CN104710482A - Carbamate compound containing ferrocene group and synthesis method thereof - Google Patents
Carbamate compound containing ferrocene group and synthesis method thereof Download PDFInfo
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- CN104710482A CN104710482A CN201510066390.7A CN201510066390A CN104710482A CN 104710482 A CN104710482 A CN 104710482A CN 201510066390 A CN201510066390 A CN 201510066390A CN 104710482 A CN104710482 A CN 104710482A
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- ferrocene
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- carbamate compounds
- ferrocene group
- compounds containing
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 87
- -1 Carbamate compound Chemical class 0.000 title abstract description 8
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- MBVFRSJFKMJRHA-UHFFFAOYSA-N 4-fluoro-1-benzofuran-7-carbaldehyde Chemical compound FC1=CC=C(C=O)C2=C1C=CO2 MBVFRSJFKMJRHA-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004809 thin layer chromatography Methods 0.000 claims description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- 229960001708 magnesium carbonate Drugs 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000010687 lubricating oil Substances 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000002816 fuel additive Substances 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000003921 oil Substances 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003500 flue dust Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003747 fuel oil additive Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- BJLRVFDWAOVFCI-UHFFFAOYSA-N 1h-imidazole;quinoline Chemical class C1=CNC=N1.N1=CC=CC2=CC=CC=C21 BJLRVFDWAOVFCI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- SPKJCVZOZISLEI-UHFFFAOYSA-N cyclopenta-1,3-diene;1-cyclopenta-1,3-dien-1-ylethanone;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CC(=O)C1=CC=C[CH-]1 SPKJCVZOZISLEI-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000036178 pleiotropy Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a carbamate compound containing a ferrocene group and a synthesis method thereof, and belongs to the macromolecule field. The invention also discloses a preparation method of the carbamate compound containing the ferrocene group. The carbamate compound containing the ferrocene group has good chemical property stability and has various catalytic properties; the carbamate compound is used in a lubricating oil additive, and besides, has good oxidation resistance, abrasion resistance and corrosion resistance; and the carbamate compound is used in a fuel additive, and has the advantages of suppressing smoke, supporting combustion and reducing pollution.
Description
Technical field
The invention belongs to field of polymer technology, particularly a kind of carbamate compounds containing ferrocene group and synthetic method thereof.
Background technology
Ferrocene is excellent combustion supporting catalyst, and it can not only make the carbon deposit of power machine combustion chamber reduce, prolonged mechanical work-ing life, can improve fuel availability simultaneously, reduces flue dust to the pollution of air.
Ferrocene is also known as the luxuriant dialkylene iron of dicyclo, and it is a kind of organometallics with sandwich structure, at normal temperatures in orange crystal shape, water insoluble, is soluble in the organic solvents such as diesel oil, gasoline, benzene, ethanol, stable chemical nature, tasteless nontoxic.Ferrocene and its derivative, because of the feature of itself, as hydrophobicity, biological oxidizability, aromaticity, stability, hypotoxicity, biological activity etc., and is widely used.The liquid fuels such as gasoline, diesel oil, heavy gas oil are usually used in as fume-eliminating energy-saving additive, to save energy, minimizing flue dust, prevented the pollution of the environment positive effect, and thus it possesses application prospect widely in fields such as various tractor, scraper, cargo truck and diesel locomotives.In addition, it also can be used as gasoline antiknock, rubber ripening agent, plastics from the catalyzer etc. putting out agent, initiator, sensitive materials, liquid crystal material, chemical reagent and synthetic ammonia.The existing domestic petroleum chemical industry consumer's goods, machinery consumes finish, and different kind organism chemical industry catalyzer, additive mostly are energy consumption type, environmental disruption type compound, exacerbates environmental pollution and Nonrenewable resources utilize.
In addition, thermal characteristics and the hydrolysis property of refrigeration lubrication agent can be improved containing the silane polymer of aminosilane ferrocene.Along with the fast development of industrial technology, lubricating oil and additive thereof are also developed very well.For lubricating oil additive, high temperature resistant, environmental protection, efficient and pleiotropy will be the directions of future development.Nitrogen-containing heterocycle compound, such as benzotriazole, alkyl substituted imidazole quinoline, 2,5-dimercapto-1,3-thiadiazoles and derivative thereof are all that lubricating oil, antioxidant and anticorrosive agent, some derivative that people know also has good extreme pressure and antiwear behavior.Because they have the features such as toxicity is little, ashless, so Chinese scholars is just studied them from the beginning of the eighties, synthesize the nitrogen heterocyclic official much in same a part with dense structure successively and can talk the Hete rocyclic derivatives combined with containing extreme-pressure anti-wear active element group (organic compound of sulfur-bearing, phosphorus, chlorine etc.), and their friction and wear behavior and anti-oxidant and Corrosion Protection have been studied.
Summary of the invention
The object of the invention is to overcome existing petrochemical industry and utilize Nonrenewable resources more, cause energy shortage, environmental pollution is serious, and provide a kind of pollution-free, environmental protection, chemical stability is good, possesses biological activity, possesses the carbamate compounds containing ferrocene group of application prospect widely.
For achieving the above object, a kind of carbamate compounds containing ferrocene group, is characterized in that, described a kind of carbamate compounds structural formula containing ferrocene group:
，
Wherein R is CH
2(CH
2)
6cH
3.
The preparation method of above-mentioned a kind of carbamate compounds containing ferrocene group, comprises the following steps:
A. under protection of inert gas, ice bath cools, dimethyl formamide is slowly instilled in the chloroformic solution of ferrocene, then slowly adds phosphorus oxychloride, be heated to temperature of reaction, react complete, poured into by reaction mixture in frozen water, suction filtration falls solid insoluble, neutralization filtrate, repeatedly extract, after washing, drying, obtain ferrocene carboxaldehyde crystal;
B. under protection of inert gas, ferrocene carboxaldehyde is dissolved in anhydrous diethyl ether and then slowly instills in Lithium Aluminium Hydride solution, drip backflow after finishing, monitor reaction simultaneously, after completion of the reaction, add ether, remove excessive Lithium Aluminium Hydride, isolate organic layer, washing, drying, distillation obtain yellow ferrocene methanol powder;
C. under protection of inert gas, be dissolved into by ferrocene methanol in methylene dichloride, then instill oxalyl chloride, after completion of the reaction, distillation is except desolventizing, and solid residue use water rinses, and obtains chloro ferrocene methane after drying;
D. take two n-octyl amine, triethylamine, under condition of ice bath, slowly drip the ethanolic soln of dithiocarbonic anhydride, stir, remove ice bath, room temperature continues to stir, then add the ethanolic soln of chloro ferrocene methane, control temperature below 5 DEG C, then temperature rising reflux, monitor reaction, after having reacted, steam ethanol, add anhydrous diethyl ether, filter out throw out, after filtrate washing, desiccant dryness, filters and steams ether to obtain solid be carbamate compounds containing ferrocene group.
Preferably, rare gas element described in step a, b, c is helium, nitrogen.
Preferably, temperature of reaction described in step a is 55-60 DEG C, and described neutralization filtrate adopts the powder such as sodium carbonate, magnesiumcarbonate, sodium bicarbonate.
Preferably, Lithium Aluminium Hydride excessive described in step b, utilizes the ethyl acetate of cooling and mixture of ice and water to remove.
Preferably, monitor reaction described in step b, d, utilize TLC thin-layer chromatography, solvent system is developping agent (volume ratio of benzene and acetone is 1: 1).
Preferably, described siccative is anhydrous magnesium sulfate, molecular sieve.
The present invention has following beneficial effect: a kind of carbamate compounds containing ferrocene group, and chemistry is steady
Qualitative good, there is multiple catalysis characteristics; For lubricating oil additive, there is good oxidation-resistance, resistance to abrasion and non-corrosibility simultaneously; For fuel oil additive, there is smoke-eliminating combustion-aid, fall oligosaprobic advantage.
Embodiment
The present invention narrates reagent and is market products, and preparation method of the present invention is this area customary preparation methods without specified otherwise, and described reagent manufacturer is as follows:
Ferrocene Shanghai cyclopentadienyl chemical reagent company limited analytical pure
Lithium Aluminium Hydride Tianjin Huan Wei Fine Chemical Co., Ltd analytical pure
Oxalyl chloride Shanghai White aurification work Group Co., Ltd analytical pure
Dithiocarbonic anhydride Shanghai White aurification work Group Co., Ltd analytical pure
Two n-octyl amine Shanghai Kun Hua Fine Chemical Co., Ltd analytical pure
Ferrocene is a kind of high performance rocket fuel additive, there is uprising and smoke-eliminating combustion-aid effect significantly, also can be used as the catalyzer of curable polyester, its special sandwich structure and aromaticity, chemical property is more stable, and in its structure, ferrous iron is in excited state, there is multiple catalysis characteristics, ferrocene is non-BTX aromatic compound, has easy substituted, can prepare various dissimilar derivative.In different compounds, introduce ferrocene can show special character, the ring of ferrocene can carry out monocycle, dicyclo electrophilic substitution reaction, just because of these special propertys of ferrocene, so purposes is also more and more wider.The domestic and international research to ferrocene deriv at present the earliest synthesis of acetyl base ferrocene, 2-ferrocenyl methyl ketone base-p-methylstyrene, etc. small molecules ferrocene deriv; prepare high molecular poly-ferrocene alkane silicon finally; academia expands large quantity research to the synthetic method of ferrocene-based polymer and polymerization mechanism, has developed multiple polymerization process.
Along with going deep into of research, the purposes of Ferrocene and its derivative is familiar with gradually and is developed, dissimilar ferrocene deriv has different functions, concludes and has fetched following four aspects (1) in functional materials, for fuel oil additive, liquid crystal material, superconducting material, stablizer etc.(2) biologically artificial antibody, antitumour activity medicine and bacillary medicine, biologic enzyme electrode and agrochemical is being used.(3) on analytical chemistry, membrane electrode, titrating solution etc. is used as.(4) in finish chemical reaction as the catalyzer of asymmetric reaction and the intermediate etc. of organic synthesis.In diesel oil, add a certain amount of ferrocene, the effect of smoke-eliminating combustion-aid can be played, and then reduce the content of carbon monoxide in the exhaust smoke level of diesel motor and tail gas, alleviate the pollution of emission to environment, strengthen the power of engine.In addition, ferrocene can also eliminate the carbon deposit of diesel engine combustor surface, and at its surface deposition one deck ferric oxide film, can effectively prevent the redeposited of carbon granule.Ferrocene and its derivative is added in gasoline, not only can improve the octane value of gasoline but also enhance the capability of antidetonance.In addition, thermal characteristics and the hydrolysis property of refrigeration lubrication agent can be improved containing the silane polymer of aminosilane ferrocene.
Embodiment 1
Containing a carbamate compounds for ferrocene group, chemical formula:
。
(1) synthesis of ferrocene carboxaldehyde: under nitrogen protection, in ice bath cooling, in the chloroformic solution that 75 mL that in constant pressure funnel, 14.6g (0.2 mol) dimethyl formamide instilled 18.6g (0.1 mol) ferrocene in 10 minutes do; Then, 30.6g (0.2 mol) phosphorus oxychloride instills in reaction flask, dropwises within half an hour, and oil bath is warming up to 55 DEG C, heated and stirred 20hr, makes oil bath temperature all the time lower than 60 DEG C; React complete, poured into by reaction mixture in frozen water, solid is wherein mostly unreacted ferrocene, suction filtration elimination solid insoluble, filtrate neutralizes carefully with powdered sodium carbonate, then use cycling extraction device repeatedly extractive reaction mixture repeatedly, all extracts merge, washing, organic over anhydrous sodium carbonate is dry, except desolventizing obtains thick product 18.21g, obtain red-brown crystals 15.0g with methylene dichloride-normal hexane recrystallization, productive rate is 70.1%.
(2) synthesis of ferrocene methanol: ferrocene carboxaldehyde (10g, 0.047mol) is dissolved in anhydrous diethyl ether, and transferred in constant pressure funnel; In three neck round-bottomed flasks, add Lithium Aluminium Hydride (1.8g, 0.047mol), under nitrogen protection, ferrocene carboxaldehyde solution is slowly added dropwise in the Lithium Aluminium Hydride solution in stirring, drip after finishing and to reflux at 45 DEG C 2h, monitor the carrying out of reaction simultaneously with thin-layer chromatography; After completion of the reaction, be cooled to room temperature, then add 60ml ether, excessive Lithium Aluminium Hydride adds ethyl acetate and the mixture of ice and water removing of cooling; Isolate organic layer with separating funnel, and rinse three times (using 100ml water) with water at every turn.Organic phase, with after anhydrous magnesium sulfate drying 24h, after Rotary Evaporators underpressure distillation, obtains yellow powder 7.2 g, productive rate 96%, fusing point 76-78 DEG C.
(3) synthesis of chloro ferrocene methane: under nitrogen protection; by ferrocene methanol (250 mg; 1.16 mmol) be dissolved in methylene dichloride (20 mL); then by oxalyl chloride (6, excessive) instillation wherein, drip after finishing; stir 4h under nitrogen protection; after completion of the reaction, underpressure distillation is except desolventizing, and fixing residuum use water (10 mL) rinses.
(4) containing the synthesis of the carbamate compounds of ferrocene group: measure 0. 6 mL (1.0 mmol) dithiocarbonic anhydride and be dissolved in the ethanol of 5 mL, 2.4 g (1.0 mmol) two n-octyl amine are measured and 1.4 mL (I.0 1.0 mmol) triethylamine adds in the there-necked flask of 1 50 mL respectively; Under the condition of ice bath, slowly drip the ethanolic soln of dithiocarbonic anhydride, stir 1h; Remove ice bath, at room temperature continue stirring 2 h; Then add ethanolic soln 10 mL of 0.25 g (1.0 mmol) chloro ferrocene methane, control temperature reacts 1 h below 5 DEG C, and then intensification stirring and refluxing reacts 2 h.TLC monitors reaction, and solvent system is developping agent (volume ratio of benzene and acetone is 1: 1).Steam ethanol, add anhydrous diethyl ether 20mL, filter out throw out, filtrate water washes 3 times, then uses anhydrous magnesium sulfate drying, filters, steams ether and obtain faint yellow solid, productive rate 82. 4 %, fusing point 100-102 DEG C.
Embodiment 2
(1) synthesis of ferrocene carboxaldehyde: under nitrogen protection, in ice bath cooling, in the chloroformic solution that 75 mL that in constant pressure funnel, 14.6g (0.2 mol) dimethyl formamide was added dropwise to 18.6g (0.1 mol) ferrocene in 10 minutes do; Then, 30.6g (0.2 mol) phosphorus oxychloride instills in reaction flask, dropwises within half an hour, and oil bath is warming up to 60 DEG C, heated and stirred 20hr, makes oil bath temperature all the time lower than 60 DEG C; React complete, poured into by reaction mixture in frozen water, solid is wherein mostly unreacted ferrocene, suction filtration elimination solid insoluble, filtrate neutralizes carefully by sodium bicarbonate powder, then use cycling extraction device repeatedly extractive reaction mixture repeatedly, all extracts merge, washing, organic over anhydrous sodium carbonate is dry, except desolventizing obtains thick product 18.21g, obtain red-brown crystals 15.2g with methylene dichloride-normal hexane recrystallization, productive rate is 71.3%.
(2) synthesis of ferrocene methanol: ferrocene carboxaldehyde (10g, 0.047mol) is dissolved in anhydrous diethyl ether, and is transferred in constant pressure funnel.In three neck round-bottomed flasks, add Lithium Aluminium Hydride (1.8g, 0.047mol), under nitrogen protection, ferrocene carboxaldehyde solution is slowly added dropwise in the Lithium Aluminium Hydride solution in stirring, drip after finishing and to reflux at 45 DEG C 2h, monitor the carrying out of reaction simultaneously with thin-layer chromatography; After completion of the reaction, be cooled to room temperature, then add 60ml ether, excessive Lithium Aluminium Hydride adds ethyl acetate and the mixture of ice and water removing of cooling; Isolate organic layer with separating funnel, and rinse three times (using 100ml water) with water at every turn; Organic phase, with after molecular sieve drying 24h, after Rotary Evaporators underpressure distillation, obtains yellow powder 7.3 g, productive rate 97%, fusing point 76-78 DEG C.
(3) synthesis of chloro ferrocene methane: under nitrogen protection; by ferrocene methanol (250 mg; 1.16 mmol) be dissolved in methylene dichloride (20 mL); then by oxalyl chloride (6, excessive) instillation wherein, drip after finishing; stir 4h under nitrogen protection; after completion of the reaction, underpressure distillation is except desolventizing, and fixing residuum use water (10 mL) rinses.
(4) containing the synthesis of the carbamate compounds of ferrocene group: measure 0. 6 mL (1.0 mmol) dithiocarbonic anhydride and be dissolved in the ethanol of 5 mL, 2.4 g (1.0 mmol) two n-octyl amine are measured and 1.4 mL (I.0 1.0 mmol) triethylamine adds in the there-necked flask of 1 50 mL respectively; Under the condition of ice bath, slowly drip the ethanolic soln of dithiocarbonic anhydride, stir 1h, remove ice bath, at room temperature continue stirring 2 h; Then add ethanolic soln 10 mL of 0.25 g (1.0 mmol) chloro ferrocene methane, control temperature reacts 1 h below 5 DEG C, and then intensification stirring and refluxing reacts 2 h; TLC monitors reaction, and solvent system is developping agent (volume ratio of benzene and acetone is 1: 1); Steam ethanol, add anhydrous diethyl ether 20mL, filter out throw out, filtrate water washes 3 times, then uses anhydrous magnesium sulfate drying, filters, steams ether and obtain faint yellow solid, productive rate 82. 6 %, fusing point 100-102 DEG C.
Embodiment 3
(1) synthesis of ferrocene carboxaldehyde: under helium protection, in ice bath cooling, in the chloroformic solution that 75 mL that in constant pressure funnel, 14.6g (0.2 mol) DMF dimethyl formamide instilled 18.6g (0.1 mol) ferrocene in 10 minutes do; Then, 30.6g (0.2 mol) phosphorus oxychloride instills in reaction flask, dropwises within half an hour, and oil bath is warming up to 60 DEG C, heated and stirred 20hr, makes oil bath temperature all the time lower than 60 DEG C; React complete, poured into by reaction mixture in frozen water, solid is wherein mostly unreacted ferrocene, suction filtration elimination solid insoluble, filtrate neutralizes carefully with magnesium carbonate powder, then use cycling extraction device repeatedly extractive reaction mixture repeatedly, all extracts merge, washing, organic over anhydrous sodium carbonate is dry, except desolventizing obtains thick product 18.21g, obtain red-brown crystals 15.0g with methylene dichloride-normal hexane recrystallization, productive rate is 72.4%.
(2) synthesis of ferrocene methanol: ferrocene carboxaldehyde (10g, 0.047mol) is dissolved in anhydrous diethyl ether, and transferred in constant pressure funnel; In three neck round-bottomed flasks, add Lithium Aluminium Hydride (1.8g, 0.047mol), under helium protection, ferrocene carboxaldehyde solution is slowly added dropwise in the Lithium Aluminium Hydride solution in stirring, drip after finishing and to reflux at 45 DEG C 2h, monitor the carrying out of reaction simultaneously with thin-layer chromatography; After completion of the reaction, be cooled to room temperature, then add 60ml ether, excessive Lithium Aluminium Hydride adds ethyl acetate and the mixture of ice and water removing of cooling; Isolate organic layer with separating funnel, and rinse three times (using 100ml water) with water at every turn; Organic phase, with after anhydrous magnesium sulfate drying 24h, after Rotary Evaporators underpressure distillation, obtains yellow powder 7.32 g, productive rate 97%, fusing point 76-78 DEG C.
(3) synthesis of chloro ferrocene methane: under helium protection; by ferrocene methanol (250 mg; 1.16 mmol) be dissolved in methylene dichloride (20 mL); then by oxalyl chloride (6, excessive) instillation wherein, drip after finishing; 4h is stirred under helium protection; after completion of the reaction, underpressure distillation is except desolventizing, and fixing residuum use water (10 mL) rinses.
(4) containing the synthesis of the carbamate compounds of ferrocene group: measure 0. 6 mL (1.0 mmol) dithiocarbonic anhydride and be dissolved in the ethanol of 5 mL, 2.4 g (1.0 mmol) two n-octyl amine are measured and 1.4 mL (I.0 1.0 mmol) triethylamine adds in the there-necked flask of 1 50 mL respectively; Under the condition of ice bath, slowly drip the ethanolic soln of dithiocarbonic anhydride, stir 1h; Remove ice bath, at room temperature continue stirring 2 h; Then add ethanolic soln 10 mL of 0.25 g (1.0 mmol) chloro ferrocene methane, control temperature reacts 1 h below 5 DEG C, and then intensification stirring and refluxing reacts 2 h; TLC monitors reaction, and solvent system is developping agent (volume ratio of benzene and acetone is 1: 1); Steam ethanol, add anhydrous diethyl ether 20mL, filter out throw out, filtrate water washes 3 times, then uses molecular sieve drying, filters, steams ether and obtain faint yellow solid, productive rate 82. 8 %, fusing point 100-102 DEG C.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. containing a carbamate compounds for ferrocene group, it is characterized in that, described a kind of carbamate compounds structural formula containing ferrocene group:
，
Wherein R is CH
2(CH
2)
6cH
3.
2. the preparation method of a kind of carbamate compounds containing ferrocene group described in the claims 1, comprises the following steps:
A. under protection of inert gas, ice bath cools, dimethyl formamide is slowly instilled in the chloroformic solution of ferrocene, then slowly adds phosphorus oxychloride, be heated to temperature of reaction, react complete, poured into by reaction mixture in frozen water, suction filtration falls solid insoluble, neutralization filtrate, repeatedly extract, after washing, drying, obtain ferrocene carboxaldehyde crystal;
B. under protection of inert gas, ferrocene carboxaldehyde is dissolved in anhydrous diethyl ether and then slowly instills in Lithium Aluminium Hydride solution, drip backflow after finishing, monitor reaction simultaneously, after completion of the reaction, add ether, remove excessive Lithium Aluminium Hydride, isolate organic layer, washing, drying, distillation obtain yellow ferrocene methanol powder;
C. under protection of inert gas, be dissolved into by ferrocene methanol in methylene dichloride, then instill oxalyl chloride, after completion of the reaction, distillation is except desolventizing, and solid residue use water rinses, and obtains chloro ferrocene methane after drying;
D. take two n-octyl amine, triethylamine, under condition of ice bath, slowly drip the ethanolic soln of dithiocarbonic anhydride, stir, remove ice bath, room temperature continues to stir, then add the ethanolic soln of chloro ferrocene methane, control temperature below 5 DEG C, then temperature rising reflux, monitor reaction, after having reacted, steam ethanol, add anhydrous diethyl ether, filter out throw out, after filtrate washing, desiccant dryness, filters and steams ether to obtain solid be carbamate compounds containing ferrocene group.
3. the preparation method of a kind of carbamate compounds containing ferrocene group according to claim 2, rare gas element described in step a, b, c is helium, nitrogen.
4. the preparation method of a kind of carbamate compounds containing ferrocene group according to claim 2, temperature of reaction described in step a is 55-60 DEG C, and described neutralization filtrate adopts the powder such as sodium carbonate, magnesiumcarbonate, sodium bicarbonate.
5. the preparation method of a kind of carbamate compounds containing ferrocene group according to claim 2, Lithium Aluminium Hydride excessive described in step b, utilizes the ethyl acetate of cooling and mixture of ice and water to remove.
6. the preparation method of a kind of carbamate compounds containing ferrocene group according to claim 2, monitor reaction described in step b, d, utilize TLC thin-layer chromatography, solvent system is developping agent (volume ratio of benzene and acetone is 1: 1).
7. the preparation method of a kind of carbamate compounds containing ferrocene group according to claim 2, described steps d, described siccative is anhydrous magnesium sulfate, molecular sieve.
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