CN101250203B - 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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- FWMRUAODTCVEQK-UHFFFAOYSA-N CC1CC=CC1 Chemical compound CC1CC=CC1 FWMRUAODTCVEQK-UHFFFAOYSA-N 0.000 description 1
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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 ether 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.
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 (5)
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, 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, wherein dip represents 4,7-phenylbenzene-1,10-phenanthrolene.
4. adopt the sulfo--1 of the described preparation method's preparation of claim 1,2-two carbon generation-enclosed-12 carborane organic derivatives, it is characterized in that: it has molecular formula: Ph (CCH) (S
2C
2B
10H
10), and have following structural formula:
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