CN108003043A - A kind of synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene - Google Patents
A kind of synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene Download PDFInfo
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- CN108003043A CN108003043A CN201810077941.3A CN201810077941A CN108003043A CN 108003043 A CN108003043 A CN 108003043A CN 201810077941 A CN201810077941 A CN 201810077941A CN 108003043 A CN108003043 A CN 108003043A
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- diaminourea
- hexadecane epoxide
- epoxide benzene
- hexadecane
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 135
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 150000002118 epoxides Chemical class 0.000 title claims abstract description 44
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000011017 operating method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001952 rubidium oxide Inorganic materials 0.000 claims description 2
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 abstract 2
- 229960000541 cetyl alcohol Drugs 0.000 abstract 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- 238000001514 detection method Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 3
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- KMWHQYDMBYABKL-UHFFFAOYSA-N 1-iodohexadecane Chemical compound CCCCCCCCCCCCCCCCI KMWHQYDMBYABKL-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- -1 dinitro compound Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 150000005224 alkoxybenzenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of synthetic method of 4 hexadecane epoxide benzene of 1,3 diaminourea, including following operating procedure：Using 1 hexadecanol and dinitrofluorobenzene as reactant, under certain reaction condition, a hydroxyl on 1 hexadecanol substitutes the chlorine on dinitrofluorobenzene to obtain preliminary product 1 under the action of alkali, 3 dinitro, 4 hexadecane epoxide benzene, then 1, the nitro of 3 dinitro, 4 hexadecane epoxide benzene hydrogenating reduction under the action of catalyst obtains 1,3 diaminourea of final products, 4 hexadecane epoxide benzene.It is all very convenient to be bought and transported using program raw material, and product yield is high, and purity is high, and cost is low, easy to operate.
Description
Technical field
The present invention relates to polyimide monomers synthesis technical field, and in particular to one kind 1,3- diaminourea -4- hexadecane oxygen
The synthetic method of base benzene.
Background technology
Polyimides (PI) is the polymer of a kind of structure characterized by imide ring.This kind of high polymer has the resistance to of protrusion
Hot, excellent mechanical performance, electric property and stability etc..Its all kinds of polyimide monomers product can be made film, glue
The products such as mixture, coating, laminate and moulding compound, and these products be widely used to aerospace, electron and electrician, automobile,
The numerous areas such as precision instrument.
1,3- diaminourea -4- hexadecane epoxides benzene (16PDA) is a kind of polyimide monomers therein, and structural formula is as follows：
At present, the synthetic route of 16PDA is mainly the following：
(1) synthesis of intermediate 1,3- dinitros -4- hexadecane epoxides benzene (16PDN)：
Scheme one and analysis：
The program is will to be controlled with excessive alcohol after 1-CHLORO-2,4-DINITROBENZENE DMAC (DMAC N,N' dimethyl acetamide) dissolvings
NaOH aqueous solutions are added dropwise in temperature at 50-60 DEG C, terminate after reaction 4-6h.Yield is 92.5% and 95% respectively.If to anti-
More preferable reaction effect can be obtained by answering condition to optimize.For example potassium carbonate or potassium hydroxide can be selected as catalysis
Agent, reaction dissolvent can select the higher boiling non-protonic solvent such as DMAC.Catalytic action of the DMAC to this substitution reaction is very bright
It is aobvious, and be also the common solvent of industrialization.The boiling point of DMAC itself is higher, can so further improve the temperature of reaction
So as to further increase the efficiency of reaction.If using the reactive mode of no secondary solvent, can by 2,4-dinitrochlorobenzene and
1- hexadecanols use base catalyzed reactions, in order to improve the catalytic efficiency of inorganic base, can add one after heating and melting at high temperature
Exchange between a little phase transfer catalyst increase solid-liquid two-phases.
Scheme two and analysis：
Document Molecular Crystals and Liquid Crystals Science andTechnology,
SectionA:Molecular Crystals and Liquid Crystals；vol.353；(2000)；P.355-371 are exactly
Synthetically prepared, the yield 60% carried out using 2,4-DNP and iodohexadecane.But from the point of view of angle is industrialized
And it is improper, because 2,4-DNP comes from 2,4-dinitrochlorobenzene, the price of iodohexadecane is obviously higher than 1- ten
The price of six alkanols.And the phenolic hydroxyl group in 2,4-DNP is subject to the passivation of substitution nitro on aromatic ring, reaction is lived
Property is not high.
(2) synthesis of 1,3- diaminourea -4- hexadecane epoxides benzene (16PDA)：
Scheme one and analysis：
Document Molecular Crystals and Liquid Crystals Science and Technology,
Section A:Molecular Crystals and Liquid Crystals；vol.353；(2000)；P.355-371 scheme
It is described as follows：It is catalyzed by the use of ethanol as solvent, 5%Pd/C, 2h is hydrogenated at 60 DEG C, and the reaction was complete, after purification yield 70%.But
The method has used expensive catalyst and Hydrogen Vapor Pressure is bigger, and safety coefficient is low, and is unfavorable for industrialized production.
Scheme two and analysis：
Document Journal ofPolymer Science:PartA:Polymer Chemistry,Vol.38,1943–
1950 (2000) are then to use SnCl2/ HCl systems are reduced.But the mode of catalytic hydrogenation is preferred for industrialization.From
From the point of view of some hydrogenation cases, simultaneously technological difficulties are not present in the catalytic hydrogen reduction of dinitro compound, but to avoid violent
Hydrogenation conditions (such as catalyst is more, and pressure is high, temperature height etc.), no person's phenyl ring, which can be hydrogenated, is reduced into cycloaliphatic ring.Reason is virtue
It is not very stable that the presence of dinitro compound, which can allow phenyl ring, on ring, causes phenyl ring under violent hydrogenation conditions by open loop.
The content of the invention
In order to solve the above technical problems, the synthesis side the present invention provides one kind 1,3- diaminourea -4- hexadecane epoxide benzene
Method, to reach synthesis yield height, raw material and the easier purpose of accumulating.
To reach above-mentioned purpose, technical scheme is as follows：
The synthetic method of one kind 1,3- diaminourea -4- hexadecane epoxide benzene, including following operating procedure：
(1) using 1- hexadecanols, dinitrofluorobenzene as raw material, given birth under the action of alkali and non-proton intensive polar solvent into ether
Into 1,3- dinitro -4- hexadecane epoxide benzene；
(2) 1, the 3- dinitro -4- hexadecane epoxide benzene of gained is dissolved in ethanol, under catalyst, hydrogen atmosphere also
Original prepares 1,3- diaminourea -4- hexadecane epoxide benzene.
In such scheme, 1- hexadecanols, alkali, the molar ratio of dinitrofluorobenzene in the step (1) are (1-1.5:
1.2-1.7:1-1.5), and in 80-160 DEG C of heating reaction 4-12h.
In such scheme, the alkali in the step (1) refers to sodium methoxide, potassium tert-butoxide, sodium tert-butoxide, monoethanolamine, three
One or more in ethamine, lithium diisopropyl amido, hexamethyldisilazane lithium.
In such scheme, the non-proton intensive polar solvent in the step (1) is referred in DMF, DMAC, DMSO, NMP
It is a kind of.
In such scheme, the catalyst in the step (2) is referred in nickel, palladium carbon, platinum carbon, stannous chloride, rubidium oxide
One or more.
In such scheme, the catalyst amount in the step (2) is 1,3- dinitro -4- hexadecane epoxide benzene quality
5%-20%, pressurized with hydrogen scope are 2-5MPa, react 2-4h in 60-90 DEG C.
Through the above technical solutions, the synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene provided by the invention passes through
First prepare intermediate 1,3- dinitro -4- hexadecane epoxide benzene, then using 1,3- dinitro -4- hexadecane epoxides benzene hydrogenation also
Original prepares 1,3- diaminourea -4- hexadecane epoxide benzene, and technical process is as follows：
In step (1), a hydroxyl on 1- hexadecanols substitutes two under the action of alkali and non-proton intensive polar solvent
Chlorine on nitro-chlorobenzene obtains preliminary product 1,3- dinitro -4- hexadecane epoxide benzene, 1,3- dinitros -4- ten in step (2)
The nitro of six alkoxy benzenes hydrogenating reduction under the action of catalyst obtains final products 1,3- diaminourea -4- hexadecane epoxides
Benzene.It is all very convenient to be bought and transported using program raw material, and product yield is high, and purity is high, and cost is low, easy to operate.
Embodiment
To the description below of the disclosed embodiments, professional and technical personnel in the field are enable to realize or use the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, defined general former
Reason can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will not
Be intended to be limited to the embodiments shown herein, and be to fit to it is consistent with the principles and novel features disclosed herein most
Wide scope.
The technical solution in the embodiment of the present invention will be clearly and completely described below.
The present invention provides the synthetic method of one kind 1,3- diaminourea -4- hexadecane epoxide benzene, embodiment are as follows：
Embodiment 1
60g 1- hexadecanols are added into flask, the triethylamine of 12g, the DMF of 200ml, is heated with stirring to reflux, reflux
50g dinitrofluorobenzene and the mixture of 150ml DMF are added dropwise afterwards, keeps the temperature 120 DEG C of reaction 6h；Reaction Mother liquor is cooled to room
Temperature, is added dropwise 400ml water, continues to stir, and stops stirring after being added dropwise and then filters to obtain 1,3- dinitro -4- hexadecane epoxides
Benzene, sampling detection, yield 98.6%.
1,3- dinitro -4- hexadecane epoxide benzene is added in autoclave again, the ethanol of 120ml, 3g nickel, pressurized with hydrogen
To 4MPa, 1,3- diaminourea -4- hexadecane epoxide benzene, sampling detection, yield is made to 80 DEG C, insulation reaction 2h in heating stirring
92.0%.
Embodiment 2
55g 1- hexadecanols are added into flask, the triethylamine of 15g, the DMF of 250ml, is heated with stirring to reflux, reflux
40g dinitrofluorobenzene and the mixture of 200ml DMF are added dropwise afterwards, keeps the temperature 140 DEG C of reaction 8h；Reaction Mother liquor is cooled to room
Temperature, is added dropwise 500ml water, continues to stir, and stops stirring after being added dropwise and then filters to obtain 1,3- dinitro -4- hexadecane epoxides
Benzene, sampling detection, yield 96.2%.
1,3- dinitro -4- hexadecane epoxide benzene is added in autoclave again, the ethanol of 100ml, 4g nickel, pressurized with hydrogen
To 4MPa, 1,3- diaminourea -4- hexadecane epoxide benzene, sampling detection, yield is made to 60 DEG C, insulation reaction 2h in heating stirring
93.5%.
Embodiment 3
65g 1- hexadecanols are added into flask, the triethylamine of 10g, the DMF of 200ml, is heated with stirring to reflux, reflux
55g dinitrofluorobenzene and the mixture of 250ml DMF are added dropwise afterwards, keeps the temperature 130 DEG C of reaction 6h；Reaction Mother liquor is cooled to room
Temperature, is added dropwise 600ml water, continues to stir, and stops stirring after being added dropwise and then filters to obtain 1,3- dinitro -4- hexadecane epoxides
Benzene, sampling detection, yield 97.8%.
1,3- dinitro -4- hexadecane epoxide benzene is added in autoclave again, the ethanol of 100ml, 4g palladium carbons, hydrogen adds
3MPa is depressed into, to 70 DEG C, insulation reaction 3h 1,3- diaminourea -4- hexadecane epoxide benzene is made, sampling detection, is received in heating stirring
Rate 91.2%.
Embodiment 4
50g 1- hexadecanols are added into flask, the triethylamine of 10g, the DMF of 200ml, is heated with stirring to reflux, reflux
50g dinitrofluorobenzene and the mixture of 200ml DMF are added dropwise afterwards, keeps the temperature 130 DEG C of reaction 8h；Reaction Mother liquor is cooled to room
Temperature, is added dropwise 500ml water, continues to stir, and stops stirring after being added dropwise and then filters to obtain 1,3- dinitro -4- hexadecane epoxides
Benzene, sampling detection, yield 90.1.%.
1,3- dinitro -4- hexadecane epoxide benzene is added in autoclave again, the ethanol of 120ml, 4g palladium carbons, hydrogen adds
2MPa is depressed into, to 80 DEG C, insulation reaction 2h 1,3- diaminourea -4- hexadecane epoxide benzene is made, sampling detection, is received in heating stirring
Rate 90.9%.
Claims (6)
1. one kind 1, the synthetic method of 3- diaminourea -4- hexadecane epoxide benzene, it is characterised in that including following operating procedure：
(1) using 1- hexadecanols, dinitrofluorobenzene as raw material, 1 is generated into ether under the action of alkali and non-proton intensive polar solvent,
3- dinitro -4- hexadecane epoxide benzene；
(2) 1, the 3- dinitro -4- hexadecane epoxide benzene of gained is dissolved in ethanol, system is reduced under catalyst, hydrogen atmosphere
Standby 1,3- diaminourea -4- hexadecane epoxide benzene.
A kind of 2. synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene according to claim 1, it is characterised in that
1- hexadecanols, alkali, the molar ratio of dinitrofluorobenzene in the step (1) are (1-1.5:1.2-1.7:1-1.5), and in
80-160 DEG C of heating reaction 4-12h.
A kind of 3. synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene according to claim 1, it is characterised in that
Alkali in the step (1) refer to sodium methoxide, potassium tert-butoxide, sodium tert-butoxide, monoethanolamine, triethylamine, lithium diisopropyl amido,
One or more in hexamethyldisilazane lithium.
A kind of 4. synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene according to claim 1, it is characterised in that
Non-proton intensive polar solvent in the step (1) refers to one kind in DMF, DMAC, DMSO, NMP.
A kind of 5. synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene according to claim 1, it is characterised in that
Catalyst in the step (2) refers to the one or more in nickel, palladium carbon, platinum carbon, stannous chloride, rubidium oxide.
A kind of 6. synthetic method of 1,3- diaminourea -4- hexadecane epoxide benzene according to claim 1, it is characterised in that
Catalyst amount in the step (2) is the 5%-20% of 1,3- dinitro -4- hexadecane epoxide benzene quality, pressurized with hydrogen model
Enclose for 2-5MPa, react 2-4h in 60-90 DEG C.
Priority Applications (1)
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6046303A (en) * | 1997-09-12 | 2000-04-04 | Korea Research Institute Of Chemical Technology | Soluble polyimide resin having alkoxy substituents and the preparation method thereof |
| EP1132770A2 (en) * | 2000-03-07 | 2001-09-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6046303A (en) * | 1997-09-12 | 2000-04-04 | Korea Research Institute Of Chemical Technology | Soluble polyimide resin having alkoxy substituents and the preparation method thereof |
| EP1132770A2 (en) * | 2000-03-07 | 2001-09-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
Non-Patent Citations (1)
| Title |
|---|
| KIL-YEONG CHOI ET AL: "Synthesis and Characterization of Colorless Polyimides for Liquid Crystal Alignment Layer", 《MOLECULAR CRYSTALS AND LIQUID CRYSTALS》 * |
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