9 (MeOCOCHCHS)
2C
2B
10H
10(Z, Z) (compound 5 is seen reaction formula), (MeOCOCHCHS)
2C
2B
10H
10(E, Z) (compound 6 is seen reaction formula) and (MeOCOCHCHS)
2C
2B
10H
10(E, E) preparation of (compound 7 is seen reaction formula)
Under the room temperature, Li
2[Ni (S
2C
2B
10H
10)
2] (49mg, 0.1mmol) (0.17mL 2.0mmol) is dissolved in CH with the propynoic acid methyl esters
2Cl
2In/THF (20mL, 1: the 1) mixed solvent, reacted 24 hours, reaction solution becomes scarlet, the decompressing and extracting reaction solution.TLC separates, sherwood oil/CH
2Cl
2(1: 1) is elutriant, gets three kinds of whitening compounds, and analytical data shows the compound 5,6 and 7 that obtains with embodiment 8.The productive rate of compound 5 is 21mg, 28%, and the productive rate of compound 6 is 18mg, 24%, the productive rate of compound 7 is 27mg, 36%.
Embodiment 10 (MeOCOCHCHS)
2C
2B
10H
10(Z, Z) (compound 5 is seen reaction formula), (MeOCOCHCHS)
2C
2B
10H
10(E, Z) (compound 6 is seen reaction formula) and (MeOCOCHCHS)
2C
2B
10H
10(E, E) preparation of (compound 7 is seen reaction formula)
Under the room temperature, [(dip) Pt (S
2C
2B
10H
10)] (147mg, 0.2mmol) (0.17mL 2.0mmol) is dissolved in CH with the propynoic acid methyl esters
2Cl
2In/THF (20mL, 1: the 1) mixed solvent, reacted 24 hours, reaction solution becomes scarlet, the decompressing and extracting reaction solution.TLC separates, sherwood oil/CH
2Cl
2(1: 1) is elutriant, gets three kinds of whitening compounds, and analytical data shows the compound 5,6 and 7 that obtains with embodiment 8.The productive rate of compound 5 is 25mg, 33%, and the productive rate of compound 6 is 23mg, 30%, the productive rate of compound 7 is 23mg, 31%.
Claims (6)
1. one kind prepares sulfo--1, the method of 2-two carbon generation-enclosed-12 carborane (12) organic derivatives, it is characterized in that: plane four sulfenyl coordinate metal complexess and alkynes are dissolved in the organic solvent, reacted 1～24 hour down at-20～110 ℃, obtaining demetallated pair of sulphur replaces or sulphur hydrogenant organic product---sulfo--1,2-two carbon generation-enclosed-12 carborane (12) organic derivatives, described alkynes comprises Terminal Acetylenes hydrocarbon or two replacement alkynes, the mol ratio of described plane four-coordination metallic compound and alkynes is: 1: 10～20, and described organic solvent comprises CH
2Cl
2, tetrahydrofuran (THF) or toluene or their mixture.
2. preparation method according to claim 1 is characterized in that: described plane four sulfenyl coordinate metal complexess are [{ Li (THF)
4}
2Ni (S
2C
2B
10H
10)
2], [4-MeC
5H
4NMe] [Pd (S
2C
2B
10H
10) I
2], [(dip) Pt (S
2C
2B
10H
10)] or [Co (Cp)
2] Co (S
2C
2B
10H
10)
2
3. adopt the sulfo--1 of the described preparation method's preparation of claim 1,2-two carbon generation-enclosed-12 carborane (12) organic derivatives, it is characterized in that: it has molecular formula: Fc (CCH) (S
2C
2B
10H
10), and have following structural formula:
4. adopt the sulfo--1 of the described preparation method's preparation of claim 1,2-two carbon generation-enclosed-12 carborane (12) organic derivatives, it is characterized in that: it has molecular formula: [(FcC (CH
2) S)]
2C
2B
10H
10, and have following structural formula:
5. adopt the sulfo--1 of the described preparation method's preparation of claim 1,2-two carbon generation-enclosed-12 carborane (12) organic derivatives, it is characterized in that: it has molecular formula: Ph (CCH) (S
2C
2B
10H
10), and have following structural formula:
6. adopt the sulfo--1 of the described preparation method's preparation of claim 1,2-two carbon generation-enclosed-12 carborane (12) organic derivatives, it is characterized in that: they have molecular formula: (MeOCOCHCHS)
2C
2B
10H
10, and have following structural formula respectively:
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| CN106565789A (en) * | 2016-03-29 | 2017-04-19 | 上饶师范学院 | A nido-carborane containing organometallic compound crystal and a preparing method thereof |
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| CN106565789A (en) * | 2016-03-29 | 2017-04-19 | 上饶师范学院 | A nido-carborane containing organometallic compound crystal and a preparing method thereof |
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