CN106083939A - 1,3 pairs of (R base ferrocene) 2 propanol and synthetic method - Google Patents
1,3 pairs of (R base ferrocene) 2 propanol and synthetic method Download PDFInfo
- Publication number
- CN106083939A CN106083939A CN201610453580.9A CN201610453580A CN106083939A CN 106083939 A CN106083939 A CN 106083939A CN 201610453580 A CN201610453580 A CN 201610453580A CN 106083939 A CN106083939 A CN 106083939A
- Authority
- CN
- China
- Prior art keywords
- ferrocene
- solvent
- base
- double
- propanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- 229960004592 isopropanol Drugs 0.000 title abstract 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 208000035126 Facies Diseases 0.000 claims description 40
- 239000002585 base Substances 0.000 claims description 40
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 230000006837 decompression Effects 0.000 claims description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 17
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 1,3-dibromoacetone Acetone Chemical compound 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 11
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005304 joining Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 2
- 239000002841 Lewis acid Substances 0.000 claims 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 2
- 150000007517 lewis acids Chemical class 0.000 claims 2
- 239000011592 zinc chloride Substances 0.000 claims 2
- 235000005074 zinc chloride Nutrition 0.000 claims 2
- LQQKDSXCDXHLLF-UHFFFAOYSA-N 1,3-dibromopropan-2-one Chemical class BrCC(=O)CBr LQQKDSXCDXHLLF-UHFFFAOYSA-N 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 239000004449 solid propellant Substances 0.000 abstract description 5
- 241001597008 Nomeidae Species 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- 239000003380 propellant Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- CEQKTLFMTIWDBQ-UHFFFAOYSA-N C(C)[Fe](C1C=CC=C1)C1C=CC=C1 Chemical compound C(C)[Fe](C1C=CC=C1)C1C=CC=C1 CEQKTLFMTIWDBQ-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 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)
Abstract
The present invention relates to the synthetic method (R is C2 C4 alkyl) of a kind of 1,3 pairs of (R base ferrocene) 2 propanol.It is dissolved in solvent with ferrocene, is slowly added to halo (or hydroxyl, alkene) compound and catalyst reaction that carbon number is 24, obtain R base ferrocene through washing, steaming solvent, rectification.Add acetone, solvent in another reactor, be slowly added to after bromine reacts a period of time, through washing, steam solvent, be recrystallized to give 1,3 dibromoacetones.R base ferrocene and 1,3 dibromoacetones obtain 1 through paying a gram alkylated reaction, 3 pairs of (R base ferrocene) acetone, and 1,3 pairs of (R base ferrocene) acetone obtain product 1 in reducing agent effects such as sodium borohydrides, 3 pairs of (R base ferrocene) 2 propanol.Biferrocene derivant synthesized by the present invention serves as reacting with firming agent in solid propellant combustion rate regulator and is not susceptible to migrate.
Description
Technical field
The invention belongs to organic chemical synthesis field, particularly to a kind of 1, double (R base the ferrocene)-2-propanol of 3-and synthesis
Method.
Background technology
Ferrocene derivatives can be used as HTPB composite propellant burning ratemodifier, the catalytic performance good because of it and
Processing performance is widely used.But ferrocene derivatives combustion velocity modulation the most useful industrially in solid propellant field at present
Joint agent is almost monokaryon ferrocene product, owing to its molecular weight is little, functional group simple, there is product and occurs in solid propellant
Migration problem, causes propellant burning rate unstable.AUS is derivative for have developed several biferrocene with first-class problem
Thing burning ratemodifier, including double ethyl dicyclopentadienyl iron methylmethanes (Hycat 6D) and double ethyl dicyclopentadienyl iron base propane (Catocene)
Deng, catalytic effect is excellent, boiling point is high, Heat stability is good, the advantage such as the most volatile to have combustion speed, although burning ratemodifier molecular weight
Increase and reduce in use migration problem, but solved the most at all.
Biferrocene derivant burning ratemodifier has excellent combination property, in double-core is cyclopentadienyl ferrum derivative molecular
Introduce single or multiple hydroxyl as functional group, during propellant casting, hydroxyl and firming agent generation condensation reaction, double
Core ferrocene derivatives " is grafted " with propellant and is connected, and makes burningrate catalyst be secured firmly to propellant molecule by covalent bond and ties
In structure, thus solve the animal migration problem in solid composite propellant system.
The present invention have developed and a kind of novel not migrate biferrocene derivant burning ratemodifier, and its chemical name is 1,3-
Double (R base ferrocene)-2-propanol, biferrocene is connected the hydroxyl on carbon bridge can be anti-with the firming agent generation condensation in propellant
Should, make biferrocene engage with propellant on molecular structure, solve migration problem during propellant storage.R base two cyclopentadienyl
The R base of ferrum, can increase the compatibility of biferrocene and macromolecule propellant, improves manufacturability during solid propellant uses
Energy.
Summary of the invention
Technical scheme:
Double (R base the ferrocene)-2-propanol of a kind of 1,3-, its chemical formula structure is
R is C2-C4 alkyl.
The synthesis technique flow process of double (R base the ferrocene)-2-propanol of 1,3-is as follows
The synthetic method of double (R base the ferrocene)-2-propanol of 1,3-is as follows
(1) synthesis of 1,3-dibromoacetone
With acetone, bromine as raw material, acetone and solvent are added in reactor, opens stirring, control temperature 5-50 DEG C, will
Bromine is slowly added in reactor in 2-60 minute by Dropping funnel, anti-by bromine dropwise adding speed controlling in regulation funnel
Answering temperature, feed time is 0.5-6h, and reaction temperature, in dropping temperature ± 5 DEG C, is warming up to 60-70 DEG C of backflow insulation 1-8h, instead
After should terminating, cooling mixed liquid is to room temperature, washes 2-4 time and takes organic facies, uses anhydrous MgSO4Being dried organic facies, decompression is steamed
Distillating solvent, mixture carries out recrystallization at-20 to 10 DEG C, and filter at low temperature obtains 1,3-DBA.Reaction equation is:
(2) synthesis of R base ferrocene
Ferrocene and solvent are added in reactor, open stirring and make ferrocene dissolve, temperature is adjusted to-10-50 DEG C,
By Dropping funnel or add by several times R-X, add catalyst by several times, during control reaction temperature in temperatures above ± 5 DEG C, protect
Temperature, after 0.1-5 hour, is washed 2-4 time with clear water, is separated organic facies, use anhydrous MgSO4Organic facies is dried, subtracts at 60 DEG C
Pressure distilling off solvent solvent, then decompression distillation obtains R base ferrocene fraction at 100-140 DEG C.Reaction equation is:
(3) synthesis of double (the R base ferrocene) acetone of 1,3-
By 1,3-DBA, catalyst dissolution in a solvent, at a temperature of-10 to 10 DEG C, it is slowly added to R base ferrocene,
Being incubated 1-3 hour at such a temperature after completion of dropwise addition, be warming up to 30-50 DEG C, insulated and stirred is reacted 2-4 hour, terminates reaction, cold
But, add water and wash 2-4 time, separate and take organic facies, use anhydrous MgSO4Organic facies is dried.Filtering, decompression boils off molten
Agent, obtains 1, double (the R base ferrocene) acetone of 3-.Reaction equation is:
(4) synthesis of double (R base the ferrocene)-2-propanol of 1,3-
By 1, in double (R base ferrocene) acetone solution of 3-to mixed solvent, at-5-10 DEG C, it is slowly added to reducing agent, control
Reaction temperature processed, at 0-10 DEG C, continues stirring 1-3 hour, and adding a certain amount of 1mol/L HCl is neutrality to solution, washes with water
2-4 time, separate and take organic facies, with anhydrous MgSO4, organic facies is dried.Filter, decompression boil off solvent, after at 160 DEG C
Decompression steams monosubstituted compound, obtains 1, double (R base the ferrocene)-2-propanol of 3-.Reaction equation is:
Beneficial effects of the present invention
The 1 of present invention proposition, double (R base the ferrocene)-2-propanol of 3-, iron content is high, catalytic in solid propellant
Can be good, the hydroxyl between biferrocene reacts with firming agent and does not migrate, and on ferrocene side chain, R base and propellant have the most compatible
Property, it is possible to improve propellant pharmaceutical technology performance.The reaction condition that the present invention proposes is the gentleest controlled, is suitable for industry metaplasia
Produce.
Detailed description of the invention
The present invention being expanded on further below by embodiment, the present embodiment will not limit the invention.In the present invention
The technological parameter enumerated of technical scheme on roll off the production line value, interval can realize the product of application claims.
Embodiment 1
(1) synthesis of 1,3-dibromoacetone
In 1L four-hole boiling flask, lower 416g chloroform, the 54g acetone of adding of stirring, regulation temperature in the kettle, to 10 DEG C, passes through constant voltage
Dropping funnel adds 312g bromine, and the joining day is 20 minutes, controls reaction temperature 10-15 DEG C, feed time about 0.5h, heats up
To 62 DEG C of backflow insulation 5h.Reaction terminates rear cooling mixed liquid to room temperature, washes and separates organic facies 2 times, uses anhydrous MgSO4Right
Organic facies is dried, and reduce pressure under the conditions of 50 DEG C of 1mmHg distilling off solvent, and solution is recrystallization at-10 DEG C, obtains after filtration
184g 1,3-dibromoacetone.
(2) synthesis of ethyl dicyclopentadienyl iron
In 5L four-hole boiling flask, stirring is lower adds 396g ferrocene and 2400g dichloroethanes, temperature is adjusted to-5 DEG C,
Being slowly added to 233g bromoethane by Dropping funnel, time for adding is 10 minutes.Be slowly added to 400g tri-chlorination zinc, during control
Reaction temperature processed is temperatures above 0 ± 5 DEG C, after being incubated 1.5 hours, washs 2 times with clear water, separates organic facies, anhydrous with 500g
MgSO4Being dried organic facies, reduce pressure under the conditions of 60 DEG C of 1mmHg distilling off solvent dichloroethanes, then at 100-140 DEG C
Decompression distillation obtains 372g ethyl dicyclopentadienyl iron fraction.
(3) synthesis of double (ethyl dicyclopentadienyl iron) acetone of 1,3-
184g 1,3-DBA, 226g aluminum chloride are dissolved in the reactor equipped with 1300g dichloroethanes, 0 DEG C
At a temperature of, it being slowly added to 372g ethyl dicyclopentadienyl iron, the joining day is 10 minutes.Control reaction temperature at 0 ± 2 DEG C, insulation reaction
1.5 hours, it is warming up to 35 DEG C, continues reaction 2 hours, terminate reaction.It is cooled to room temperature, washes and obtain organic facies 2 times, add
The anhydrous MgSO of 200g4Organic facies is dried.Filtering, under the conditions of 50 DEG C of 1mmHg, decompression boils off solvent, obtains 1, the double (second of 3-
Base ferrocene) acetone 297g.
(4) synthesis of double (the ethyl dicyclopentadienyl iron)-2-propanol of 1,3-
240g petroleum ether, 110g ethanol, 297g 1 is added in 1L four-hole boiling flask, double (ethyl dicyclopentadienyl iron) acetone of 3-,
At 20 DEG C add 28g sodium borohydride, control reaction temperature at 5 DEG C, continue stirring 2 hours, add 1mol/L HCl to solution in
Neutrality, washes with water 3 times, separates and takes organic facies, uses anhydrous MgSO4Organic facies is dried.Natural filtration, 60 DEG C of 1mmHg
Under the conditions of lower decompression boil off solvent petroleum ether, ethanol, after under the conditions of 160 DEG C of 1mmHg decompression steam monosubstituted compound,
To double (the ethyl dicyclopentadienyl iron)-2-propanol 276g of 1,3-.
Embodiment 2
(1) synthesis of 1,3-dibromoacetone
In 1L four-hole boiling flask, lower 340g dichloroethanes, the 52g acetone of adding of stirring, regulation temperature in the kettle, to 15 DEG C, passes through
Constant pressure funnel adds 344g bromine, and the joining day is 15 minutes.Control reaction temperature 13-18 DEG C, feed time about 0.5h,
It is warming up to 62 DEG C of backflow insulation 4h.Reaction terminates rear cooling mixed liquid to room temperature, washes and separates organic facies 2 times, uses anhydrous MgSO4
Being dried organic facies, 50 DEG C of decompression distillations, solution is recrystallization at-10 DEG C, obtains 180g 1,3-dibromo third after filtration
Ketone.
(2) synthesis of butyl ferrocene
In 5L four-hole boiling flask, stirring is lower adds 400g ferrocene and 2140g dichloromethane, temperature is adjusted to 0 DEG C, logical
Crossing Dropping funnel and be slowly added to 304g bromination of n-butane, feed time is 2 minutes, is slowly added to 520g aluminum chloride, during charging
Between be 30 minutes.During control reaction temperature temperatures above 0 ± 5 DEG C, after be incubated 2 hours, with clear water washing 3 times, separate
Organic facies, with the anhydrous MgSO of 500g4Being dried organic facies, reduce pressure under the conditions of 60 DEG C of 1mmHg distilling off solvent dichloromethane,
Distillation of reducing pressure at 100-140 DEG C again obtains 405g butyl ferrocene fraction.
(3) synthesis of double (butyl ferrocene) acetone of 1,3-
180g 1,3-DBA, 220g tri-chlorination zinc are dissolved in the reactor equipped with 1200g dichloromethane, 0 DEG C
At a temperature of, in 40 minutes add 405g butyl ferrocene, control reaction temperature at 0 ± 2 DEG C, insulation reaction 1.5 hours, be warming up to
35 DEG C, continue reaction 2 hours, terminate reaction.It is cooled to room temperature, washes and obtain organic facies for 3 times, add the anhydrous MgSO of 200g4Right
Organic facies is dried.Filtering, under the conditions of 50 DEG C of 1mmHg, decompression boils off solvent, obtains 1, double (butyl ferrocene) acetone of 3-
312g。
(4) synthesis of double (the butyl ferrocene)-2-propanol of 1,3-
Adding 230g petroleum ether, 60g methanol, 312g 1 in 1L four-hole boiling flask, double (butyl ferrocene) acetone of 3-, in room
Being slowly added to 62g potassium borohydride under temperature, the joining day is 20 minutes, and control reaction temperature, at 0 DEG C, continues stirring 2 hours, adds
A certain amount of 1mol/L HCl is neutrality to solution, washes with water 4 times, separates and takes organic facies, uses anhydrous MgSO4Organic facies is carried out
It is dried.Natural filtration, under the conditions of 60 DEG C of 1mmHg decompression boil off solvent petroleum ether, ethanol, after under the conditions of 160 DEG C of 1mmHg reduce pressure
Steam monosubstituted compound, obtain 1, double (the butyl ferrocene)-2-propanol 260g of 3-.
Embodiment 3
(1) synthesis of 1,3-dibromoacetone
In 1L four-hole boiling flask, lower 420g chloroform, the 42g acetone of adding of stirring, regulation temperature in the kettle, to 20 DEG C, passes through constant voltage
Dropping funnel adds 270g bromine, controls reaction temperature 18-22 DEG C, feed time about 0.5h, is warming up to 62 DEG C of backflow insulation 3h.
Reaction terminates rear cooling mixed liquid to room temperature, washes and separates organic facies 2 times, uses anhydrous MgSO4Organic facies is dried, 50 DEG C
Decompression distillation under the conditions of 1mmHg, solution is recrystallization at-15 DEG C, obtains 147g 1,3-DBA after filtration.
(2) synthesis of ethyl dicyclopentadienyl iron
In 5L four-hole boiling flask, stirring is lower adds 329g ferrocene and 2500g dichloroethanes, temperature is adjusted to 0 DEG C, logical
Crossing Dropping funnel and be slowly added to 212g bromoethane, average mark adds 220g aluminum chlorides 8 times, during control reaction temperature with
Upper temperature 5 ± 5 DEG C, after being incubated 3 hours, washs 2 times with clear water, separates organic facies, with the anhydrous MgSO of 500g4Organic facies is carried out
Being dried, reduce pressure under the conditions of 60 DEG C of 1mmHg distilling off solvent dichloroethanes, then decompression is steamed under the conditions of 100-140 DEG C of 1mmHg
Evaporate and obtain 307g ethyl dicyclopentadienyl iron fraction.
(3) synthesis of double (ethyl dicyclopentadienyl iron) acetone of 1,3-
147g 1,3-DBA, 205g aluminum chloride are dissolved in the reactor equipped with 812g dichloroethanes, 0 DEG C
At a temperature of, it is slowly added to 307g ethyl dicyclopentadienyl iron, controls reaction temperature at-5 DEG C, insulation reaction 2 hours, it is warming up to 40 DEG C, continues
Continuous reaction 2 hours, terminates reaction.It is cooled to room temperature, washes and obtain organic facies for 3 times, add the anhydrous MgSO of 200g4Organic facies is entered
Row is dried.Filtering, under the conditions of 50 DEG C of 1mmHg, decompression boils off solvent, obtains 1, double (ethyl dicyclopentadienyl iron) the acetone 310g of 3-.
(4) synthesis of double (the ethyl dicyclopentadienyl iron)-2-propanol of 1,3-
230g petroleum ether, 119g ethanol, 312g 1 is added in 1L four-hole boiling flask, double (ethyl dicyclopentadienyl iron) acetone of 3-,
Adding 44g lithium aluminium hydride reduction under room temperature, control reaction temperature, at 0 DEG C, continues stirring 2 hours, adds a certain amount of 1mol/L HCl extremely
Solution is neutrality, washes with water 4 times, separates and takes organic facies, uses anhydrous MgSO4Organic facies is dried.Natural filtration, 60 DEG C
Under the conditions of 1mmHg decompression boil off solvent petroleum ether, ethanol, after under the conditions of 160 DEG C of 1mmHg decompression steam monosubstituted compound,
Obtain double (the ethyl dicyclopentadienyl iron)-2-propanol 260g of 1,3-.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention
The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.
Sample tests
| Sample | Iron content |
| Embodiment 1 | 21.5% |
| Embodiment 2 | 19.2% |
| Embodiment 3 | 22.1% |
Claims (7)
1.1,3-double (R base ferrocene)-2-propanol, it is characterised in that chemical formula structure is:
Double (R base the ferrocene)-2-propanol of the most according to claim 11,3-, it is characterised in that: R base is C2-C4 alkyl.
3. one kind 1, the synthetic method of double (R base the ferrocene)-2-propanol of 3-, it is characterised in that comprise the steps:
1) synthesis of 1,3-dibromoacetone
Acetone, bromine are raw material, and molar ratio example is acetone: bromine: solvent=1:2-3:3-6；Acetone is added with solvent
In reactor, open stirring, reaction temperature 5-50 DEG C, bromine is passed through Dropping funnel and adds in reactor in 2-60 minute, instead
Answering temperature in reaction temperature ± 5 DEG C, be warming up to 60-70 DEG C of insulation 1-8h, reaction terminates rear cooling mixed liquid to room temperature, washes 2-
Take organic facies 4 times, use anhydrous MgSO4Being dried organic facies, reduce pressure distilling off solvent, and mixture enters at-20 to 10 DEG C
Row recrystallization, filter at low temperature obtains 1,3-DBA；
2) synthesis of R base ferrocene
With ferrocene, R-X (C2-C4 halogenide), catalyst as raw material, ferrocene: R-X: catalyst: solvent molar ratio example is 1:
0.8-1.2:0.5-3:8-18；
Ferrocene and solvent are added in reactor, opens stirring and make ferrocene dissolve, temperature is adjusted to-10-50 DEG C, passes through
Dropping funnel adds R-X, and the joining day is 2-100 minute, and point 2-10 time addition catalyst, after being incubated 0.1-5 hour, with clear
Water washs 2-4 time, separates organic facies, uses anhydrous MgSO4Being dried organic facies, reducing pressure under the conditions of 60 DEG C of 1mmHg distills out
Solvent, more lower vacuum distilling obtains R base ferrocene fraction under the conditions of 100-140 DEG C of 1mmHg；
3) synthesis of double (the R base ferrocene) acetone of 1,3-
With solvent, R base ferrocene, 1,3-DBA, catalyst as raw material, 1,3-DBA: R base ferrocene: catalyst:
Solvent molar ratio example is 1:2-2.2:1.5-3:10-20；
By 1,3-DBA, catalyst dissolution in a solvent, at a temperature of-10 to 10 DEG C, R base in 5-120 minute, it is slowly added to
Ferrocene, is incubated 1-3 hour after completion of dropwise addition at such a temperature, is warming up to 30-50 DEG C, and insulated and stirred is reacted 2-4 hour, terminates
Reaction, is cooled to room temperature, adds water and washs 2-4 time, separates and take organic facies, use anhydrous MgSO4Organic facies is dried, mistake
Filter, decompression boils off solvent, obtains 1, double (the R base ferrocene) acetone of 3-；
4) synthesis of double (R base the ferrocene)-2-propanol of 1,3-
With solvent orange 2 A-B, 1, double (the R base ferrocene) acetone of 3-, reducing agent are raw material, 1,3-double (R base ferrocene) acetone: reduction
Agent: solvent orange 2 A-B molar ratio is: 1:1-2.2:8-20；
By 1, in double (R base ferrocene) acetone solution of 3-to solvent orange 2 A, solvent B solvent, at-5-30 DEG C in 2-60 minute slowly
Add reducing agent, control reaction temperature at 0-10 DEG C, continue stirring 1-3 hour, add 1mol/L HCl solution to solution in
Property, wash with water 2-4 time, separate and take organic facies, use anhydrous MgSO4Organic facies is dried；
Filter, under the conditions of 40-80 DEG C of 1mmHg under boil off Solvents Solvent A, solvent B, after at 160 DEG C, steam monosubstituted compound,
Obtain double (R base the ferrocene)-2-propanol of 1,3-.
The synthetic method of double (R base the ferrocene)-2-propanol of the most according to claim 31,3-, it is characterised in that: step 1) institute
Solvent be the protons such as chloroform, dichloromethane, dichloroethanes, ethanol, methanol, aprotic atmospheric boiling point less than 140 DEG C molten
Agent.
The synthetic method of double (R base the ferrocene)-2-propanol of the most according to claim 31,3-, it is characterised in that: step 2) institute
Catalyst be the lewis acids such as aluminum chloride, ferric chloride, zinc chloride；Step 2) used by solvent be dichloroethanes, two
The proton such as chloromethanes, chloroform, aprotic atmospheric boiling point are less than 140 DEG C of solvents.
The synthetic method of double (R base the ferrocene)-2-propanol of the most according to claim 31,3-, it is characterised in that: step 3) institute
Catalyst be the lewis acids such as aluminum chloride, ferric chloride, zinc chloride；Step 3) used by solvent be dichloroethanes, two
The proton such as chloromethanes, chloroform, aprotic atmospheric boiling point are less than 120 DEG C of solvents.
The synthetic method of double (R base the ferrocene)-2-propanol of the most according to claim 31,3-, it is characterised in that: step 4) institute
Reducing agent be sodium borohydride, potassium borohydride, lithium aluminium hydride reduction etc.；Step 4) used by solvent orange 2 A be petroleum ether, chloroform, benzene, first
Benzene etc.；Solvent B used is ethanol, methanol one of them or a combination thereof；Mixed solvent used can be the mixed of two kinds of solvents of A, B
Compound and individually A, B solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610453580.9A CN106083939A (en) | 2016-06-21 | 2016-06-21 | 1,3 pairs of (R base ferrocene) 2 propanol and synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610453580.9A CN106083939A (en) | 2016-06-21 | 2016-06-21 | 1,3 pairs of (R base ferrocene) 2 propanol and synthetic method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106083939A true CN106083939A (en) | 2016-11-09 |
Family
ID=57237713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610453580.9A Pending CN106083939A (en) | 2016-06-21 | 2016-06-21 | 1,3 pairs of (R base ferrocene) 2 propanol and synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106083939A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872328A (en) * | 1996-03-06 | 1999-02-16 | Chemische Betriebe Pluto Gmbh | Ferrocene derivatives |
| CN101186625A (en) * | 2007-12-18 | 2008-05-28 | 苏州大学 | Ethylene group diferrocene derivative and synthetic method thereof |
-
2016
- 2016-06-21 CN CN201610453580.9A patent/CN106083939A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872328A (en) * | 1996-03-06 | 1999-02-16 | Chemische Betriebe Pluto Gmbh | Ferrocene derivatives |
| CN101186625A (en) * | 2007-12-18 | 2008-05-28 | 苏州大学 | Ethylene group diferrocene derivative and synthetic method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 唐孝明，: "双核二茂铁衍生物合成及燃速催化研究进展", 《武汉工程大学学报》 * |
| 国际英等，: "一元羟甲基-双(二茂铁)丙烷的合成与应用研究", 《西北工业大学学报》 * |
| 段新娥等，: "羟甲基-双(二茂铁基)丙烷的合成方法研究", 《山西大学(自然科学版)》 * |
| 边占喜等，: "双(烷基二茂铁基)丙烷的合成及其燃速催化性质", 《应用化学》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2649605B2 (en) | p-substituted l-phenoxy-3-amino-2-propanols, process for their preparation and pharmaceuticals containing them | |
| CN112479957A (en) | Synthesis method of thiodicarb | |
| CN108689866B (en) | Synthesis method of (R) -3-aminobutanol | |
| CN106083939A (en) | 1,3 pairs of (R base ferrocene) 2 propanol and synthetic method | |
| CN115433056B (en) | Preparation method of biphenyl alcohol intermediate | |
| CN103566972B (en) | A kind of Ferrocene oligomer and preparation method thereof | |
| CN111793056A (en) | Preparation method of duloxetine intermediate | |
| US2978523A (en) | Production of alpha-olefins | |
| CN111217690B (en) | Preparation method of propafenone hydrochloride and intermediate 2' -hydroxy dihydrochalcone thereof | |
| Cope et al. | Cyclic Polyolefins. XXVIII. Functionally Substituted Cycloöctatetraenes from Acetylenic Alcohols1 | |
| Cope et al. | Amine Oxides. IX. Comparison of the Elimination Reactions Forming Olefins from the N-Oxides and Methohydroxides of Amines of the Type R2CHCH2N (CH3) 21, 2 | |
| CN102531843A (en) | Method for catalytically hydrogenating difluoroacetic acid | |
| CN106554805B (en) | Solvent and method used by a kind of producing ethylene with acetylene hydrogenation | |
| Houston et al. | Nitrogen tetroxide as a reagent for diazotization | |
| Kuran et al. | Reactions of methylaluminium compounds with acrylonitrile | |
| CN114014829B (en) | Method for synthesizing 7,4' -dimethylnaringenin | |
| Lutz et al. | Antimalarials. Some Notes on the Attempted Synthesis of 7-Chloro-6-dialkylaminoalkylaminoquinolines1 | |
| US2408607A (en) | Manufacture of nitrocompounds | |
| JPS6042795B2 (en) | Carbamoylpiperazine derivatives | |
| US1992489A (en) | Process for producing nitrogeneous products of the aliphatic series | |
| CN107200708A (en) | A kind of preparation method of vismodegib | |
| US3391208A (en) | Trans-di(omega-alkenyl) cyclobutanes | |
| Monson | Dehydrohalogenation of primary alkyl halides in hexamethylphosphoric triamide | |
| CN114804994A (en) | Method for preparing substituted aryl fluorene and derivatives thereof | |
| WO2021092794A1 (en) | Catalyst for carbonylation of dimethyl ether to produce methyl acetate, preparation method therefor, and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161109 |