CN102030684A - Clean production method for symmetrical N,N'-dialkylurea - Google Patents
Clean production method for symmetrical N,N'-dialkylurea Download PDFInfo
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- CN102030684A CN102030684A CN2009100191243A CN200910019124A CN102030684A CN 102030684 A CN102030684 A CN 102030684A CN 2009100191243 A CN2009100191243 A CN 2009100191243A CN 200910019124 A CN200910019124 A CN 200910019124A CN 102030684 A CN102030684 A CN 102030684A
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000004202 carbamide Substances 0.000 claims abstract description 46
- 150000001412 amines Chemical class 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 235000013877 carbamide Nutrition 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 28
- 150000003672 ureas Chemical class 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 2
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960003263 cyclopentamine Drugs 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940067157 phenylhydrazine Drugs 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 abstract description 16
- JEZZOKXIXNSKQD-UHFFFAOYSA-N 1,3-bis(4-nitrophenyl)urea Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC(=O)NC1=CC=C([N+]([O-])=O)C=C1 JEZZOKXIXNSKQD-UHFFFAOYSA-N 0.000 abstract description 3
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- IQYXJABOEQTHKY-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C1(=CC=CC=C1)NC(NC1=CC=CC=C1)=O.C1(=CC=CC=C1)NC(NC1=CC=CC=C1)=O IQYXJABOEQTHKY-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ZSIJOEFUDVYXGY-UHFFFAOYSA-N aniline urea Chemical compound NC(=O)N.NC1=CC=CC=C1 ZSIJOEFUDVYXGY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a clean production method for symmetrical N,N'-dialkylurea, which is particularly suitable for production of N,N'-diphenylurea, N,N'-dicyclohexylurea and 4,4'-dinitrodiphenylurea. The method comprises the following steps of: mixing mother liquor, amine and urea and recovering solvent; reacting to obtain an amine and N,N'-dialkylure-containing mixture; and simply soaking or recrystallizing the mixture with the solvent, and separating to obtain crystalline high-purity N,N'-dialkylurea and the mother liquor, wherein the amine dissolved in the mother liquid is subjected to cyclic reaction of next production naturally in the using and recovery processes.
Description
Invention field: the present invention relates to a kind of symmetric N, the clean preparation method of N '-2-substituted carbamide, particularly suitable is N, N '-diphenyl urea, N, N '-dicyclohexylurea (DCU) and 4, the production of 4 '-dinitro diphenyl urea.
Background technology: to the N that takes by weighing, N '-2-substituted carbamide has extensive use owing to have its unique symmetrical structure in Chemical Manufacture.For example: N, N '-diphenyl urea (N, N '-Diphenylurea) have another name called diphenylurea can be used for synthetic herbicide and sterilant at pesticide industry, also the intermediate of useful as drug phenalgin sulfonic acid and preparation sulfa drugs can be used as the intermediate of producing phenyl urethan; N, N '-dicyclohexylurea (DCU) is preparation N, the intermediate of N '-dicyclohexylcarbodiimide; 4,4 '-dinitro diphenyl urea is the intermediate of dyestuff, medicine and veterinary drug.N, N '-2-substituted carbamide prior synthesizing method is direct or indirect raw material with hypertoxic phosgene, discharge a large amount of poisonous hydrogen chloride gas, seriously polluted, have major safety risks, now less employing, present N, N '-2-substituted carbamide synthetic mainly contains two kinds of methods: the one, and traditional amine method, this method are to be reacted in aqueous solution of hydrochloric acid and got by amine and urea, shortcoming content is low, yield is low, plant factor is low, waste water is many, it is big to separate the purification difficulty; Another kind method is to get with the reduction oxonation of nitro substituent, relatively has the advantage that raw material is easy to get, step is few, productive rate is high with traditional method, but catalyzer costliness, severe reaction conditions, catalyst recovery and N, the purification difficult of N '-2-substituted carbamide; Patent CN1440964A has introduced a kind of production phenylurea and N, the method for N '-diphenyl urea, but need repetitive operation in order to improve yield, and to use a large amount of water to make solvent, plant factor is low, waste water is many; It is that solvent promotes reaction to be prepared N with water that patent CN101279932A introduces row a kind of, the method for N '-dicyclohexylurea (DCU), and what obtain is cured article, productive rate 65～95%, 205～230 ℃ of fusing points; It is raw material with p-Nitroaniline and solid phosgene that patent CN1463965A has introduced a kind of, is solvent with ester, but needs the method for synthetic 4,4 '-dinitro diphenyl urea under the acid binding agent existence condition; U.S. Pat 5591883 has been mentioned in the process of producing dialkyl carbonate with amine and urea pyrolysis and has been produced N, the intermediate steps of N '-2-substituted carbamide and amine mixt, but there is not effective separation scheme and directly application, " Zhejiang Agricultural Univ's journal " 1995,21 (2): it is solvent that 214-216. replaces water with primary isoamyl alcohol, does not add catalyzer, with aniline and urea in 140～148 ℃ of heating reflux reactions, can make productive rate bring up to 88%, but the reaction times reach 20h; The N that CN101407477A and CN101440049 obtain aniline urea pyrolysis method, N '-diphenyl urea with take separating of aniline mixture to filter or the method for decompression separation all can obtain target product with very high yield, but with regard to industrial-scale production may be difficult: 1. aniline and N, N '-diphenyl urea normally produces with the form of pasty state or block, filtration is difficult to realize aniline and N, effective separation of N '-diphenyl urea, 2. unnecessary amine is thoroughly reclaimed, very hard diphenyl urea solid will be produced, industrial production can produce the dead angle, be unfavorable for quality and production control, 3. because the boiling point of aniline is higher and industrial condition its activity decompression separation may require quite harsh, cause the neutrality of molecule to lose the generation unknown impuritie most probably, make product content low.Do not find that up to now document, publication, the relevant only soaked in solvent of patent record or recrystallization reach effective separation of amine, urea pyrolysis method synthetic N, N '-2-substituted carbamide and amine mixt, mother liquor dissolved amine has been realized the method for the circulating reaction of next production naturally in applying mechanically removal process.
Summary of the invention: the object of the present invention is to provide the symmetric N that a kind of technology is simple, reaction conditions is gentle, environmental protection is friendly, cost is low, plant factor is high, the production method of N '-2-substituted carbamide.
The present invention is achieved through the following technical solutions: with mother liquor, amine and urea are at the reactor internal heating, reclaim solvent, also can after reclaiming the solvent end, add amine and urea again to mother liquor, and constantly promote temperature and begin until the reaction of amine and urea, produce a large amount of ammonia this moment, control reaction temperature and available various possible modes guarantee to make the ammonia of generation constantly to overflow reactor to promote the carrying out of reaction, obviously reduce or stop up to the generation of ammonia, in recovery part or do not reclaim under the situation of amine and obtain with symmetric N, N '-2-substituted carbamide and amine are main mixture; What obtain contains N, the mixture of N '-2-substituted carbamide and amine through after the fragmentation with solvent or with solvent after carry out fragmentation so that solid is loose, separate then, washing, drying obtain symmetric N, N '-2-substituted carbamide and the mother liquor that contains amine, also can obtain the higher symmetric N of purity by recrystallization with solvent, symmetrical urea of N '-two and the mother liquor that contains amine, mother liquor dissolved amine begin the next circulating reaction of producing in applying mechanically removal process.
Aforesaid amine can be selected from: aniline; fluorine-containing on the aromatic ring, chlorine, alkyl, aryl, nitro, alkoxyl group, aryloxy, alkylthio, arylthio, cyano group, N; amino, alkyl carbonyl, aromatic carbonyl, the alkyl sulphonyl that the N-dialkyl group replaces is not limited to the aniline of a substituted radical; contain or do not contain the hexahydroaniline that alkyl replaces; phenylhydrazine; cyclopentamine, methylphenylamine, N-ethylaniline.
The method of aforesaid immersion and recrystallization can be with liquid or solid-state form and solvent with the mixture of amine and 2-substituted carbamide, described solvent is under immersion or recrystallization condition reactant and resultant to be organic solvent inert, at least can and preferably alcohol, the halohydrocarbon of C1～C5, the more preferably extremely corresponding mother liquor of methyl alcohol, ethanol, chloroform, trichloroethane.
Aforesaid immersion and recrystallization temperature can be below the relevant pressure boiling points.
Aforesaid method also can adopt pressure reducing mode to make the ammonia of the generation reactive system of constantly overflowing, to promote the reaction of amine and urea; Reaction also can be adopted normal pressure or decompression, distillation or filtering mode recovery part amine after finishing, and described recovery part amine is meant unnecessary amine is not carried out complete isolating reclaimer operation.
Aforesaid operating process can or select for use a kind of gas that is not limited in helium, neon, argon gas, nitrogen, the ammonia to protect, and what preferably use is nitrogen and ammonia.
Aforesaid operating process feeds intake first can be without mother liquor and the operation of reclaiming solvent.
Aforesaid method can be by using but is not limited to by rejecting organic impurity with activated carbon decolorizing, rejecting mechanical impurity by filtering, and the also available fresh solvent dissolution filter that feeds intake is first rejected mechanical impurity.
Advantage of the present invention:
(1) raw material is easy to get, does not have contaminated wastewater, and it is few to soak the solvent load that uses, the plant factor height.
(2) but the reaction atmospheric operation, without catalyzer.
(3) lack reaction time, the unit equipment production capacity is big.
(4) mother liquor and washings dissolved amine have been realized the round-robin reaction of next production, equipment and energy utilization rate height naturally in applying mechanically removal process.
(5) reaction conditions gentleness, the symmetric N of product, the selectivity height of N '-2-substituted carbamide, near 100%, the symmetric N of product, the yield height of N '-2-substituted carbamide, yield is near 100%.
(6) mixture to amine and 2-substituted carbamide just can obtain the symmetric N of highly purified crystallization through simply immersing and recrystallization, N '-2-substituted carbamide, the crystallization N that obtains after the immersion, the content of N '-2-substituted carbamide can reach 99%[HLPC] more than, and can get content near 100%[HLPC through a recrystallization] N, N '-2-substituted carbamide.
Embodiment: following with N, the example that is prepared as of N '-diphenyl urea is done nonrestrictive explanation to this programme.
Embodiment 1:
In the there-necked flask of 250ml, add 40g aniline, 5g urea; use nitrogen protection, extremely dissolving of heat temperature raising under whipped state, and have ammonia to produce; continue to heat up; the generation of ammonia also strengthens gradually, is warmed up to 170～190 ℃, and at 170～190 ℃ of insulation 90min; cool to 25 ℃ and carry out liquid-phase chromatographic analysis; conversion rate of urea 100%, N, the selectivity 99.6% of N '-diphenyl urea.Add the 50ml dehydrated alcohol, it is loose fully to be stirred to dope under the normal temperature, and pumping rate is used the 10ml absolute ethanol washing, drying, product N, N '-diphenyl urea content 99.61%, productive rate 95.1%.
Embodiment 2:
In the there-necked flask of 250ml, add the mixing mother liquor that embodiment 1 separates and washs; add 15ml aniline, 5g urea; stirring makes the urea dissolving; filter; filtrate is used nitrogen protection; heat temperature raising reclaims ethanol; be recycled to still liquid and stop to reclaim ethanol for about 140 ℃, continue to heat up, and the ammonia that produces is in time discharged reactor; be warmed up to 170～190 ℃; and, cool to 25 ℃ and carry out liquid-phase chromatographic analysis, conversion rate of urea 100% at 170～190 ℃ of insulation 90min; N, the selectivity 99.7% of N '-diphenyl urea.Add and reclaim ethanol 50ml, it is loose fully to be stirred to dope under the normal temperature, and pumping rate is used the 20ml absolute ethanol washing, drying, product N, N '-diphenyl urea content 99.67%, productive rate 100.4%.
Embodiment 3:
In the there-necked flask of 250ml, add the mixing mother liquor that embodiment 2 separates and washs; add 15ml aniline, 5g urea; add about 0.2g gac; in 50～60 ℃ of insulation 30min; filter; filtrate is used nitrogen protection in reactor, heat temperature raising reclaims ethanol, is recycled to still liquid and stops to reclaim ethanol for about 140 ℃; continue to heat up; and the ammonia that produces in time discharged reactor, be warmed up to 170～190 ℃, and at 170～190 ℃ of insulation 90min; cool to 25 ℃ and carry out liquid-phase chromatographic analysis; conversion rate of urea 100%, N, the selectivity 100% of N '-diphenyl urea.Add 50ml and reclaim ethanol, it is loose fully to be stirred to dope under the normal temperature, and pumping rate is used the 20ml absolute ethanol washing, drying, product N, N '-diphenyl urea content 99.64%, productive rate 99.3%.
Embodiment 4:
In the there-necked flask of 250ml, add 25g aniline 3g urea; use nitrogen protection; extremely dissolving of heat temperature raising under whipped state, and have ammonia to produce, continue to heat up; the generation of ammonia also strengthens gradually; be warmed up to 170～190 ℃, and, cool to 30 ℃ and add the 150ml dehydrated alcohol at 170～190 ℃ of insulation 90min; it is loose fully to be stirred to dope; transfer in the reaction flask of 500ml and add 200ml ethanol, add a little gac reflux 30min, pumping rate; the filtrate crystallisation by cooling; separate solid 10ml absolute ethanol washing, drying, product N; N '-diphenyl urea content 99.91%, productive rate 96.5%.
Embodiment 5:
The mother liquor 150ml that in the there-necked flask of 250ml, adds embodiment 4, heating recovery ethanol, and with the adding gradually under the recovery state of remaining mother liquor, be recycled to about 140 ℃ and stop to reclaim ethanol, add 9ml aniline, 3g urea, continue to heat up, and the ammonia that produces is in time discharged reactor, be warmed up to 170～190 ℃, and be incubated 90min at 170～190 ℃, cool to 80 ℃ and add 150ml ethanol, it is loose fully to be stirred to dope, transfers in the reaction flask of 500ml and adds 200ml ethanol, add 0.1g gac reflux 30min, pumping rate, filtrate crystallisation by cooling, separate solid 10ml absolute ethanol washing, dry, product N, N '-diphenyl urea content 99.96%, productive rate 101.7%.
Claims (8)
1. symmetric N, the clean preparation method of N '-2-substituted carbamide is characterized in that: will contain amine and symmetric N, the mixture soaked in solvent of N '-2-substituted carbamide or use solvent recrystallization, isolate symmetric N then, producing the mother liquor that contains amine in N '-2-substituted carbamide crystalline process.
2. as condition 1 described method, it is characterized in that: contain amine and symmetric N, the mixture of N '-2-substituted carbamide is obtained by the method for amine and two kinds of material Hybrid Heating of urea at least, amine can and preferably excessive.
3. as condition 1,2 described methods, reaction finish the unnecessary amine in back can be earlier by but be not limited to add then that solvent soaks or recrystallization with normal pressure or decompression, distillation or filtering mode recovery part amine, or do not reclaim amine and add directly that solvent soaks or recrystallization, described recovery part amine is not meant unnecessary amine is carried out complete isolating reclaimer operation.
4. according to each method in the aforementioned claim; described amine can be selected from: aniline; fluorine-containing on the aromatic ring, chlorine, alkyl, aryl, nitro, alkoxyl group, aryloxy, alkylthio, arylthio, cyano group, N; amino, alkyl carbonyl, aromatic carbonyl, the alkyl sulphonyl that the N-dialkyl group replaces is not limited to the aniline of a substituted radical; contain or do not contain the hexahydroaniline that alkyl replaces, phenylhydrazine, cyclopentamine; methylphenylamine, N-ethylaniline.
5. according to each method in the aforementioned claim, to soak and the method for recrystallization can be will contain the mixture of amine and 2-substituted carbamide with liquid or solid-state form and solvent, immersion and recrystallization temperature can be below the boiling points of relevant pressure solvent.
6. according to each method in the aforementioned claim, described solvent be soak or the recrystallization condition under reactant and resultant are organic solvent inert, alcohol, halohydrocarbon that can and preferably select C1～C5 at least for use is mother liquor extremely.
7. according to each method in the aforementioned claim, reaction can or be selected for use at helium, neon, argon gas, nitrogen, ammonia and is not limited to carry out under a kind of gas shield.
8. according to each method in the aforementioned claim, the processing of can decolouring to the mixed solution of mother liquor or mother liquor and amine, urea.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100191243A CN102030684A (en) | 2009-09-25 | 2009-09-25 | Clean production method for symmetrical N,N'-dialkylurea |
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| CN2009100191243A CN102030684A (en) | 2009-09-25 | 2009-09-25 | Clean production method for symmetrical N,N'-dialkylurea |
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| CN102030684A true CN102030684A (en) | 2011-04-27 |
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| CN (1) | CN102030684A (en) |
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| CN106748891A (en) * | 2016-12-30 | 2017-05-31 | 陕西煤业化工技术开发中心有限责任公司 | A kind of method that aniline prepares diphenyl urea with urea |
| CN109503431A (en) * | 2018-12-28 | 2019-03-22 | 山东广浦生物科技有限公司 | A kind of synthetic method of N, N- dicyclohexylurea (DCU) |
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| CN101407477A (en) * | 2007-10-10 | 2009-04-15 | 中国石油天然气股份有限公司 | Method for synthesizing diphenyl urea from urea and aniline |
| CN101440049A (en) * | 2007-11-22 | 2009-05-27 | 中国科学院过程工程研究所 | Cleaning method for synthesizing N,N'-diphenylurea |
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| GB769130A (en) * | 1954-03-16 | 1957-02-27 | Allied Chem & Dye Corp | Process for the manufacture of substituted ureas |
| GB776069A (en) * | 1954-05-26 | 1957-06-05 | Ici Ltd | Manufacture of substituted ureas |
| CN101407477A (en) * | 2007-10-10 | 2009-04-15 | 中国石油天然气股份有限公司 | Method for synthesizing diphenyl urea from urea and aniline |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106748891A (en) * | 2016-12-30 | 2017-05-31 | 陕西煤业化工技术开发中心有限责任公司 | A kind of method that aniline prepares diphenyl urea with urea |
| CN109503431A (en) * | 2018-12-28 | 2019-03-22 | 山东广浦生物科技有限公司 | A kind of synthetic method of N, N- dicyclohexylurea (DCU) |
| CN109503431B (en) * | 2018-12-28 | 2021-04-06 | 山东广浦生物科技有限公司 | Synthesis method of N, N-dicyclohexylurea |
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