CN104030898A - Amphipathic fullerene derivative and preparation method thereof - Google Patents
Amphipathic fullerene derivative and preparation method thereof Download PDFInfo
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- CN104030898A CN104030898A CN201410210202.9A CN201410210202A CN104030898A CN 104030898 A CN104030898 A CN 104030898A CN 201410210202 A CN201410210202 A CN 201410210202A CN 104030898 A CN104030898 A CN 104030898A
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- preparation
- soccerballene
- bromo
- amphipathic
- fullerene
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- -1 bromo soccerballene Chemical compound 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000003612 virological effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000725303 Human immunodeficiency virus Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C43/196—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an amphipathic fullerene derivative. Brominated fullerene is well dispersed in an organic alcohol, an alkali solution is added, and a brown transparent mixed solution is obtained after a stirring reaction; the solution is separated to obtain the fullerene derivative. The fullerene derivative contains both hydroxyl and alkoxy, so that the fullerene derivative can be dissolved not only in water but also in various organic solvents. The amphipathicity characteristic provides new possibilities for fullerene to be applied in the biomedical field. The method has the advantages of simple operation and controllable conditions, and can realize large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of amphipathic fullerene derivate, refer in particular to and a kind ofly take bromo soccerballene, organic alcohols and alkaline solution as raw material, reaction generates the method for strangling alcohol with the richness of alkoxyl group.This fullerene derivate can be used for biomedical sector.The invention still further relates to and improve soccerballene C
60water miscible technical field.
Background technology
Soccerballene C
60to be obtained first with the graphite of laser bombardment vaporization by people such as Kroto in 1985.Soccerballene is the third allotropic substance of carbon after graphite and diamond.The people such as nineteen ninety Huffman have synthesized the soccerballene of gram magnitude, make maroscopic quantity and study C
60become possibility.C
60that molecular diameter is about 0.71nm, is the hollow sphere with high symmetry by 12 pentagons and 20 32 bodies of cage shape that hexagon forms.C
60structures shape the physicochemical property of its uniqueness.C
60the hole size at the volume of molecule and HIV virus activity center matches, and can be seated in virus activity central lumen, cuts off viral source, suppresses viral activity.C
60there are 30 two keys, there is abundant chemical reactivity, can to it, carry out modification as required, be called " the chemical cushion " of medicinal design.C
60can reversibly absorb or ejected electron, absorb a large amount of free radicals, under photoinduction condition, produce a large amount of singlet oxygens.C
60these character it is had a good application prospect at biomedical sector.At biomedical aspect, in the environment of the vital movement major part of organism in water.C
60solvability in water is very poor, and this has just seriously limited it in the application of biomedical sector.Therefore, do not destroying C
60on the basis of this body structure, the consistency that how to improve it and organism is called a difficult problem urgently to be resolved hurrily.
Amphipathic referring to contained hydrophobic grouping and hydrophilic radical simultaneously in molecular structure.For amphipathic fullerene derivate: itself can be used as medicine on the one hand, amphipathicly make it pass through smoothly the hydrophilic and oleophylic region of cytolemma, good with the consistency of organism; Can be used as on the other hand pharmaceutical carrier, increase oil-soluble medicine solubleness in vivo, the effect that effectively improves medicine; In addition can also take amphipathic fullerene derivate as matrix, different group in grafting, the synthetic needed material of design.
Summary of the invention
One of object of the present invention, be to provide a kind of can be water-soluble, can be dissolved in again the amphipathic soccerballene C of various organic solvents
60derivative.
In fullerene derivate of the present invention, both contain hydroxyl, contained again alkoxyl group.
Two of object of the present invention, is to provide the preparation method of above-mentioned substance.
Concrete steps of the present invention comprise:
1) with culture dish, contain bromo fullerene powder and be placed in vacuum drying oven, drying for standby.
2) under magnetic agitation, make bromo soccerballene be dispersed in organic alcohols, then add alkaline solution, constant temperature stirring reaction in water-bath.
3) use hydrochloric acid neutralization procedure 2) mixing solutions of gained, makes pH≤7.Solution is divided into solid-liquid two-phase, gets liquid phase and revolves steaming, then with acetone, methylene dichloride and benzene, extracts respectively successively and revolves steaming, obtains strangling the thick product of alcohol with the richness of alkoxyl group.
4) with eluent, carry out silica gel column chromatography separating purification, vacuum-drying, obtains product.
Described step 1) in, bromo soccerballene is C
60br
6, C
60br
8, C
60br
24, vacuum drying relative vacuum degree is-0.095～-0.1MPa, and temperature is 60 ℃, and the time is 2～24h.
Described step 2) in, to be that methyl alcohol, ethanol, Virahol, isopropylcarbinol, primary isoamyl alcohol, polyoxyethylene glycol etc. are all take the organic solvent that hydroxyl is main functional group to organic alcohols.Alkaline solution is the aqueous solution of sodium hydroxide or potassium hydroxide, and concentration is 6～25wt%.In bromo soccerballene, in bromine atoms and organic alcohols, the mol ratio of hydroxyl is 1:50～200.Bath temperature is 20～30 ℃, and the reaction times is 6～48h.
Described step 3) in, the concentration of hydrochloric acid is any concentration.
Described step 4) in, the order number of silica gel is 200～400 orders, and described eluent is that volume ratio is the methylene dichloride of 1:0～4 and the mixed solvent that methyl alcohol forms.
Described step 4) in, vacuum drying relative vacuum degree is-0.095～-0.1MPa, and temperature is 30～60 ℃, and preferably 40 ℃, the time is 48h.
Soccerballene C of the present invention
60the advantage of derivative and preparation method thereof is:
1) C
60itself is soluble in water hardly, is only slightly soluble in the organic solvents such as benzene, toluene.The present invention had both improved C
60solubleness in various organic solvents, has increased again its solubleness in water, is a kind of amphipathic soccerballene C
60derivative.
2) the amphipathic soccerballene C of the present invention
60derivative has anti-oxidant and anti-cancer function.
3) reaction conditions is easy, simple to operate.
4) reaction times is short.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of an example of this amphipathic fullerene derivate.
Fig. 2 is the infrared spectrogram of this amphipathic another example of fullerene derivate.
Embodiment
Embodiment given below further illustrates the present invention; but be not limiting the scope of the invention, some nonessential improvement that person skilled in art makes the present invention according to the invention described above content and adjustment must belong to protection scope of the present invention.
Embodiment 1:
1, with culture dish, contain C
60br
24powder is placed in vacuum drying oven, and relative vacuum degree is-0.095～-0.1Mpa, and dry 24h is standby at 60 ℃.
2, take 6g sodium hydrate solid, be dissolved in 40ml deionized water, stirring and dissolving, obtains massfraction and is 13% sodium hydroxide solution.
3, take above-mentioned C
60br
24powder 500mg, is placed in 100ml single necked round bottom flask.With graduated cylinder, measure 25ml dehydrated alcohol, add and fill C
60br
24in the flask of powder, add magneton, stir.
4, to the sodium hydroxide solution that adds step 2 to make in the above-mentioned mixing solutions stirring.Flask is placed in to water-bath, constant temperature stirring reaction 6h at 23 ℃.
5, after above-mentioned reaction completes, adding wherein massfraction is 37% concentrated hydrochloric acid, makes pH value of solution≤7, and salt is precipitated out, and gets supernatant liquor.
6, at 40 ℃, supernatant liquor is revolved to steaming, then, with extracting and revolve steaming with acetone, methylene dichloride and benzene successively, obtain solid product.
7, with the silica gel column chromatography product obtained above of purifying, first the mixed solvent of using methylene dichloride: methyl alcohol=12:1 (volume ratio) to form is done eluent, impurity drip washing is got off, the mixed solvent of using again methylene dichloride: methyl alcohol=1:4 (volume ratio) to form is done eluent, the product that drip washing obtains is to strangle alcohol with the richness of oxyethyl group, and its infrared spectrogram as shown in Figure 1.
Embodiment 2:
Embodiment 2 is identical with embodiment 1 step, but one of difference is that organic alcohols used is anhydrous methanol.Two of difference is that first eluent is methylene dichloride: methyl alcohol=13:1 (volume ratio), is secondly methylene dichloride: methyl alcohol=1:4 (volume ratio).
The product obtaining is to strangle alcohol with the richness of methoxyl group, and its infrared spectrogram as shown in Figure 2.
Claims (10)
1. an amphipathic fullerene derivate, is characterized in that: on compound, both contains hydroxyl, contained again alkoxyl group, therefore can be water-soluble, and can be dissolved in various organic solvents again, present amphipathic feature.
2. the preparation method of amphipathic fullerene derivate as claimed in claim 1, it is characterized in that: take bromo soccerballene, organic alcohols and highly basic as raw material, after stirring reaction, obtain the transparent mixing solutions of brown, this solution is carried out to separation and obtain fullerene derivate.Its synthetic route is:
N≤24 in formula, R is alkyl.
3. preparation method according to claim 2, is characterized in that comprising the following steps:
1) with culture dish, contain bromo fullerene powder and be placed in vacuum drying oven, drying for standby.
2) under magnetic agitation, make bromo soccerballene be dispersed in organic alcohols, then add alkaline solution, constant temperature stirring reaction in water-bath.
3) use hydrochloric acid neutralization procedure 2) mixing solutions of gained, makes pH≤7.Solution is divided into solid-liquid two-phase, gets liquid phase and revolves steaming, then with acetone, methylene dichloride and benzene, extracts respectively successively and revolves steaming, obtains strangling the thick product of alcohol with the richness of alkoxyl group.
4) with eluent, carry out silica gel column chromatography separating purification, vacuum-drying, obtains product.
4. preparation method according to claim 3, is characterized in that step 1) described in bromo soccerballene be C
60br
6, C
60br
8, C
60br
24; The relative vacuum degree of vacuum drying oven is-0.095～-0.1MPa, and temperature is 60 ℃, and the time is 2～24h.
5. preparation method according to claim 3, is characterized in that step 2) described in organic alcohols to be that methyl alcohol, ethanol, Virahol, isopropylcarbinol, primary isoamyl alcohol, polyoxyethylene glycol etc. are all take the organic solvent that hydroxyl is main functional group.
6. preparation method according to claim 3, is characterized in that step 2) described in bromo soccerballene in bromine atoms and organic alcohols the mol ratio of hydroxyl be 1:50～200.
7. preparation method according to claim 3, is characterized in that step 2) described in alkaline solution be the aqueous solution of sodium hydroxide or potassium hydroxide, concentration is 6～25wt%.
8. preparation method according to claim 3, is characterized in that step 2) described in bath temperature be 20～30 ℃, the reaction times is 6～48h.
9. preparation method according to claim 3, is characterized in that step 3) described in the concentration of hydrochloric acid be any concentration.
10. preparation method according to claim 3, is characterized in that step 4) described in silica gel column chromatography step, the order number of silica gel is 200～400 orders; The mixed solvent that the methylene dichloride that described eluent is is 1:0～4 by volume ratio and methyl alcohol form; Vacuum drying relative vacuum degree is-0.095～-0.1MPa, and temperature is 30～60 ℃, and the time is 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410210202.9A CN104030898A (en) | 2014-05-17 | 2014-05-17 | Amphipathic fullerene derivative and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410210202.9A CN104030898A (en) | 2014-05-17 | 2014-05-17 | Amphipathic fullerene derivative and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104030898A true CN104030898A (en) | 2014-09-10 |
Family
ID=51461923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410210202.9A Pending CN104030898A (en) | 2014-05-17 | 2014-05-17 | Amphipathic fullerene derivative and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104030898A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316411A (en) * | 2001-03-14 | 2001-10-10 | 陈滇宝 | Process for preparing Cy(OH)n |
-
2014
- 2014-05-17 CN CN201410210202.9A patent/CN104030898A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316411A (en) * | 2001-03-14 | 2001-10-10 | 陈滇宝 | Process for preparing Cy(OH)n |
Non-Patent Citations (2)
| Title |
|---|
| STEPHEN R.WILSON等: "Detection of Methoxylated Anions of Fullerenes by Electrospray Ionization Mass Spectrometry", 《J.AM.CHEM.SOC.》 * |
| 张鑫等: "水溶性C60衍生物在生物医学领域的研究现状", 《高分子通报》 * |
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